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• 130 .江苏预防医学 2〇21年 3 月第32 卷第2 期Jiangsu] PrevM ed，M ar.,2021,V ol.32,N o. 2•专题论著•改良硝酸银比色法测定车间空气中的硫化氢王育常州市天宁区疾病预防控制中心，江苏常州213000摘要：目的建立用分光光度法测定车间空气中硫化氢的方法。
方法通过改变稳定剂，减少硫化银体系的散射.发现在420 nm处产生吸收峰.该处的吸收光强度与硫化氢的含量呈良好的线性关系，据此建立测定车间空气中硫化氢的新方法.并优化最佳反应条件•建立标准曲线。
结果硫化氢质量浓度在0.66〜2 m l范围内线性关系良好，其线性回归方程为3；=0.031 4x+0. 024 7,相关系数r=0.999 6,方法的检出限为0.2捭/m l。
样品的加样回收率为90.5%〜105.0%。
结论通过()P(聚乙二醇辛基苯基醚)增稳.用分光光度法测定空气中的硫化氢更加准确、重现性好、简便、稳定。
本法用于劳动卫生的车间空气检测可获得满意的结果。
关键词：硫化氢;硝酸银比色法;分光光度法;聚乙二醇辛基苯基醚中图分类号：R113 文献标识码：A文章编号：1006-9070(2021)02-0130-03Determination of hydrogen sulfide in the air ofworkplace by improved silver nitrate methodW A N G YuTiamiin^; D istrict Center fo r Disease Control and Prevention ian^su Changzhou213000,C72/V/^ Abstract：Objective T o establish a novel method to determinate hydrogen sulfide in the air of workplace by spectorpho-tometry.Methods The scattering loss was reduced by changing stabilizer,resulting enhancement of absorbance intensity at420 nm,demonstring a good linear relationship between the absorption light intensity and the content of hydrogen sulfide.A rapid, convenient novel spectrophotometry method to determine hydrogen sulfide was established*the reaction parameters were optimized,the standard curve was generated.Results The linear correlation between hydrogen sulfide mass concentration and absorption was good in the range of0.66-2 /M g/m l.The linear regression equation was,y=0.031 4j'+0. 024 7, with correlation coefficient of0.999 6.The detection limit was0.2 /ig/m l and the average spiked recovery was90. 5%-105. 0%.Conclusion The determination of hydrogen sulfide in air by spectrophotometry is more accurate?reproducible,simple and stable by adding O P (polyethylene glycol octyl phenyl ether)for stabilization.The established method has been used successfully for the determination of H：-S in the air of workplace with satisfactory results.Key words：Hydrogen sulfide；Silver nitrate colorim etry；Spectrophotometry；Polyethylene glycol phenyl ether硫化氢职业病危害检测的重点[1]。
九年级化学元素英语阅读理解25题1<背景文章>Hydrogen is the first element on the periodic table. It is a very light gas with unique properties. Hydrogen has a low density and is colorless, odorless, and tasteless. It is highly flammable and can react explosively with oxygen.Hydrogen has many important uses. It is used as a fuel in fuel cells to generate electricity. Fuel cells are clean and efficient, producing only water as a by-product. Hydrogen is also used in the production of ammonia for fertilizers. In addition, hydrogen can be used to power vehicles, such as hydrogen fuel cell cars.There are several methods for producing hydrogen. One common method is steam reforming of natural gas. In this process, natural gas is reacted with steam to produce hydrogen and carbon dioxide. Another method is electrolysis of water. In electrolysis, an electric current is passed through water to split it into hydrogen and oxygen.Hydrogen plays a crucial role in our lives. It is essential for many chemical processes and is used in a wide range of industries. It also has the potential to be a clean and sustainable energy source in the future.1. Hydrogen is ________.A. heavy and colorfulB. light and colorlessC. smelly and tastelessD. dense and explosive答案：B。
Hydrogen sorption enhancement by Nb 2O 5and Nb catalysts combined with MgH 2M.O.T.da Conceição a ,M.C.Brum a ,⇑,D.S.dos Santos a ,M.L.Dias ba Universidade Federal do Rio de Janeiro/COPPE,Rio de Janeiro,RJ,Brazil bUniversidade Federal do Rio de Janeiro/IMA,Rio de Janeiro,RJ,Brazila r t i c l e i n f o Article history:Received 26July 2012Received in revised form 21September 2012Accepted 24September 2012Available online 29September 2012Keywords:Hydrogen absorbing materials Mechanical alloying Metal hydridesa b s t r a c tThree Nb materials,synthesized oxide (s-Nb 2O 5),commercial oxide (c-Nb 2O 5)and metallic Nb,were applied as catalysts to promote the enhancement of hydrogen sorption in MgH 2.A high specific surface area,around 100m 2g À1,was obtained for both oxides used as catalysts,s-Nb 2O 5and c-Nb 2O 5after being heat treated at 350°C.X-ray diffraction (XRD)tests,performed prior to milling,revealed the amorphous structure of both oxides .All the catalysts were mixed for only 20min with MgH 2by mechanical milling forming composites.Differential Scanning Calorimetric curves of the s-Nb 2O 5and c-Nb 2O 5showed the presence of exothermic crystallization peaks.A total capacity of 5.8wt.%was attained when the hydrogen absorption kinetic tests were conducted at 350°C,with the MgH 2+5wt.%s-Nb 2O 5sample.Ó2012Elsevier B.V.All rights reserved.1.IntroductionThe use of metal hydrides for hydrogen storage has been stud-ied due to their high hydrogen absorption capacity.Magnesium has a low cost and can absorb 7.6wt.%of hydrogen what meets the standards of the American Department of Energy (DOE).How-ever,it is necessary to overcome some limitations such as the high temperatures used to achieve such capacity as well as the poor kinetics.Addition of catalysts has been an interesting approach to reduce the reaction temperature and to improve the kinetics,helping to overcome the limitations described above.The hydrogen sorption on magnesium hydride can be improved by the use of metal oxides such as Sc 2O 3,TiO 2,V 2O 5,Cr 2O 3,Mn 2O 3,Fe 3O 4,CuO,Al 2O 3,SiO 2and Nb 2O 5that have been studied in the past decade [1–9].Up to now,one of the most promising metal oxides tested to improve the hydrogen sorption kinetics was Nb 2O 5[5].The effectiveness of Nb 2O 5as a catalyst for hydrogen absorption/desorption kinetics has been showed recently in many studies [3–9].Most of them use the crystalline form of Nb 2O 5to investigate their role in improving hydrogen sorption [3,7,8].Recently,efforts have been made to synthesize an amorphous Nb 2O 5with a high specific surface area of approximately 200m 2g À1.However,when this material was heated up to 350°C this value reduced to 46m 2g À1[4].Hydrogen kinetic tests with MgH 2are carried out at temperatures around 300°C,and therefore,the overheating of Nb 2O 5can significantly reduce its surface area [10].This work reports the influence of a high surfacearea synthesized Nb 2O 5catalyst on the improvement of the hydro-gen sorption kinetics of magnesium hydride as well as the effect of metallic Nb and commercial Nb 2O 5on this sorption behavior.2.Materials and methodsThe Nb 2O 5was synthesized (s-Nb 2O 5)via templating with amine surfactant by mixing niobium ethoxide with dodecylamine.The synthesis of this material was based on a procedure described previously in the literature [11].Commercial Nb 2O 5(c-Nb 2O 5)and metallic Nb (99.8%)used also as a catalyst were both obtained by CBMM (Brazil).Commercial MgH 2powder with a purity of 99.4%from Sigma–Aldrich was ball milled with tungsten carbide balls in a hermetically closed steel vial,under H 2atmosphere for 24h using a PM 400planetary mill at 300rpm.After that,the MgH 2was ball milled for 20min more with 1and 5wt.%of s-Nb 2O 5cat-alysts and 5wt.%of c-Nb 2O 5and Nb.The samples were identified as MgH 2+1wt.%s-Nb 2O 5,MgH 2+5wt.%s-Nb 2O 5,MgH 2+5wt.%c-Nb 2O 5and MgH 2+5wt.%Nb and handled in a glove box under argon atmosphere.After milling,the samples struc-tural properties were examined using X-ray diffraction measurements (Shimadzu XRD-6000,CuK a ).The hydride phase stability was examined by using a Differential Scanning Calorimeter (DSC-Setaram).In the DSC tests Ar was adopted as carrier gas.The surface area of the samples was determined by the BET equation employing MICROMETRICS ASAP 2020equipment,using nitrogen as adsorbate.The kinetics sorption tests and pressure-composition isotherms were measured by an automatic Sievert’s type apparatus designed by PCT-Pro 2000.Hydrogen absorption/desorp-tion measurements were performed at 1MPa and 0.1kPa of hydrogen pressure,respectively,and at two different temperatures,300and 350°C.3.Results and discussionFig.1a shows the XRD patterns of s-Nb 2O 5and c-Nb 2O 5that show two large and diffuse peaks,prior to their addition to MgH 2,which are characteristic of amorphous metallic structures (Fig.1a).The XRD results of s-Nb 2O 5and c-Nb 2O 5were similar de-spite the differences in the procedures used to synthesize them.0925-8388/$-see front matter Ó2012Elsevier B.V.All rights reserved./10.1016/j.jallcom.2012.09.094Corresponding author.Tel.:+552125628506.E-mail address:mbrum@metalmat.ufrj.br (M.C.Brum).Fig.1b shows the XRD patterns of MgH2milled without catalyst, MgH2+1wt.%s-Nb2O5,MgH2+5wt.%s-Nb2O5,MgH2+5wt.% c-Nb2O5and MgH2+5wt.%Nb composites after being milled. The elemental Mg was detected due to incomplete hydrogenation in the absorption process.Two MgH2-phases appeared:b-MgH2 and c-MgH2.The last one is a metastable phase resulted from mechanical milling that is able to transform the tetragonal struc-ture b-MgH2to orthorhombic,c-MgH2[12]due to the free energy increasing of the system by the insertion of deformations and structural defects[13].The MgH2+5wt.%Nb diffraction pattern show two extra peaks at36°and53°,that correspond to the NbH0.89phase.During mechanical milling there is enough energy generation to promote the reaction between hydrogen and Nb to form the NbH0.89phase.The formation of this phase was also observed in other studies in which metallic Nb was used as catalyst [14,15].The DSC results shown in Fig.2,obtained with a non-isothermal test and a heating rate of10K minÀ1,revealed two exothermic peaks at580and625°C related to the crystallization of c-Nb2O5 and s-Nb2O5,respectively.Based on these results it is possible to conclude that the temperature used to perform the kinetic tests (300and350°C)is not enough to crystallize the oxides that remain in their amorphous state.Fig.3shows the DSC curves for MgH2after being milled with and without catalysts at a heating rate of10K minÀ1.All the samples showed two endothermic peaks which correspond to the b-MgH2and c-MgH2phases,also shown from the analysis of the XRD results.The hydride decomposition temperature was lower for the MgH2sample without catalyst.At this heating rate, a significant difference between the samples containing1and 5wt.%of s-Nb2O5can be observed(Fig.3),with the decomposition reaction of the hydride beginning at around350and330°C,180M.O.T.da Conceição et al./Journal of Alloys and Compounds550(2013)179–184respectively.The results suggest that the hydride decomposition temperature decreases when a higher amount of Nb2O5is added. However,according to Polanski and Bystrzycki[16],it is not possible to directly relate a material that shows a lower peak temperature in its thermogram with a faster desorption kinetics, because DSC peaks do not always correspond to a higher reaction rate,since the exothermic and endothermic peaks can overlap and consequently shift the peak value.The hydrogen absorption/desorption kinetics of samples were investigated at300and350°C under an initial pressure of10bar for the absorption tests and0.1bar for the desorption ones(Figs.4 and5).The sample containing5wt.%of s-Nb2O5was the one that presented the fastest absorption kinetics at300°C,since it can ab-sorb5.2wt.%of hydrogen in1.3min at300°C(Fig.4a).On the other hand,the sample with a smaller amount of s-Nb2O5, MgH2+1wt.%s-Nb2O5,attained only 4.6wt.%of hydrogen in 8.5min.This result suggests that the increasing of Nb2O5amount enhanced the absorption kinetics.At300°C,the MgH2+5wt.% c-Nb2O5sample can absorb5.2wt.%of hydrogen in8.1min.There-fore,the niobium oxides used have the same hydrogen capacity at 300°C,but the synthesized one is six times faster than the com-mercial one.The MgH2+5wt.%Nb showed the slowest kinetics, absorbing5.2wt.%of hydrogen in27min.The majority of the tran-sition metals do not present the same catalytic effect when com-pared to its oxide.According to the literature,the hydrogenation capacity at300°C,for pure niobium mixed to MgH2,attained 5.5wt.%in50s only when a high amount of Nb,15wt.%,was com-bined with MgH2[17].Fig.4b shows the hydrogen desorption kinetic curves of all samples at300°C.The MgH2+5wt.%s-Nb2O5and MgH2+5wt.% c-Nb2O5showed similar behavior,the samples desorbing approxi-mately6.0wt.%in5.8min.On the other hand,the sample with 1wt.%of s-Nb2O5desorbed 5.5wt.%in16.3min at300°C (Fig.4b).Thisfinding suggests that the increase in the amount ofM.O.T.da Conceição et al./Journal of Alloys and Compounds550(2013)179–184181Nb2O5also improves the desorption kinetics.However,the sample containing5wt.%of Nb showed a slower kinetics compared to the other samples at300°C,since it took30min to attain1.4wt.%of the hydrogen desorption.Fig.5a shows the hydrogen absorption kinetic curves at350°C and by comparing them with the results at300°C(Fig.4a)it is pos-sible to notice that the absorption kinetic is negatively influenced by the temperature increase from300to350°C for all the samples, MgH2+1wt.%s-Nb2O5,MgH2+5wt.%s-Nb2O5and MgH2+5wt.% Nb.The same was observed for Nb2O5by Barkhordarian et al.[5]at two different temperatures and they suggest that Nb2O5reduces kinetic barriers,and the thermodynamic driving force dominates the reaction speed and overcompensates for changes of the kinetic barriers.The hydrogen thermodynamic equilibrium pressure is lower at300°C than350°C and the plateau pressure of the hydrogen absorption is directly proportional to the temperature increase.The pressure used in the test is10bar for both tempera-tures and generates a higher thermodynamic driving force for the lowest temperature(300°C).Differently from what took place in the test carried out at300°C,the MgH2+5wt.%c-Nb2O5sample showed a slower kinetics than the MgH2+5wt.%Nb sample,at 350°C.Despite the difference in the thermodynamic driving force between these temperatures,the sharp decrease of the absorption kinetics of the MgH2+5wt.%c-Nb2O5sample could be due to the formation of some phase from the elements that are present in the commercial material.It can also be noticed,by comparing Fig.4a with Fig.5a,that differently from the other absorption curves, the one for MgH2+5wt.%c-Nb2O5sample is S-shaped at350°C and this could be attributed to the variation of the hydride forma-tion kinetics.According to Barkhordarian et al.[6],there are three different models used to describe the hydrogen absorption and desorption.Fig.5b shows that the MgH2+5wt.%s-Nb2O5has the fastest hydrogen desorption kinetic,at350°C,compared to the other sam-ples at the same temperature.In contrast to the absorption results, the ones obtained for desorption were positively influenced by the temperature increase(Figs.4b and5b).The hydrogen absorption capacity for the MgH2+5wt.%s-Nb2O5sample was reduced with182M.O.T.da Conceição et al./Journal of Alloys and Compounds550(2013)179–184the temperature increase.The decrease of the initial specific sur-face area of the catalyst,287m2gÀ1,considering its synthesized temperature around150°C[10]to100m2gÀ1at350°C could have contributed to reduce the hydrogen capacity.Another evidence is that the hydrogen desorption rate obtained was1.5wt.%minÀ1 at350°C for the MgH2+5wt.%s-Nb2O5sample being twice the va-lue reported in the literature(0.7wt.%minÀ1)by Bhat et al.[4]that used a Nb2O5that has an area of46m2gÀ1at the same tempera-ture.On the other hand,the surface area may not be the only rea-son for the hydrogen sorption enhancement since the kinetic results obtained with MgH2+5wt.%(c-Nb2O5and s-Nb2O5)are different and they have a similar surface area of100m2gÀ1at 350°C.Fig.6shows the P–C–I curves obtained at300°C for all the three samples.The plateaus observed correspond to the formation and decomposition of magnesium hydride.The increase in the catalyst amount from1to5wt.%of s-Nb2O5reduces the plateau pressure since more defects are generated during milling when the amount of catalyst used is higher.These results can be related to the DSC ones that show that the sample containing5wt.%of s-Nb2O5was the one that presented the hydride decomposition peak in the low-est temperature.The samples containing5wt.%of s-Nb2O5showed a similar hydrogen storage capacity,6.1wt.%for s-Nb2O5and5.8wt.%for c-Nb2O5(Fig.6).The sample that contains5wt.%of s-Nb2O5 showed a higher reduction of the pressure plateau than the one with5wt.%of c-Nb2O5,from2.5to2.3bar versus1.6to1.4bar for the absorption and desorption,respectively.The kinetics results found here and the ones studied before were summarized in Table1.Some parameters,such as the sam-ple preparation method(milling time)and the pressure used in the tests were considered since they are important when evalu-ating the hydrogen absorption/desorption kinetics.The results showed that the same capacity value was obtained at300°C by Bhat et al.[4]for the MgH2sample also ball milled with a high surface area Nb2O5,but the plateau was attained only after 20min.Despite being all niobium oxides,in Table1,the differ-ent conditions that are used to perform the tests and to synthe-size the material results in some difficulties of direct comparison of the data.M.O.T.da Conceição et al./Journal of Alloys and Compounds550(2013)179–1841834.ConclusionsThe kinetics tests conducted with two niobium oxides having similar surface area,milled with MgH2showed different results at350°C.However,since the efforts are always made to increase the hydrogen capacity in a lower temperature,when using MgH2, both oxides used are equally promising due to their fast kinetics at300°C.The results show that the high surface area of the niobium oxides applied as catalysts improves the kinetics.On the other hand,there are other important factors to be considered such as the amount of niobium oxide used to form the composite and also the different experimental conditions used to synthesize the oxide materials and the composites as well.The MgH2+5wt.% s-Nb2O5sample results were compared to the ones reported in the literature since they showed the best results in the present work absorbing5.2wt.%of hydrogen in1.3min at300°C.AcknowledgmentsThe authors thank Companhia Brasileira de Metalurgia e Mineração(CBMM)for supplying the samples of niobium and niobium oxide;the Brazilian agencies FINEP,CNPq and CAPES for itsfinancial support and NUCAT/COPPE/UFRJ for the BET analysis.References[1]W.Oelerich,T.Klassen,R.Bormann,J.Alloys Compd.315(2001)237–242.[2]K.S.Jung,E.Y.Lee,K.S.Lee,J.Alloys Compd.421(2006)179–184.[3]V.V.Bhat,A.Rougier,L.Aymard,X.Darok,G.A.Nazri,J.-M.Tarascon,J.PowerSources159(2006)107–110.[4]V.V.Bhat,A.Rougier,L.Aymard,G.A.Nazri,J.-M.Tarascon,J.Alloys Compd.460(2008)507–512.[5]G.Barkhordarian,T.Klassen,R.Bormann,Scripta Mater.49(2003)213–217.[6]G.Barkhordarian,T.Klassen,R.Bormann,J.Alloys Compd.407(2006)249–255.[7]O.Friedrichs,F.Aguey-Zinsou,J.R.Ares Fernández,J.C.Sánchez-López,A.Justo,T.Klassen,R.Bormann,A.Fernández,Acta Mater.54(2006)105–110.[8]O.Friedrichs,T.T.Klassen,J.C.Sánchez-López,R.Bormann, A.Fernández,Scripta Mater.54(2006)1293–1297.[9]N.Hanada,T.Ichikawa,H.Fujii,Physica B383(2006)49–50.[10]M.C.Brum,M.O.T.Conceição,C.S.Guimarães,D.S.dos Santos,M.L.Dias,Int.J.Mater.Res.09(2012)1144–1146.[11]D.M.Antonelli,Micropor.Mesopor.Mater.33(1999)209–214.[12]F.C.Gennari,F.J.Castro,G.Urretavizcaya,J.Alloys Compd.321(2001)46–53.[13]J.Huot,G.Liang,S.Boily,A.Van Neste,R.Schulz,J.Alloys Compd.295(1999)495–500.[14]S.D.Vincent,ng,J.Huot,J.Alloys Compd.512(2012)290–295.[15]N.Bazzanella,R.Checchetto,A.Miotello,J.Nanomater.2011(2011)1–11.[16]M.Polanski,J.Bystrzycki,J.Alloys Compd.486(2009)697–701.[17]J.Huot,J.F.Pelletier,L.B.Lurio,M.Sutton,R.Schulz,J.Alloys Compd.348(2003)319–324.Table1Kinetic results and experimental parameters of tests conducted at300°C.Sample Pressure Hydrogen capacity(wt.%)Kinetic(s)Preparation method References MgH2+0.2mol%Nb2O5P des=vacuum 5.2720Ball milling76h(MgH2)+2h(Nb2O5)[4]MgH2+0.2mol%Nb2O5P abs=8.4barP des=vacuum 6.96.960140Ball milling120h[5]MgH2+0.05mol%Nb2O5P abs=8.4barP abs=8.4bar 3.06.04040Ball milling20h(MgH2)+2h(Nb2O5)Ball milling20h(MgH2)+100h(Nb2O5)[6][6]MgH2+2.0mol%Nb2O5P abs=1MPaP des=0.1kPa 6.36.5130140Ball milling200h[7]MgH2+10wt.%Nb2O5-nano P des=0.1kPa 6.5160Ball milling20h(MgH2)+5min(Nb2O5)[8]MgH2+5wt.%s-Nb2O5P abs=1MPaP des=0.1kPa 5.26.078300Ball Milling24h(MgH2)+20min(s-Nb2O5)[present]184M.O.T.da Conceição et al./Journal of Alloys and Compounds550(2013)179–184。
催化重整油英文翻译作文英文：Catalytic reforming is a process used to convert low-quality naphtha into high-quality gasoline components. It involves the use of a catalyst to break down the hydrocarbons in the naphtha and rearrange them into more desirable molecules.The catalyst used in catalytic reforming is typically a mixture of platinum, palladium, and/or rhenium on a porous support material. The naphtha is heated and mixed with hydrogen gas before being passed over the catalyst bed. The catalyst promotes the dehydrogenation, isomerization, and cyclization of the hydrocarbons in the naphtha, resultingin the production of high-octane gasoline components.One of the advantages of catalytic reforming is that it allows refiners to produce high-quality gasoline components from low-quality feedstocks. For example, if a refinery hasa surplus of heavy naphtha, which is typically low in octane, it can be converted into high-octane gasoline components through catalytic reforming. This can help the refinery optimize its production and maximize its profits.Another advantage of catalytic reforming is that it can be used to produce aromatics, which are valuable chemical intermediates used in the production of plastics, synthetic fibers, and other materials. By controlling the operating conditions of the reformer, refiners can produce different ratios of aromatics to gasoline components, depending on market demand.Overall, catalytic reforming is an important process in the refining industry, as it allows refiners to producehigh-quality gasoline components and valuable chemical intermediates from low-quality feedstocks.中文：催化重整是一种将低质量石脑油转化为高质量汽油组分的过程。
怎么治疗海洋污染英语作文英文回答：In recent years, ocean pollution has escalated into a pressing global crisis. The insidious effects of plastic waste, chemical runoff, and other pollutants have wreaked havoc on marine ecosystems, threatening the health of both wildlife and humans. Tackling this daunting challenge requires a multifaceted approach that combines individual actions, government regulations, and technological advancements.Reducing plastic consumption: Single-use plastics, such as straws, bags, and bottles, account for a significant portion of ocean litter. By opting for reusable alternatives, we can drastically reduce our plastic footprint. Reusable bags, stainless steel straws, and glass or metal water bottles are eco-friendly options that can make a world of difference.Proper waste disposal: Mismanaged waste, including sewage and industrial effluents, poses a major threat to coastal environments. Implementing effective waste management systems, such as recycling programs and wastewater treatment facilities, is crucial for preventing pollutants from entering our oceans.Limiting chemical runoff: Agricultural activities, such as fertilizer application, can contribute to water pollution. By adopting sustainable farming practices that minimize chemical inputs, we can help reduce nutrientrunoff and protect marine ecosystems.Supporting conservation efforts: Marine protected areas (MPAs) play a vital role in safeguarding ocean biodiversity and habitat. Establishing and enforcing MPAs helps to mitigate human impacts, such as overfishing and pollution, and provides a safe haven for marine life.Investing in research and innovation: Technological advancements offer promising solutions for addressing ocean pollution. Advanced filtration systems, biodegradablematerials, and remote sensing technologies can enhance our ability to monitor, detect, and clean up pollutants.Government regulations: Governments have a criticalrole to play in regulating industries and setting environmental standards. By implementing strict laws to prevent pollution and promote sustainable practices, governments can create a framework for responsible ocean stewardship.Education and awareness: Raising public awareness about the importance of ocean health is essential. Educational campaigns, media coverage, and community outreach programs can help foster a sense of environmental responsibility and encourage people to take action.By embracing these measures, we can work collectively to restore the health of our oceans and ensure the well-being of future generations. As John F. Kennedy once said, "The ocean is a vast untapped resource, and it is our job to protect it for our children's future."中文回答：近年来，海洋污染已升级为一个紧迫的全球性危机。
富羧酸基团的共轭微孔聚合物：结构单元对孔隙和气体吸附性能的影响姚婵;李国艳;许彦红【摘要】共轭微孔聚合物(CMPs)骨架中的孔和极性基团对聚合物的气体吸附性能起着重要作用.阐明聚合物中极性基团的效果对该领域的进一步发展是必不可少的.为了解决这个根本问题,我们使用最简单的芳香系统-苯作为建筑单体,构筑了两个新颖的富羧酸基团的CMPs (CMP-COOH@1,CMP-COOH@2),并探讨了CMPs中游离羧酸基团的量对其孔隙、吸附焓、气体吸附和选择性的深远影响.CMP-COOH@1和CMP-COOH@2显示的BET比表面积分别为835和765 m2·g-1.这两种聚合物在二氧化碳存储方面显示了高潜力.在273 K和1.05 x 105 Pa条件下,CMP-COOH@1和CMP-COOH@2的CO2吸附值分别为2.17和2.63 mmol·g-1.我们的研究结果表明,在相同的条件下增加聚合物中羧基基团的含量可以提高材料对气体的吸附容量和选择性.%Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance.Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field.To address this fundamental issue,we used benzene,the simplest aromatic system,as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2).We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity,isosteric heat,gas adsorption,and gas selectivity.CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of835 and 765 m2·g-1,respectively,displaying high potential for carbon dioxide storage applications.CMP-COOH@1 and CMP-COOH@2 exhibited CO2 capture capabilities of 2.17 and 2.63 mmol·g-1 (at 273 K and 1.05 x 105 Pa),respectively,which were higher than those of their counterpart polymers,CMP-1 and CMP-2,which showed CO2 capture capabilities of 1.66 and 2.28 mmol·g-1,respectively.Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.【期刊名称】《物理化学学报》【年(卷),期】2017(033)009【总页数】7页(P1898-1904)【关键词】共轭微孔聚合物;羧酸;孔;气体吸附;选择性【作者】姚婵;李国艳;许彦红【作者单位】吉林师范大学,环境友好材料制备和应用教育部重点实验室,长春130103;吉林师范大学,环境友好材料制备和应用教育部重点实验室,长春130103;吉林师范大学,环境友好材料制备和应用教育部重点实验室,长春130103;吉林师范大学,功能材料物理与化学教育部重点实验室,吉林四平136000【正文语种】中文【中图分类】O647Carbon dioxide is one of the main greenhouse gases that cause global issues, such as climate warming and increases in sea level and oceanacidity. Modern climate science predicts that the accumulation of greenhouse gases in the atmosphere will contribute to an increase ins urface air temperature of 5.2 °C between the years 1861 and 2100. Carbon capture and sequestration (CCS), a process of CO2 separation and concentration can contribute to solve. For this aim, the use of porous materials tailored for selective CO2 absorption is energetically efficient and technically feasible. Among the numerous and diversified examples of novel porous materials, such as metal-organic frameworks1,2, zeolites3,4, and purely organic materials5,6 are a class of porous organic materials that allow an elaborate design of molecular skeletons and a fine control of nanopores.Conjugated microporous polymers (CMPs) are a unique class of porous organic materials that combine π-conjugated skeletons with permanent nanopores7–10, which is rarely observed in other porous polymers. CMPs have emerged as a powerful platform for synthesizing functional materials that exhibit excellent functional applications, such as heterogeneous catalysts11,12, guest encapsulation13–15, super-capacitive energy storage devices16,17, light-emitting materials18,19, and fluorescent sensors20,21 and so on. Recently, CMPs have emerged as a designable material for the adsorption of gases, such as hydrogen, carbon dioxide, and methane22–24. Although great achievements in synthesizing CMPs have been realized, extremely high Brunauer-Emmet-Teller specific surface areas as high as 6461 m2·g−125, the other pore parameters, such as pore volume, pore size, and pore size distribution, are important in determining the gas sorptionperformance26,27. Moreover, previous work has shown the surface modification of porous polymers with polar group can significantly enhance their CO2 binding energy, resulting in enhancement in CO2 uptake and/or CO2 selectivity28–30. Carboxylic-rich framework interaction is expected due to hydrogen bonding and/or dipole-quadrupole interactions between CO2 and the functional groups of porous polymers31,32. Cooper et al.33,34 reported increasing the heat of adsorption through the introduction of tailored binding functionalities could have more potential to increase the amount of gas adsorbed. Their results demonstrated that carboxylic groups functionalised polymer showed the higher isosteric heat of sorption for CO2. Torrisi et al.35 predicted that the incorporation of carboxylic groups would lead to the higher isosteric heat, challenging the current research emphasis in the literature regarding amine groups for CO2 capture.Herein, we report the synthesis and characterization two high carboxylic groups of porous polymers and investigate their performances in CO2 storage application under high pressure and cryogenic conditions (Scheme 1, CMP-COOH@1 and CMP-COOH@2). The CMPs are highly efficient in the uptake of CO2 by virtue of a synergistic structural effect, and that the carboxylic units improve the uptake, the high porosity provides a large interface, and the swellable skeleton boosts the capacity.1,3,5-Triethynylbenzene (98%) was purchased from TCI, 2,5-dibromobenzoic-3-carboxylic acid (97%) and 2,5-dibromoterephthalicacid(97%) were purchased from Alfa. Tetrakis(4-ethynylphenyl)methane was synthesized according to the literature36. Tetrakis(triphenylphosphine)palladium(0), copper(I) iodide (CuI) andtetra(4-bromophenyl)methane (97%) were purchased from Aladdin. N,N-Dimethylformamide (DMF) (99.9%), triethylamine (99%), methanol (95%) and acetone (95%) were purchased from Aladdin.1H NMR spectra were recorded on Bruker Avance III models HD400 NMR spectrometers, where chemical shifts (δ) were determined with a residual proton of the solventas standard.Fourier transform Infrared (FT-IR) spectra were recorded on a Perkin-Elmer spectrum one model FT-IR-frontier infrared spectrometer.The UV-visible analyzer was used for shimadzu UV-3600. Field-emission scanning electron microscopy (FE-SEM) images were performed on a JEOL model JSM-6700 operating at an accelerating voltage of 5.0 kV. The samples were prepared by drop-casting a tetrahydrofunan (THF) suspension onto mica substrate and then coated with gold.High-resolution transmission electron microscopy (HR-TEM) images were obtained on a JEOL model JEM-3200 microscopy.Powder X-ray diffraction (PXRD) data were recorded on a Rigaku model RINT Ultima III diffractometer by depositing powder on glass substrate, from 2θ = 1.5° up to 2θ = 60° with 0.02° increment. The elemental analysis was carried out on a EuroEA-3000. TGA analysis was carried out using a Q5000IR analyzer with an automated vertical overhead thermobalance. Before measurement, the samples were heated at a rate of 5 °C min−1 under a nitrogen atmosphere. Nitrogen sorption isotherms were measured at 77 K with ASIQ (iQ-2) volumetric adsorption analyzer.Before measurement, thesamples were degassed in vacuum at 150 °C for 12 h. The Brunauer-Emmett-Teller (BET) method was utilized to calculate the specific surface areas and pore volume. BET surface areas were calculated over the relative pressure (p/p0) range of 0.015–0.1. Nitrogen NLDFT pore size distributions were calculated from the nitrogen adsorption branch using a cylindrical pore size model. Carbon dioxide, methane and nitrogen sorption isothermswere measured at 298 or 273 K with a Bel Japan Inc. model BELSORP-max analyzer, respectively. In addition, carbon dioxide sorption isotherms were measured at 318 K and 5 × 106 Pa with a iSorb HP2 analyzer. Before measurement, the samples were also degassed in vacuum at 120 °C for more than 10 h.2.2.1 Synthesis of CMP containing carboxylic groupsAll of the polymer networks containing multi-carboxylic groups were synthesized by palladium(0)-catalyzed cross-coupling polycondensation. All the reactions were carried out at a fixed reaction temperature and reaction time (120 °C/48 h).2.2.2 Synthesis of CMP-COOH@1 and CMP-COOH@22,5-Dibromoterephthalic acid (107 mg, 0.33 mmol) and 1,3,5-triethynylbenzene (50 mg, 0.33 mmol) (CMP-COOH@1)/tetrakis(4-ethynylphenyl)methane (104 mg, 0.25 mmol) (CMP-COOH@2) were put into a 50 mL round-bottom flask, the flask exchanged three cycles under vacuum/N2. Then added to 2 mL N,N-dimethylformamide (DMF) and 2 mL triethylamine (Et3N), the flask was degassed by threefreeze-pump-thaw cycles, purged with N2. When the solution had reached reactiontemperature, a slurry of tetrakis(triphenylphosphine)palladium(0) (23.11 mg, 0.02 mmol) in the 1 mL DMF and copper(I) iodide (4.8 mg, 0.025 mmol) in the 1 mL Et3N (CMP-COOH@1)/(CMP-COOH@2) was added respectively, and the reaction was stirred at 120 °C under nitrogen for 48 h. The solid product was collected by filtration and washed well with hot reaction solvent for 4 times with THF, methanol, acetone, and water, respectively. Further purification of the polymer was carried out by Soxhlet extraction with methanol, and THF for 24 h, respectively, to give CMP-COOH@1(claybank solid, 98 mg, 94% yield), CMP-COOH@2(olivine solid, 142 mg, 90% yield). Elemental Analysis (%) Calcd. (Actual value for an infinite 2D polymer), (CMP-COOH@1) C 67.61, H 2.35. Found: C 64.84, H 2.05. (CMP-COOH@2) C 73.03, H 3.02. Found: C 70.02, H 2.19. Carboxylic-CMP was synthesized by the Sonogashira- Higihara reaction of 1,3,5-triethynylbenzene, tetrakis(4- ethynylphenyl)methane and 2,5-dibromoterephthalic acid in the presence of Pd(0) as catalyst. These two samples were unambiguously characterized by elemental analysis confirmed that the weight percentages of C and H contents are close to the calculated values expected for an infinite 2D polymer. The CMPs were further characterized by infrared spectroscopy (Fig.1). Band soft he primary bromo and borate groups of 2,5-dibromoterephthalic acid at about 598 and 1368 cm−1are absent, respectively. From 2900 to 3200 cm−1aromatic C―H stretching bands appear. A C＝C stretching mode at 1600 cm−1is also observed. All networks show the typical C≡C and COOH stretching mode at about 2200and 1700 cm−1, respectivel y, indicating the successfulincorporation of the carboxylic and alkynyl groups into the polymer materials.Field-emission scanning electron microscopy (FE-SEM) displayed that the CMPs adopt a spherical shape with sizes of 100–500 nm (Fig.2). High-resolution transmission electron microscopy (HR-TEM) revealed the homogeneous distribution of nanometer-scale pores in the textures (Fig.S1 (Supporting Information)). Powder X-ray diffraction (PXRD) revealed no diffraction, implying that all the polymers are amorphous (Fig.S2 (Supporting Information)). The TGA results show that the polymers have a good thermal stability, and the thermal degradation temperature is up to ca. 300 °C (Fig.S3 (Supporting Information)). The weight loss below 100 °C is generally attributed to the evaporation of adsorbed water and gas molecules trapped in the micropores.The conjugated polymer networks were dispersed in THF to obtain UV/Vis spectra (Fig.S4 (Supporting Information)). The polymer CMP-COOH@1 shows mainly one wide absorption peak at about 396 nm. Compared to monomer 1,3,5-triethynylbenzene, with narrow absorption maxima at 305 nm, the polymer networks exhibit a large bathochromic shift of around 111 nm. CMP-COOH@2 show similar phenomenon, compared totetrakis(4-ethynylphenyl)methane monomer, with absorption maxima at 325 and 345 nm, the polymer frameworks display a large bathochromic shift of around 68 and 48 nm, respectively. This indicates the effective enlargement of the π-conjugated system through the polycondensation reaction.The porosity of the polymer networks was probed by nitrogen sorption at 77 K. According to the IUPAC classification37, adsorption/desorption isotherms of two polymers showed mainly a type I isotherms. As seen in Fig.3(a), remarkably, the two polymer samples exhibit a steep uptake at a relative pressure of p/p0 < 0.1, suggesting that these samples have micropores. There is a sharp rise in the isotherm for the CMP-COOH@1 at higher relative pressures (p/p0 > 0.8), which indicates the presence of meso/macropores in the samples. These textural meso/macropores can be also found in the corresponding FE-SEM images (Fig.2(a)). However, the shape of the isotherm for the CMP-COOH@2 is significantly different from that of CMP-COOH@1, which displays a significant H2 type hysteresis loop in the desorption branch, characteristic of nanostructured materials with a mesoporous structure (Fig.3(a)). These meso/macropores can be ascribed mostly to interparticulate porosity that exists between the highly aggregated nanoparticles38.The pore size distribution calculated from nonlinear density functional theory (NLDFT) shows that the two polymer networks have relatively broad pore size distribution (Fig.3(b)). CMP-COOH@1 and CMP-COOH@2 showed apparent peaks in the size range 0–2 nm, whereas small fluctuations can be observed at 2–12 nm regions. The pore size distribution curves agree with the shape of the N2 isotherms (Fig.3(a)) and imply the presence of both micropores and mesopores in the two polymers. The contribution of microporosity to the networks can be calculated as the ratio of the micropore volume (Vmicro), over the totalpore volume (Vtotal). The microporosities of CMP-COOH@1 and CMP-*******************%and52.3%,respectively.Thisresultindicates that the two carboxylic networks are predominantly microporous. In addition, the BET surface area of CMP-COOH@1 and CMP-COOH@2 were calculated to be 835 and 765 m2·g−1 in the relative pressure range 0.015–0.1, respectively. The decreased surface area of CMP-COOH@2 compared to CMP-COOH@1 could be due to the CMPs constructed with longer connecting struts have lower BET surface areas39,40.In view of the fact that the CMPs possess two key properties generally associated with high CO2 uptake capacity, e.g., good porosity and abundant COOH sites, the CO2 adsorption of the polymers were investigated up to 1.05 × 105 Pa at both 298 K and 273 K (Fig.4(a, b)), respectively. Remarkably, CMP-COOH@1 and CMP-COOH@2 showed the CO2 adsorption capacities of 1.61 and 1.92 mmol·g−1 at 298 K and 1.05 × 105 Pa, respectively (Fig.4(a)). When the temperature was elevated to 273 K, the polymers CMP-COOH@1 and CMP-COOH@2 displayed the higher CO2 capture of 2.17 and 2.63 mmol·g−1(Fig.4(b)), respectively, which were comparable to that of other microporous hydrocarbon networks41. Despite CMP-COOH@2 with a lower surface area, but which adsorbed more CO2 probably due to it has a higher pore volume. In addition, the isosteric heat of adsorption (Qst) of the polymers was calculated from the CO2 uptake data at 273 K and 298 K by using Clausius-Clapeyron equation (Fig.4(c)). The two polymer networks show the isosteric heats of CO2 adsorption around 35.5 and 30.9 kJ·mol−1. Because there is less carboxylicacid in the structural unit, the CO2Qst of CMP-COOH@2 is lower than that of CMP-COOH@1, which is consistent with that of the previous reported polymers33,34. Moreover, the high pressure CO2 sorption properties of the two polymers were also investigated at 5 × 106 Pa and 318 K. As seen in Fig.4(d), CMP-COOH@1 and CMP-COOH@2 show a nearly linear increase with the increasing pressure no obviously turning point. CMP-COOH@1 and CMP-COOH@2 show the higher CO2 capture capacity of 498 and 434 mg·g−1 at 318 K and 5 × 106 Pa, respectively (Fig.4(d)). These results indicated that the CO2 uptake in these networks at high pressures is not dependent solely on the surface area, pore volume or polar groups in the skeletons, but also the measuring pressure have a large effect on the uptake of gas.In order to investigate the amount of carboxylic group in the network whether affects CO2 adsorption capacity of polymers. We synthesized another two carboxylic conjugated polymer with relatively low amount of carboxylic groups (scheme S1, CMP@1 and CMP@2 (Supporting Information)) based on 2,5-dibromobenzoic acid, 1,3,5-triethynylbenzene and tetrakis(4-ethynylphenyl)methane. They show the BET surface area of 979 and 876 m2·g−1 (Fig.S5 (Supporting Information)), respectively, which is higher to that of counterpart CMP-COOH@1 and CMP-COOH@2. CMP@***********************************–2.0 nm (Fig.S6 (Supporting Information)). The decreased surface area of CMP-COOH@1 compared to CMP@1 could be due to the volume of 2,5-dibromoterephthalic acid in CMP-COOH@1 is obviously larger than 2,5-dibromobenzoic acid in CMP@1, which made the bulky benzen–carboxylic **************************************************** phenomenon can be also observed in CMP-COOH@2 and CMP@2 system. As shown in Fig.4(b), at 273 K and 1.05 × 105 Pa, polymers C MP@1 and****************************************.28mmol·g−1, respectively. The CO2 uptake value of CMP-COOH@1 and CMP-COOH@2 is 1.31 and 1.15-times that of the counterpart CMP@1 and CMP@2, respectively, indicating that increasing amount of carboxylic groups in the CMP networks can improve CO2 uptake. In addition, we calculated the isosteric heats of these polymers, they showed the following order (Fig.4(c)):CMP-COOH@1>CMP-COOH@2>CMP@1>************* there is less carboxylic groups in the structural units of CMP@1 andCMP@2, the CO2Qst of CMP@1 and CMP@2 is lower than that of CMP-COOH@1 and CMP-COOH@2, respectively33,42. In addition, CMP-COOH@1 and CMP-COOH@2 show the higher CO2 capture capacity than that of CMP@1 (447 mg·g−1) and CMP@2 (402 mg·g−1) at 318 K and 5 × 106 Pa, respectively (Fig.4(d)). These results imply the amount of carboxylic groups effects BET surface area, pore volume and isosteric heats lead to different the uptake of gas.As for carbon dioxide capture, high separation properties towards CH4 and N2 are also necessary and important in gas separation applications. In order to investigate the gas adsorption selectivity of the microporous polymer networks, CO2, N2, and CH4 sorption properties were measured by volumetric metho ds at 273 K and 1.05 × 105 Pa. It was found that thetwo porous polymer networks show significantly higher CO2 uptake ability than N2 and CH4 in the whole measurement pressure range (Fig.S7 (Supporting Information)). CO2/CH4 and CO2/N2 selectivity was first evaluated by using the initial slope ratios estimated from Henry′s law constants for single-component adsorption isotherms. The CO2/CH4 selectivityofCMP-COOH@********************************** and 6.2, respectively (Table S1 and Fig.S8 (Supporting Information)). In addition, two polymers exhibited the CO2/N2 adsorption selectivity is 48.2 and 39.5, respectively (Table S1 and Fig.S9 (Supporting Information)). Meanwhile, the gas selective capture was also supported by the results from the ideal adsorbed solution theory (IAST), which has been widely used to predict gas mixture adsorption behavior in the porous materials43,44. Under simulated natural gas conditions (CO2/CH4, 50/50), the experimental CO2 and CH4 isotherms collected at 273 K for carboxylic CMP were fitted to the dual-site Langmuir model and the single-site Langmuir model, respectively (Fig.S10 (Supporting Information)). The calculated IAST data for carboxylic CMP are shown in Table S1. At 273 K and 1.05 × 105 Pa, CMP-COOH@1 and CMP-COOH@2 exhibit an appreciably high selectivity of CO2 over CH4 under natural gas conditions (5.5 and 5.2) (Fig.S10 (Supporting Information)), which is comparable to some reported MOPs, such as A6CMP (5.1) 45, SCMP (4.4–5.2) 30, and P-G1-T (5) 46. Furthermore, the CO2/N2 adsorption selectivities for CMP-COOH@****************************************.8at273K and 1.05 × 105 Pa (Table S1 and Fig.S11 (Supporting Information)),respectively, which is comparable to some reported MOPs, such as ALP-1(35) 38, PCN-TA (33) 47, and PCN-DC (48) 47. These excellent CO2 selective capture performance of carboxylic CMPs evaluated by IAST are consistent with the results calculated from the initial slopes method. In addition, in light of the amount of carboxylic group effect for the uptake of gas, we reasoned that it might be effective for CO2/CH4 and CO2/N2 separations. At 273 K and 1.05 × 105 Pa, CMP@1 and CMP@2 exhibit the selectivities of CO2/CH4 (4.7 and 4.1) and CO2/N2 (32.1 and 30.5) under natural gas conditions via the IAST method (Figs.S10 and S11 (Supporting Information)), respectively, which are lower that of counterpart CMP- COOH@************************************************* carboxylic groups effects selectivity of polymers. These data implys that increasing the amount of carboxylic unit of polymers can improve the adsorption capacity and selectivity of the materials, which suggested the possibility for the surface properties of microporous polymers to be controlled to interact with a specific gas by post-modification.In summary, two carboxylic CMPs with relatively high surface area have been synthesized. The clean energy applications of the polymers have also been investigated and it was found that CMP-COOH@1 and CMP-***********************.63mg·g−1 of carbon dioxide at 1.05 × 105 Pa and 273 K, respectively, which can be competitive with the reported results for porous organic polymers under the same conditions. 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tpo61三篇托福阅读TOEFL原文译文题目答案背景知识阅读-1 (2)原文 (2)译文 (5)题目 (7)答案 (13)背景知识 (15)阅读-2 (18)原文 (19)译文 (22)题目 (24)答案 (32)背景知识 (34)阅读-3 (39)原文 (39)译文 (42)题目 (45)答案 (53)背景知识 (54)阅读-1原文Physical Properties of Minerals①A mineral is a naturally occurring solid formed by inorganic processes. Since the internal structure and chemical composition of a mineral are difficult to determine without the aid of sophisticated tests and apparatus , the more easily recognized physical properties are used in identification.②Most people think of a crystal as a rare commodity, when in fact most inorganic solid objects are composed of crystals. The reason for this misconception is that most crystals do not exhibit their crystal form: the external form of a mineral that reflects the orderly internal arrangement of its atoms. Whenever a mineral forms without space restrictions, individual crystals with well-formed crystal faces will develop. Some crystals, such as those of the mineral quartz, have a very distinctive crystal form that can be helpful in identification. However, most of the time, crystal growth is interrupted because of competition for space, resulting in an intergrown mass of crystals, none of which exhibits crystal form.③Although color is an obvious feature of a mineral, it is often anunreliable diagnostic property. Slight impurities in the common mineral quartz, for example, give it a variety of colors, including pink, purple (amethyst), white, and even black. When a mineral, such as quartz, exhibits a variety of colors, it is said to possess exotic coloration. Exotic coloration is usually caused by the inclusion of impurities, such as foreign ions, in the crystalline structure. Other minerals —for example, sulfur, which is yellow, and malachite, which is bright green —are said to have inherent coloration because their color is a consequence of their chemical makeup and does not vary significantly.④Streak is the color of a mineral in its powdered form and is obtained by rubbing a mineral across a plate of unglazed porcelain. Whereas the color of a mineral often varies from sample to sample, the streak usually does not and is therefore the more reliable property.⑤Luster is the appearance or quality of light reflected from the surface of a mineral. Minerals that have the appearance of metals, regardless of color, are said to have a metallic luster. Minerals with a nonmetallic luster are described by various adjectives, including vitreous (glassy) pearly, silky, resinous, and earthy (dull).⑥One of the most useful diagnostic properties of a mineral is hardness, the resistance of a mineral to abrasion or scratching. This property is determined by rubbing a mineral of unknown hardness against one ofknown hardness, or vice versa. A numerical value can be obtained by using Mohs' scale of hardness, which consists of ten minerals arranged in order from talc, the softest, at number one, to diamond, the hardest, at number ten. Any mineral of unknown hardness can be compared with these or with other objects of known hardness. For example, a fingernail has a hardness of 2.5, a copper penny 5, and a piece of glass 5.5. The mineral gypsum, which has a hardness of two, can be easily scratched with your fingernail. On the other hand, the mineral calcite which has a hardness of three, will scratch your fingernail but will not scratch glass. Quartz, the hardest of the common minerals, will scratch a glass plate.⑦The tendency of a mineral to break along planes of weak bonding is called cleavage. Minerals that possess cleavage are identified by the smooth, flat surfaces produced when the mineral is broken. The simplest type of cleavage is exhibited by the micas. Because the micas have excellent cleavage in one direction, they break to form thin, flat sheets. Some minerals have several cleavage planes, which produce smooth surfaces when broken, while others exhibit poor cleavage, and still others exhibit no cleavage at all. When minerals break evenly in more than one direction, cleavage is described by the number of planes exhibited and the angles at which they meet. Cleavage should not be confused with crystal form. When a mineral exhibits cleavage, itwill break into pieces that have the same configuration as the original sample does. By contrast, quartz crystals do not have cleavage, and if broken, would shatter into shapes that do not resemble each other or the original crystals. Minerals that do not exhibit cleavage are said to fracture when broken. Some break into pieces with smooth curved surfaces resembling broken glass. Others break into splinters or fibers, but most fracture irregularly.译文矿物的物理性质①矿物质是由无机过程形成的天然固体。
林业工程学报，２０２４，９（２）：５５－６２ＪｏｕｒｎａｌｏｆＦｏｒｅｓｔｒｙＥｎｇｉｎｅｅｒｉｎｇＤＯＩ：１０．１３３６０／ｊ．ｉｓｓｎ．２０９６－１３５９．２０２３０７００５收稿日期：２０２３－０７－１５㊀㊀㊀㊀修回日期：２０２３－１１－１２基金项目：国家自然科学基金（５１８７３１９４）；浙江省自然科学基金华东医药企业创新发展联合基金（ＬＨＤＭＺ２３Ｈ３００００３）㊂作者简介：施宇斐，男，研究方向为复合纤维材料及应用㊂通信作者：江国华，男，教授㊂Ｅ⁃ｍａｉｌ：ｇｈｊｉａｎｇ＿ｃｎ＠ｚｓｔｕ．ｅｄｕ．ｃｎＺＩＦ⁃８／纳米纤维素对竹木复合纤维除臭性能的影响施宇斐１，２，江国华１，２∗（１．浙江理工大学材料科学与工程学院，杭州３１００１８；２．浙江省智能生物材料与功能纤维国际科技合作基地，杭州３１００１８）摘㊀要：近年来，随着人们生活品质要求的不断提升，具有除臭性能好㊁吸收性能强和价格成本低廉的纤维材料在婴幼儿㊁成人除臭纸尿裤等卫生用品中的需求量不断增高㊂但目前市场上的除臭纤维基本存在除臭性能差㊁吸水性弱以及成本高的问题，严重制约我国除臭功能性纤维材料的国际竞争力㊂笔者以国内常见的白竹炭纤维和针叶木纤维为基本原料，以ＺＩＦ⁃８纳米粒子和纳米纤维素（ＣＮＦ）为除臭改性填料，通过复合加工工艺，制备了兼具除臭和吸水功能的竹木复合除臭纤维，并探究了白竹炭纤维和针叶木纤维原料质量比㊁改性填料含量对复合除臭纤维微结构㊁吸水以及除氨气㊁硫化氢等臭味气体的影响规律㊂研究结果表明，所制备复合除臭纤维最佳工艺条件为针叶木纤维与白竹炭纤维绝干质量比为７０ʒ３０，ＺＩＦ⁃８和ＣＮＦ的质量分数分别为７％和６％，２３ħ下风干处理２４ｈ，在该工艺条件下制备的除臭纤维对氨气和硫化氢的消臭率分别为８４．５６％和８３．１１％，吸水量为８．４ｇ／ｇ，除臭纤维性能达到国家标准ＧＢ／Ｔ３３６１０．２—２０１７（消臭率ȡ７０％）的要求㊂关键词：除臭纤维；白竹炭纤维；针叶木纤维；除臭性能；ＺＩＦ⁃８中图分类号：ＴＳ７２１㊀㊀㊀㊀㊀文献标志码：Ａ㊀㊀㊀㊀㊀文章编号：２０９６－１３５９（２０２４）０２－００５５－０８ＥｆｆｅｃｔｏｆＺＩＦ⁃８／ｎａｎｏｃｅｌｌｕｌｏｓｅｏｎｄｅｏｄｏｒｉｚａｔｉｏｎｏｆｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓＳＨＩＹｕｆｅｉ１，２，ＪＩＡＮＧＧｕｏｈｕａ１，２∗（１．ＣｏｌｌｅｇｅｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅａｎｄＥｎｇｉｎｅｅｒｉｎｇ，ＺｈｅｊｉａｎｇＳｃｉ⁃ＴｅｃｈＵｎｉｖｅｒｓｉｔｙ，Ｈａｎｇｚｈｏｕ３１００１８，Ｃｈｉｎａ；２．ＩｎｔｅｒｎａｔｉｏｎａｌＳｃｉｅｎｔｉｆｉｃａｎｄＴｅｃｈｎｏｌｏｇｉｃａｌＣｏｏｐｅｒａｔｉｏｎＢａｓｅｏｆＩｎｔｅｌｌｉｇｅｎｔＢｉｏｍａｔｅｒｉａｌｓａｎｄＦｕｎｃｔｉｏｎａｌＦｉｂｅｒｓ，Ｈａｎｇｚｈｏｕ３１００１８，Ｃｈｉｎａ）Ａｂｓｔｒａｃｔ：Ｉｎｒｅｃｅｎｔｙｅａｒｓ，ｗｉｔｈｔｈｅｃｏｎｔｉｎｕｏｕｓｅｎｈａｎｃｅｍｅｎｔｏｆｐｅｏｐｌｅ ｓｒｅｑｕｉｒｅｍｅｎｔｓｆｏｒｌｉｆｅｑｕａｌｉｔｙ，ｔｈｅｄｅｍａｎｄｆｏｒｆｉｂｅｒｍａｔｅｒｉａｌｓｗｉｔｈｓｐｅｃｉｆｉｃｃｈａｒａｃｔｅｒｉｓｔｉｃｓｓｕｃｈａｓｇｏｏｄｄｅｏｄｏｒｉｚａｔｉｏｎ，ｓｔｒｏｎｇａｂｓｏｒｐｔｉｏｎａｎｄｃｏｓｔ⁃ｅｆｆｅｃｔｉｖｅｎｅｓｓｈａｓｂｅｅｎｉｎｃｒｅａｓｉｎｇｉｎｈｙｇｉｅｎｉｃａｎｄｈｅａｌｔｈｃａｒｅｐｒｏｄｕｃｔｓ，ｉｎｃｌｕｄｉｎｇｄｅｏｄｏｒｉｚｅｄｄｉａｐｅｒｓｆｏｒｉｎｆａｎｔｓａｎｄａｄｕｌｔｓ．Ｈｏｗｅｖｅｒ，ｔｈｅｄｅｏｄｏｒｉｚａｔｉｏｎｆｉｂｅｒｓｉｎｔｈｅｍａｒｋｅｔｈａｖｅｓｏｍｅｐｒｏｂｌｅｍｓ，ｓｕｃｈａｓｐｏｏｒｄｅｏｄｏｒｉｚａｔｉｏｎｐｅｒｆｏｒｍａｎｃｅ，ｗｅａｋｗａｔｅｒａｂ⁃ｓｏｒｐｔｉｏｎ，ａｎｄｈｉｇｈｃｏｓｔ，ｗｈｉｃｈｓｅｒｉｏｕｓｌｙｒｅｓｔｒｉｃｔｔｈｅｑｕａｌｉｔｙｉｍｐｒｏｖｅｍｅｎｔｏｆｄｏｍｅｓｔｉｃｈｙｇｉｅｎｉｃｐｒｏｄｕｃｔｓ．Ｚｅｏｌｉｔｉｃｉｍｉｄ⁃ａｚｏｌａｔｅｆｒａｍｅｗｏｒｋ⁃８（ＺＩＦ⁃８）ｉｓｏｎｅｏｆｍｅｔａｌ⁃ｏｒｇａｎｉｃｆｒａｍｅｗｏｒｋｍａｔｅｒｉａｌｓ（ＭＯＦｓ），ｈａｖｉｎｇｌａｒｇｅｓｐｅｃｉｆｉｃｓｕｒｆａｃｅａｒｅａａｎｄｖｏｉｄｖｏｌｕｍｅ，ｕｎｉｑｕｅｂｉｏｄｅｇｒａｄａｂｉｌｉｔｙａｎｄｐＨｓｅｎｓｉｔｉｖｉｔｙ，ａｎｄｓｉｇｎｉｆｉｃａｎｔｌｏａｄｉｎｇｃａｐａｃｉｔｙ．Ｉｔｈａｓｂｅｅｎｗｉｄｅｌｙｕｓｅｄａｓｃａｒｒｉｅｒｍａｔｅｒｉａｌｓｆｏｒａｐｐｌｉｃａｔｉｏｎｓｉｎｔｈｅｆｉｅｌｄｏｆｄａｉｌｙｌｉｆｅａｎｄｈｅａｌｔｈｃａｒｅ．Ｎａｎｏｃｅｌｌｕｌｏｓｅ（ＣＮＦ）ｉｓａｒｅｎｅｗａｂｌｅｏｒｇａｎｉｃｏｎｅ⁃ｄｉｍｅｎｓｉｏｎａｌｎａｎｏｍａｔｅｒｉａｌ，ｗｈｉｃｈｈａｓｆａｖｏｒａｂｌｅｍｕｌｔｉｆｕｎｃｔｉｏｎａｌｃｈａｒａｃｔｅｒｓ，ｓｕｃｈａｓｌａｒｇｅｓｐｅｃｉｆｉｃｓｕｒｆａｃｅａｒｅａ，ｈｉｇｈｍｅｃｈａｎｉｃａｌｐｒｏｐｅｒｔｙ，ｈｙｄｒｏｐｈｉｌｉｃｉｔｙａｎｄｂｉｏｄｅｇｒａｄａｂｉｌｉｔｙ．Ｉｎａｄｄｉｔｉｏｎ，ｂａｍｂｏｏａｎｄｗｏｏｄａｒｅｇｒｅｅｎ，ｌｏｗ⁃ｃａｒｂｏｎ，ｆａｓｔ⁃ｇｒｏｗｉｎｇ，ｅａｓｉｌｙｒｅｎｅｗａｂｌｅａｎｄｄｅｇｒａｄａｂｌｅｂｉｏｍａｓｓｍａｔｅｒｉａｌｓ．Ｍｏｄｉｆｉｃａｔｉｏｎｏｆｂａｍｂｏｏ⁃ｗｏｏｄｐｕｌｐｆｉｂｅｒｓｗｉｔｈＺＩＦ⁃８ａｎｄＣＮＦｉｓａｓｉｍｐｌｅａｎｄｅｆｆｅｃｔｉｖｅｓｔｒａｔｅｇｙｔｏｉｍｐｒｏｖｅｔｈｅｉｒｄｅｏｄｏｒｉｚａｔｉｏｎｐｅｒｆｏｒｍａｎｃｅ．Ｉｎｔｈｉｓｓｔｕｄｙ，ｔｈｅｂａｍｂｏｏ⁃ｗｏｏｄｆｉｂｅｒｓａｎｄｃｏｎｉｆｅｒｏｕｓｗｏｏｄｆｉｂｅｒｓｗｅｒｅｓｅｌｅｃｔｅｄａｓｂａｓｉｃｒａｗｍａｔｅｒｉａｌｓ．ＺＩＦ⁃８ｍｅｔａｌ⁃ｏｒｇａｎｉｃｆｒａｍｅｗｏｒｋｍａｔｅｒｉａｌｎａｎｏｐａｒｔｉｃｌｅｓａｎｄｎａｎｏｃｅｌｌｕｌｏｓｅ（ＣＮＦ）ｗｅｒｅｕｓｅｄａｓｄｅｏｄｏｒｉｚａｔｉｏｎｆｉｌｌｅｒｓｔｏｆａｂｒｉｃａｔｅｎｏｖｅｌｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓｗｉｔｈｄｅｏｄｏｒｉｚａｔｉｏｎａｎｄｗａｔｅｒａｂｓｏｒｐｔｉｏｎｆｕｎｃｔｉｏｎｓｂｙａｓｉｍｐｌｅｃｏｍｐｏｓｉｔｅｐｒｏｃｅｓｓｉｎｇｐｒｏｃｅｓｓ．Ｔｈｅｅｆｆｅｃｔｓｏｆｔｈｅｒａｗｍａｔｅｒｉａｌｒａｔｉｏｏｆｗｈｉｔｅｂａｍｂｏｏｃｈａｒｃｏａｌｆｉｂｅｒａｎｄｃｏｎｉｆｅｒｏｕｓｗｏｏｄｆｉｂｅｒ，ａｓｗｅｌｌａｓｔｈｅｔｙｐｅａｎｄｄｏｓａｇｅｏｆｔｈｅｆｉｌｌｅｒｓ，ｏｎｔｈｅｍｉｃｒｏｓｔｒｕｃｔｕｒｅ，ｗａｔｅｒａｂｓｏｒｐｔｉｏｎａｎｄｒｅｍｏｖａｌｏｆｏｄｏｒｇａｓｅｓｓｕｃｈａｓａｍｍｏｎｉａａｎｄｈｙｄｒｏｇｅｎｓｕｌｆｉｄｅｗｅｒｅｉｎｖｅｓ⁃ｔｉｇａｔｅｄ．Ｔｈｅｒｅｓｅａｒｃｈｒｅｓｕｌｔｓｉｎｄｉｃａｔｅｄｔｈａｔｔｈｅｏｐｔｉｍａｌｐｒｏｃｅｓｓｃｏｎｄｉｔｉｏｎｓｆｏｒｐｒｅｐａｒｉｎｇｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｗｅｒｅａｓｆｏｌｌｏｗｓ：ｔｈｅｄｒｙｍａｓｓｒａｔｉｏｏｆｃｏｎｉｆｅｒｏｕｓｗｏｏｄｆｉｂｅｒｓｔｏｗｈｉｔｅｂａｍｂｏｏｃａｒｂｏｎｆｉｂｅｒｓｗａｓ７０ʒ３０，ｔｈｅｍａｓｓｆｒａｃｔｉｏｎｏｆＺＩＦ⁃８ａｎｄＣＮＦｗｅｒｅ７％ａｎｄ６％，ｒｅｓｐｅｃｔｉｖｅｌｙ，ａｎｄａｉｒ⁃ｄｒｙｉｎｇｔｒｅａｔｍｅｎｔｗａｓａｔ２３ħｆｏｒ２４ｈ．Ｔｈｅｄｅｏｄｏ⁃ｒｉｚａｔｉｏｎｆｉｂｅｒｓｐｒｅｐａｒｅｄｕｎｄｅｒｔｈｉｓｐａｒａｍｅｔｅｒｃｏｎｄｉｔｉｏｎｈａｄｄｅｏｄｏｒｉｚａｔｉｏｎｒａｔｅｓｏｆ８４．５６％ａｎｄ８３．１１％ｆｏｒａｍｍｏｎｉａ林业工程学报第９卷ａｎｄｈｙｄｒｏｇｅｎｓｕｌｆｉｄｅｗｉｔｈａｗａｔｅｒａｂｓｏｒｐｔｉｏｎｃａｐａｃｉｔｙａｔ８．４ｇ／ｇ．Ｔｈｅｄｅｏｄｏｒｉｚａｔｉｏｎｐｅｒｆｏｒｍａｎｃｅｏｆｔｈｅａｓ⁃ｐｒｅｐａｒｅｄｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓｗａｓｈｉｇｈｅｒｔｈａｎｔｈｅｒｅｑｕｉｒｅｍｅｎｔｓｏｆｔｈｅｎａｔｉｏｎａｌｓｔａｎｄａｒｄＧＢ／Ｔ３３６１０．２－２０１７（ｄｅｏ⁃ｄｏｒｉｚａｔｉｏｎｒａｔｅȡ７０％）．Ｔｈｅｒｅｆｏｒｅ，ｔｈｅｄｅｏｄｏｒｉｚａｔｉｏｎｐｅｒｆｏｒｍａｎｃｅｏｆｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓｃａｎｂｅｅｆｆｅｃｔｉｖｅｌｙｉｍｐｒｏｖｅｄ，ａｃｈｉｅｖｉｎｇｔｈｅｅｎｈａｎｃｅｍｅｎｔｏｆａｄｄｅｄｖａｌｕｅｆｏｒｔｈｅｆａｓｔ⁃ｇｒｏｗｉｎｇｈｙｇｉｅｎｉｃａｎｄｈｅａｌｔｈｃａｒｅｐｒｏｄｕｃｔｓｔｏｂａｌａｎｃｅｄｅｏｄｏｒｉｚａｔｉｏｎａｎｄｗａｔｅｒａｂｓｏｒｐｔｉｏｎｐｒｏｐｅｒｔｉｅｓ．Ｋｅｙｗｏｒｄｓ：ｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒ；ｂａｍｂｏｏｃｈａｒｃｏａｌｆｉｂｅｒ；ｃｏｎｉｆｅｒｏｕｓｗｏｏｄｆｉｂｅｒ；ｄｅｏｄｏｒｉｚｉｎｇｐｅｒｆｏｒｍａｎｃｅ；ＺＩＦ⁃８㊀㊀随着健康生活理念的不断深入，个人健康护理也逐渐受到人们的广泛关注㊂在使用传统纸尿裤时，吸入尿液和粪便等排泄物会产生难闻的气味，大大降低穿戴者的舒适性㊂在纸尿裤中添加除臭纤维材料可赋予其除臭功能，能够提高产品的舒适度和提升用户体验感，极具市场应用潜力㊂目前多数国产除臭纸尿裤都是通过直接加入竹炭条㊁活性炭或植物复合酶的方式来减少气味的散发［１］，在使用过程中存在除臭和吸液无法同时兼顾的问题㊂竹炭纤维具有蜂窝状微孔结构［２］，独特的内部结构使其具有多种优良性能，例如单根纤维强度高㊁吸湿速干性能优异㊁对水分子和臭味气体吸附能力极强等［３］㊂ＺＩＦ⁃８是一种类沸石咪唑酯骨架结构材料，其继承了金属有机骨架材料（ＭＯＦｓ）和沸石的优良特性，具有极高的比表面积㊁优异的孔隙率和稳定性［４－６］㊂针叶木纤维则来源广泛，拥有优异的力学和加工性能㊂因此，利用ＺＩＦ⁃８和纳米纤维素改性提升竹炭／木浆纤维除臭性能是一种简单有效的策略㊂同时，纳米纤维素本身具有较大比表面积和丰富羟基，也增强了复合纤维的吸水性能［７－８］㊂本研究针对当前除臭纤维存在的问题，设计了一种以白竹炭纤维和针叶木纤维为主要原料，以ＺＩＦ⁃８纳米粒子和纳米纤维素为改性填料，通过一定工艺制备成型的能够协同吸液和除臭的复合纤维㊂探究了纤维原料组成㊁改性填料比例对复合除臭纤维的性能影响规律，从而确定了最佳制备工艺参数㊂１㊀材料与方法１．１㊀试验材料硝酸锌六水化合物（分析纯，ＣＡＳ：１０１９６⁃１８⁃６）㊁氨水（质量分数２８％，ＣＡＳ：１３３６⁃２１⁃６）㊁２⁃甲基咪唑（分析纯，ＣＡＳ：６９３⁃９８⁃１）和甲醇（分析纯，ＣＡＳ：６７⁃５６⁃１），购自上海阿拉丁生化科技股份有限公司；白竹碳纤维，购自南昌竹生富纳米科技有限公司；漂白硫酸盐针叶木（Ｌｉｇｎｕｍｃｏｎｉｆｅｒｏｓ）商品浆，购自智利 银星 牌针叶浆料；纳米纤维素（ＣＮＦ），购自浙江金加浩绿色纳米材料股份有限公司；氨气和硫化氢气体由淄博迪嘉特种气体有限公司提供㊂１．２㊀试验仪器Ｕｌｔｒａ５５型场发射扫描电子显微镜（ＳＥＭ，德国ＣａｒｌＺｅｉｓｓ）；ＴＤ１０⁃２００型纸页成型器（德国Ｅｓｔａｎｔ）；３⁃１８ＫＳ型台式高速离心机（德国Ｓｉｇｍａ）；Ｄ８ｄｉｓｃｏｖｅｒ型Ｘ射线衍射仪（ＸＲＤ，德国Ｂｒｕｋｅｒ）；ＭＹＰ１９⁃２型集热式恒温磁力搅拌器（郑州市亚荣仪器有限公司）；Ｎａｎｏ⁃ＺＳＺＥＮ３６００型动态光散射粒度分析仪（英国Ｍａｌｖｅｒｎ）；ＢＳＤ⁃ＰＭ型比表面积分析仪（贝士德仪器科技有限公司）㊂１．３㊀ＺＩＦ⁃８的制备在烧杯中依次加入１．４６ｇ六水合硝酸锌㊁２８．３２ｇ２⁃甲基咪唑和８０ｍＬ甲醇，搅拌均匀后，在室温下反应２２ｈ，离心收集白色晶体［９］㊂用２０ｍＬ甲醇洗涤ＺＩＦ⁃８纳米粒子３次，转速为８０００ｒ／ｍｉｎ，离心时间为１０ｍｉｎ／次；３０ħ真空干燥１２ｈ后约得０．５２ｇＺＩＦ⁃８纳米粒子㊂１．４㊀除臭纤维的制备将针叶木浆板和白竹炭纤维粉碎处理，多组针叶木纤维和白竹炭纤维具有不同质量比（１００ʒ０㊁９０ʒ１０㊁８０ʒ２０㊁７０ʒ３０和６０ʒ４０）浸泡１２ｈ并备用㊂加入相应质量分数ＺＩＦ⁃８粉末与纳米纤维素，然后将其混合溶液放入标准纤维疏解器中疏解１０ｍｉｎ，ＺＩＦ⁃８质量分数分别为原料绝干质量的１％，３％，５％，７％和９％，纳米纤维素质量分数分别为原料绝干质量的０％，３％，６％，９％和１２％㊂利用纸页成型机模型过滤上述均匀分散浆料以获得湿纸浆纤维网，然后在恒温环境２３ħ下风干处理２４ｈ，得干燥后的除臭纤维㊂１．５㊀结构表征与性能测试１．５．１㊀结构表征通过ＳＥＭ表征ＺＩＦ⁃８㊁ＣＮＦ㊁竹木混合原料纤维与除臭纤维的形态㊂通过ＸＲＤ对ＺＩＦ⁃８粉末样品结构分析，在４０ｋＶ和４０ｍＡ下，５ʎ ５０ʎ扫描范围内以５（ʎ）／ｍｉｎ的扫描速度进行测试㊂在室温下采用动态光散射仪对ＺＩＦ⁃８样品水溶液粒径分布进行测试表征㊂采用氮气低温吸附法测定ＺＩＦ⁃８粉末的比表面积和孔径分布曲线㊂６５㊀第２期施宇斐，等：ＺＩＦ⁃８／纳米纤维素对竹木复合纤维除臭性能的影响１．５．２㊀除臭性能测试根据ＧＢ／Ｔ３３６１０．２ ２０１７‘纺织品消臭性能的测定第２部分：检知管法“制备氨气和硫化氢气体样品㊂除臭纤维的除臭性能测试装置为自制装置㊂先称取一定质量除臭纤维，将除臭纤维Ｖ型对折，然后将其放置于自制检测装置中并密封装置；使用注射器从氨气生成装置中抽取１００ｍＬ氨气样品，将氨气样品注入检测装置中，注入多次使氨气初始浓度达到试验要求；使用注射器间隔一定时间从检测装置中迅速抽取２０ｍＬ气体，用检知管检测装置内氨气气体浓度变化，时间间隔为０，１，２４，４８和７２ｈ㊂每种成分除臭纤维均重复试验３次，取平均值㊂硫化氢气体除臭性能检测方式与氨气检测方式一致㊂ａ）ＸＲＤ；ｂ）粒径分布；ｃ）图２㊀ＺＩＦ⁃８的ＸＲＤ㊁粒径分布㊁吸附⁃脱附等温曲线和孔径分布图Ｆｉｇ．２㊀ＸＲＤｐａｔｔｅｒｎ，ｓｉｚｅｄｉｓｔｒｉｂｕｔｉｏｎ，ｎｉｔｒｏｇｅｎａｄｓｏｒｐｔｉｏｎ／ｄｅｓｏｒｐｔｉｏｎｉｓｏｔｈｅｒｍａｎｄｐｏｒｅｓｉｚｅｄｉｓｔｒｉｂｕｔｉｏｎｏｆＺＩＦ⁃８ｎａｎｏｐａｒｔｉｃｌｅｓ１．５．３㊀吸水性能测试采用自制吸水性能检测装置对除臭纤维进行测试分析，操作步骤参考ＧＢ／Ｔ２４３２８．６ ２０２０‘卫生纸及其制品第６部分：吸水时间和吸水能力的测试篮筐浸没法“进行㊂２㊀结果与分析２．１㊀ＺＩＦ⁃８和ＣＮＦ的表征分析通过ＳＥＭ对ＺＩＦ⁃８样品形态进行研究分析，结果如图１ａ所示㊂制备的ＺＩＦ⁃８粒子尺寸大小基本接近，单粒子平均直径为９０ １１０ｎｍ，纳米粒子呈现尖锐的菱形多面体形态，ＺＩＦ⁃８特殊的多面体形态导致粒子具有超高的比表面积㊂ＣＮＦ的表面形貌如图１ｂ所示，ＣＮＦ由条状的纳米纤维素和依附在纳米纤维素表面的球状木质素颗粒组成，纳米纤维素之间呈高度聚集的网状结构㊂注：１和２为不同放大倍数㊂图１㊀不同放大倍数下的ＺＩＦ⁃８和ＣＮＦ的ＳＥＭ图Ｆｉｇ．１㊀ＳＥＭｉｍａｇｅｓｏｆＺＩＦ⁃８ｎａｎｏｐａｒｔｉｃｌｅｓａｎｄｎａｎｏｃｅｌｌｕｌｏｓｅＣＮＦｕｎｄｅｒｄｉｆｆｅｒｅｎｔｍａｇｎｉｆｉｃａｔｉｏｎｓ所制ＺＩＦ⁃８的ＸＲＤ如图２ａ所示，ＺＩＦ⁃８在２θ＝７５林业工程学报第９卷分别对应ＺＩＦ⁃８的（０１１）㊁（００２）㊁（１１２）㊁（０２２）㊁（０１３）和（２２２）晶面粒子，与文献［１０］报道的特征衍射峰高度吻合㊂通过动态光散射进一步表征ＺＩＦ⁃８的粒径大小，结果如图２ｂ所示，ＺＩＦ⁃８平均粒径为（１００ʃ１．５５）ｎｍ，ＺＩＦ⁃８粒径越小说明吸附性能越强㊂ＺＩＦ⁃８粒子的氮气吸附⁃脱附测试结果如图２ｃ㊁ｄ所示，ＺＩＦ⁃８的氮气吸附⁃脱附等温线没有出现滞回环，属典型微孔材料Ｉ型等温线［１１］，说明所制ＺＩＦ⁃８纳米粒子为微孔结构，粒子内部不存在介孔㊂ＺＩＦ⁃８的孔径分布也证实ＺＩＦ⁃８粒子具有多级微孔结构㊂ＺＩＦ⁃８比表面积达１６１５ｍ２／ｇ，孔径为２．１５３ｎｍ，孔体积为０．８８５ｃｍ３／ｇ，说明所制备的ＺＩＦ⁃８粒子具有极高的比表面积，存在多孔结构，这使其可赋予纤维材料极强的去除异味能力㊂２．２㊀除臭纤维微观形貌表征通过ＳＥＭ对原料纤维和除臭纤维的表面形貌进行分析，结果如图３所示㊂管束状竹炭纤维和表面褶皱的针叶木纤维混合成功（图３ａ）㊂竹炭纤维纵向表面光泽均一，具有一定的透气性［１２］，同时针叶木纤维表面有分布深浅不一的沟槽，这些沟槽使针叶木具有较好的吸液性，因此纯竹木混合纤维具有一定的吸液性和透气性㊂注：１和２表示不同的放大倍数㊂图３㊀竹木混合纤维㊁ＺＩＦ⁃８改性竹木混合除臭纤维和ＣＮＦ／ＺＩＦ⁃８改性竹木混合除臭纤维的ＳＥＭ图Ｆｉｇ．３㊀ＳＥＭｉｍａｇｅｓｏｆｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓ，ＺＩＦ⁃８ｍｏｄｉｆｉｅｄｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓａｎｄＣＮＦ／ＺＩＦ⁃８ｍｏｄｉｆｉｅｄｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｆｉｂｅｒｓ㊀㊀ＺＩＦ⁃８改性处理制备的混合除臭纤维显示大量ＺＩＦ⁃８粒子团易絮成微米级颗粒聚在光滑的竹炭纤维束和褶皱粗糙的针叶木纤维表面（图３ｂ），此现象在竹炭纤维上观察更为明显㊂ＺＩＦ⁃８纳米粒子具有极高的比表面积，大量ＺＩＦ⁃８粒子团覆载在纤维表面，提高纤维吸附气体容量和除臭性能㊂ＺＩＦ⁃８和纳米纤维素改性处理制备的竹木混合除臭纤维的ＳＥＭ图（图３ｃ）显示，由于纳米纤维素加入，有效填补纤维网络产生的大孔隙，从而减小结构中的孔径［１３］㊂对比文献［１４］推测，ＺＩＦ⁃８纳米粒子与纳米纤维素发生原位配合，形成一种海胆状的核壳复合结构，增大纳米粒子的比表面积㊂２．３㊀纤维原料比对除臭纤维除氨性能的影响对不同纤维原料比所制竹木混合纤维进行除氨性能检测，探究针叶木纤维原料对氨气吸附能力和加入适量竹炭纤维对氨气吸附能力的影响［１５］㊂每一组试验重复进行３次，取平均值进行分析，并把结果换算成质量浓度Ｃ（ｍｇ／ｍ３），除氨性能效果如表１所示㊂表１㊀不同纤维原料比竹木混合纤维的７２ｈ除氨性能Ｔａｂｌｅ１㊀Ｅｆｆｅｃｔｓｏｆｒａｗｒａｔｉｏｏｆｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａａｆｔｅｒ７２ｈ针叶木与白竹炭质量比纤维原料质量／ｇ初始氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ残留氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ吸附质量浓度／（ｍｇ㊃ｍ－３）消臭率／％１００ʒ０３．０４１０．２１２０．１６５０．０４７２２．２９０ʒ１０３．０５７０．２１３０．１５９０．０５４２５．３８０ʒ２０３．１０２０．２０１０．１４８０．０５３２６．３７０ʒ３０３．０１５０．２１８０．１５２０．０６６３０．３６０ʒ４０３．１２００．２２１０．１５３０．０６８３０．７８５㊀第２期施宇斐，等：ＺＩＦ⁃８／纳米纤维素对竹木复合纤维除臭性能的影响㊀㊀针叶木纤维对氨气具有吸附作用，且随白竹炭纤维含量增加，混合纤维对氨气的吸附能力逐渐增强㊂当白竹炭纤维的质量分数从０％增至４０％时，混合纤维的氨气消臭率从２２．２％提升至３０．７％㊂纤维原料固有的吸附特性可为混合纤维提供更稳定的除臭效果㊂未加除臭剂纤维主要是靠物理方式来吸附异味，这种物理吸附是依靠范德华力相互吸引，而范德华力的强弱主要取决于纤维的比表面积㊂对于针叶木浆纤维，其在制浆过程中木质素脱除完全，木质素主要存在于纤维细胞间层［１５］，大量木质素去除导致细胞内产生大量孔洞，这使针叶木纤维具有较大的表面积，因此针叶木纤维对于氨气具有一定的吸附能力㊂对于竹炭纤维而言，其具有独特的细微孔结构，该结构赋予竹炭纤维较好的吸附能力，竹炭纤维加入提升了混合纤维的吸附性能㊂７２ｈ吸氨具体测试结果如表２所示，５组不同原料比纤维在吸附氨气前１ｈ，氨气浓度均快速下降，之后一段时间吸附速度逐渐变得平缓㊂这是由于这种物理吸附存在吸附和解吸附平衡，刚开始氨气浓度高，纤维吸附速度快，随着氨气被不断吸附于纤维表面，氨气浓度减小，纤维吸附速度减缓，并逐步达到平衡，此时纤维对氨气的吸附能力达到最大㊂结果表明，较少含量（＜３０％）白竹炭纤维对于纤维吸附性能的提升显著，随含量增加，其所起的作用逐渐减少㊂综合考虑，所选用的纤维原料针叶木纤维和白竹炭纤维的质量比为７０ʒ３０㊂表２㊀不同纤维原料比竹木混合纤维的除氨测试Ｔａｂｌｅ２㊀Ｅｆｆｅｃｔｏｆｒａｗｒａｔｉｏｏｆｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａａｔｄｉｆｆｅｒｅｎｔｉｎｔｅｒｖａｌｔｉｍｅｓ序号针叶木与白竹炭质量比不同吸附时间后的残余氨气质量浓度／（ｍｇ㊃ｍ－３）０ｈ１ｈ２４ｈ４８ｈ７２ｈＡ１００ʒ００．２１２０．１９１０．１７８０．１６９０．１６５Ｂ９０ʒ１００．２１３０．１８９０．１８００．１６５０．１５９Ｃ８０ʒ２００．２０１０．１８１０．１６９０．１５５０．１４８Ｄ７０ʒ３００．２１８０．１９３０．１７２０．１６６０．１５２Ｅ６０ʒ４００．２２１０．１９８０．１７５０．１６４０．１５３２．４㊀ＺＩＦ⁃８质量分数对除臭纤维除氨性能的影响在原料针叶木纤维和竹炭纤维质量比为７０ʒ３０的基础上，研究ＺＩＦ⁃８质量分数对除臭纤维的影响㊂为确定最佳ＺＩＦ⁃８质量分数，在６个不同质量分数的ＺＩＦ⁃８（０％，１％，３％，５％，７％和９％）中选取６组代表性数据进行分析处理，不同ＺＩＦ⁃８质量分数对除臭纤维除氨性能影响如表３所示㊂ＺＩＦ⁃８的加入大大提升纤维除氨性能，且随ＺＩＦ⁃８质量分数增加，除臭纤维７２ｈ内氨气吸附量迅速上升，当ＺＩＦ⁃８质量分数超过５％时，除臭纤维氨气吸附量增加缓慢且趋于饱和㊂表３㊀不同ＺＩＦ⁃８质量分数除臭纤维的除氨性能Ｔａｂｌｅ３㊀ＥｆｆｅｃｔｓｏｆＺＩＦ⁃８ｉｎｂａｍｂｏｏ⁃ｗｏｏｄｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａＺＩＦ⁃８质量分数／％纤维原料绝干质量／ｇ试样绝干质量／ｇ初始氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ残留氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ吸附质量浓度／（ｍｇ㊃ｍ－３）０３．０７０３．０７００．３０５０．２１２０．０９３１３．０２０３．０２９０．３１５０．１５１０．１６４３３．０４７３．０８００．３２８０．１２９０．２０１５３．１５１３．２１２０．３２１０．０９１０．２３０７３．１２３３．２２３０．３１１０．０７００．２４１９３．０３１３．１６３０．３０２０．０６８０．２４５㊀㊀由除臭纤维试样和纤维原料的绝干质量可知，ＺＩＦ⁃８纳米粒子在除臭纤维含量大大低于加入量，成功负载在除臭纤维中的粒子才能有效提升纤维除臭性能㊂因此，对除臭纤维中ＺＩＦ⁃８留着率和纤维消臭率关系进行分析，结果如图４ａ所示㊂ＺＩＦ⁃８留着率和除臭纤维７２ｈ内消臭率变化趋势大致相同，随ＺＩＦ⁃８质量分数增加，除臭纤维中ＺＩＦ⁃８留着率增加，除臭纤维７２ｈ消臭率增加㊂当ＺＩＦ⁃８质量分数为７％时，ＺＩＦ⁃８留着率变化缓慢趋于稳定，除臭纤维的吸氨量也趋于饱和，此时除臭纤维的７２ｈ消臭率为７７．１７％㊂为更直观地了解ＺＩＦ⁃８加入对除臭纤维除臭效果的影响，对除臭纤维７２ｈ内氨气变化量进行监测（图４ｂ）㊂不同质量分数ＺＩＦ⁃８除臭纤维在吸９５林业工程学报第９卷附前几小时内，氨气浓度均直线下降，而后下降速度逐渐放缓达到吸附平衡㊂ＺＩＦ⁃８质量分数不同，除臭纤维对臭气吸附量达到饱和的时间不同，随ＺＩＦ⁃８快，达到吸附⁃解吸附平衡时间逐渐变短㊂当ＺＩＦ⁃８质量分数达７％时，此状态下除臭纤维除臭性能达到最大，除臭纤维的吸附稳定性高，再增加ＺＩＦ⁃８含量，对除臭纤维氨气除臭性能提升帮助甚微㊂㊀㊀ａ）不同ＺＩＦ⁃８质量分数对氨气消臭率的影响㊀㊀㊀㊀㊀㊀㊀ｂ）不同ＺＩＦ⁃８质量分数对氨气的吸附曲线图４㊀不同ＺＩＦ⁃８质量分数对氨气消臭率的影响及其对氨气的吸附曲线Ｆｉｇ．４㊀ＥｆｆｅｃｔｏｆａｍｏｕｎｔｏｆＺＩＦ⁃８ｉｎｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａａｎｄａｍｍｏｎｉａａｄｓｏｒｐｔｉｏｎｃｕｒｖｅｓ㊀㊀ＺＩＦ⁃８改性纤维材料显示出强大除氨能力，且对氨的吸附性能与ＺＩＦ⁃８留着率密切相关，但粒子在纤维表面的留着量也存在上限，即使继续加入纳米粒子也无法改变㊂综上考虑ＺＩＦ⁃８质量分数为纤维原料绝干质量７％，该质量分数所制除臭纤维性能优异，消臭率达到７７．１７％㊂２．５㊀ＣＮＦ质量分数对除臭纤维除氨性能和吸水性能的影响㊀㊀不同ＺＩＦ⁃８留着率除臭纤维的除臭性能不同，但上述研究中发现除臭纤维中ＺＩＦ⁃８留着率存在上限㊂针对这一现象，使用ＣＮＦ纤维增加除臭纤维中ＺＩＦ⁃８留着率和提升除臭纤维吸水性能，在ＺＩＦ⁃８粒子质量分数７％基础上加入ＣＮＦ㊂探究不同ＣＮＦ质量分数对除臭纤维除氨性能和吸水性能的变化㊂为确定除臭纤维最佳ＣＮＦ纤维质量分数，在５个不同ＣＮＦ质量分数（０％，３％，６％，９％和１２％）中取代表性数据进行分析处理，不同ＣＮＦ质量分数对除臭纤维除氨性能影响如表４所示㊂ＣＮＦ纤维加入提升了除臭纤维除氨性能，当ＣＮＦ质量分数超过３％时，除臭纤维除氨气性能提升微弱㊂然而，以上不同ＣＮＦ质量分数的除臭纤维除臭性能提升是否受ＺＩＦ⁃８留着率变化影响有待考证，因此对不同ＣＮＦ纤维质量分数除臭纤维中ＺＩＦ⁃８留着率和纤维消臭率关系进行分析，如图５ａ所示㊂结果发现，随ＣＮＦ质量分数增加，除臭纤维中ＺＩＦ⁃８留着率增加，除臭纤维７２ｈ消臭率先增加后下降趋于平稳㊂当ＣＮＦ质量分数为６％时，除臭纤维吸氨性能最佳，此时除臭纤维７２ｈ消臭率为８４．５６％㊂同时，对不同ＣＮＦ质量分数除臭纤维７２ｈ内氨气吸附量进行监测，如图５ｂ所示㊂结果表明，与ＣＮＦ质量分数０％的除臭纤维相比，加ＣＮＦ的除臭纤维氨气吸附速度和氨气吸附量均得到提升，不同ＣＮＦ质量分数除臭纤维的吸附能力随吸附时间变化大致相同㊂表４㊀不同ＣＮＦ质量分数除臭纤维的除氨性能Ｔａｂｌｅ４㊀ＥｆｆｅｃｔｏｆＣＮＦｉｎｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａＣＮＦ质量分数／％纤维原料绝干质量／ｇ试样绝干质量／ｇ初始氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ残留氨气质量浓度／（ｍｇ㊃ｍ－３）７２ｈ吸附质量浓度／（ｍｇ㊃ｍ－３）０３．１２３３．２２３０．３１１０．０７００．２４１３３．０７７３．２８７０．３１２０．０５１０．２６１６３．１５１３．４５４０．３１１０．０４８０．２６３９３．１２３３．５２３０．３２００．０５００．２７０１２３．１３１３．６２３０．３１２０．０４８０．２６４㊀㊀ＣＮＦ加入可有效填补原料竹炭纤维和针叶木纤维网络产生的大孔，提高ＺＩＦ⁃８的附着上限，改善纤维吸氨性能㊂但过多ＣＮＦ纤维的加入易堵塞ＺＩＦ⁃８纳米粒子孔隙，屏蔽部分纳米粒子，导致ＺＩＦ⁃８留着率增加，除氨性能不增反降的现象㊂综上所述，ＣＮＦ质量分数为６％时所制除臭纤维性能优０６㊀第２期施宇斐，等：ＺＩＦ⁃８／纳米纤维素对竹木复合纤维除臭性能的影响㊀㊀㊀㊀㊀㊀ｂ）不同ＣＮＦ质量分数对氨气的吸附曲线图５㊀不同ＣＮＦ质量分数除臭纤维对氨气消臭率的影响及其对氨气的吸附曲线Ｆｉｇ．５㊀ＥｆｆｅｃｔｏｆａｍｏｕｎｔｏｆＣＮＦｉｎｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｒｅｍｏｖａｌｏｆａｍｍｏｎｉａａｎｄａｍｍｏｎｉａａｄｓｏｒｐｔｉｏｎｃｕｒｖｅｓ异，消臭率达到８４．５６％㊂将该除臭纤维应用于卫生用品的吸收芯层中，同时需要良好的吸水性能，但由于竹炭纤维的固有缺点，如高挺度㊁竹炭纤维之间的相互作用弱等，竹木纤维除臭纤维的吸水性能有待提高㊂ＣＮＦ本身具有较大的比表面积和丰富的羟基，可增强除臭纤维的亲水性㊂研究不同ＣＮＦ质量分数对除臭纤维吸水性能的影响，结果如图６所示㊂ＣＮＦ有效提高除臭纤维的吸水性能，当ＣＮＦ质量分数为６％时，除臭纤维的吸水量从６．８ｇ／ｇ增加至８．４ｇ／ｇ，吸水图６㊀不同ＣＮＦ质量分数对除臭纤维吸水量的影响Ｆｉｇ．６㊀ＥｆｆｅｃｔｏｆａｍｏｕｎｔｏｆＣＮＦｉｎｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｏｎｗａｔｅｒａｂｓｏｒｐｔｉｏｎｃａｐａｃｉｔｙ性能优良㊂分析可知，ＣＮＦ与原料纤维通过氢键形成稳固结构，提供均匀小尺寸，有利于除臭纤维浸入水中时的毛细管效应，ＣＮＦ提高纤维吸水性能存在巨大的潜力㊂２．６㊀除臭纤维对硫化氢的消除效果在日常生活中，除臭纤维需要消除气体不仅有氨气，还有人体排泄中所释放硫化氢气体㊂按照国家标准ＧＢ／Ｔ３３６１０．２ ２０１７测定纤维硫化氢吸附能力㊂选取针叶木纤维和竹炭纤维原料质量比为７０ʒ３０，７％ＺＩＦ⁃８和６％ＣＮＦ的除臭纤维对硫化氢和氨气进行吸附试验，试验重复进行３次，每次试验除臭纤维试样均需重新制作㊂除臭纤维７２ｈ吸附硫化氢测试结果见表５，除臭纤维吸附硫化氢能力优异㊂在２４ ４８ｈ内，除臭纤维对硫化氢的吸附已达平衡；在４８ ７２ｈ内，硫化氢浓度未发生变化，吸附性能具有较好的稳定性㊂对上述除臭纤维吸附硫化氢测试，结果表明，Ａ１㊁Ａ２和Ａ３这３组消臭率分别为８２．９３％，８３．１１％和８２．９９％，试验重复性良好㊂纺织品对硫化氢气体的消臭率国家标准为ȡ７０％，本研究所制除臭纤维对硫化氢气体的消臭率达到并超过国家标准㊂表５㊀除臭纤维７２ｈ吸附硫化氢测试Ｔａｂｌｅ５㊀Ｔｈｅｒｅｍｏｖａｌｏｆｈｙｄｒｏｇｅｎｓｕｌｆｉｄｅｏｆｃｏｍｐｏｓｉｔｅｄｅｏｄｏｒｉｚｉｎｇｆｉｂｅｒｓｗｉｔｈｉｎ７２ｈ编号试样绝干质量／ｇ不同吸附时间后的残余硫化氢质量浓度／（ｍｇ㊃ｍ－３）０ｈ１ｈ２４ｈ４８ｈ７２ｈ７２ｈ硫化氢残留质量浓度／（ｍｇ㊃ｍ－３）７２ｈ吸附质量浓度／（ｍｇ㊃ｍ－３）７２ｈ消臭率／％Ａ１３．５０８０．０７５００．０３５２０．１７８００．０１２８０．０１２８０．０１２８０．０６２２８２．９３Ａ２３．５０５０．０７４００．０３７５０．１７２００．０１２５０．０１２５０．０１２５０．０６１５８３．１１Ａ３３．５０１０．０７７００．０３８４０．１７５００．０１３１０．０１３１０．０１３１０．０６３９８２．９９３㊀结㊀论笔者在原料针叶木纤维和竹炭纤维质量比为７０ʒ３０的基础上，以ＺＩＦ⁃８纳米粒子和纳米纤维素（ＣＮＦ）为除臭改性填料，通过复合加工工艺，成功制备了新型兼具除臭和吸水功能的竹木复合除臭纤维，主要结论如下：１）ＺＩＦ⁃８和ＣＮＦ作为除臭改性填料显著提高１６林业工程学报第９卷了竹炭／木浆复合纤维的除臭性能，当ＺＩＦ⁃８和ＣＮＦ的质量分数分别为７％和６％时，竹炭／木浆复合纤维的除臭性能最优，具有８４．５６％的氨气消臭率和８３．１１％的硫化氢消臭率㊂２）ＣＮＦ与原料纤维通过氢键形成的稳固结构，利于除臭纤维浸入水中时形成毛细管效应，从而显著提高了除臭纤维的吸水性能㊂参考文献（Ｒｅｆｅｒｅｎｃｅｓ）：［１］ＭＡＪＪ，ＺＨＡＮＧＮ，ＣＨＥＮＧＹ，ｅｔａｌ．Ｇｒｅｅｎｆａｂｒｉｃａｔｉｏｎｏｆｍｕｌ⁃ｔｉｆｕｎｃｔｉｏｎａｌｔｈｒｅｅｄｉｍｅｎｓｉｏｎａｌｓｕｐｅｒａｂｓｏｒｂｅｎｔｎｏｎｗｏｖｅｎｓｗｉｔｈｔｈｅｒｍｏｓ⁃ｂｏｎｄｉｎｇｆｉｂｅｒｓ［Ｊ］．ＡｄｖａｎｃｅｄＦｉｂｅｒＭａｔｅｒｉａｌｓ．２０２２，４（２）：２９３－３０４．ＤＯＩ：１０．１００７／ｓ４２７６５－０２１－００１０８－５．［２］东旭，于明娇，赵宏宇，等．竹炭纤维及其纺织品的开发现状和应用发展［Ｊ］．辽宁丝绸，２０２０（２）：４１－４２．ＤＯＩ：１０．３９６９／ｊ．ｉｓｓｎ．１６７１－３３８９．２０２０．０２．０１８．ＤＯＮＧＸ，ＹＵＭＪ，ＺＨＡＯＨＹ，ｅｔａｌ．Ｄｅｖｅｌｏｐｍｅｎｔｓｔａｔｕｓａｎｄａｐｐｌｉｃａｔｉｏｎｏｆｂａｍｂｏｏ⁃ｃａｒｂｏｎｆｉｂｅｒａｎｄｉｔｓｔｅｘｔｉｌｅｓ［Ｊ］．ＬｉａｏｎｉｎｇＴｕｓｓａｈＳｉｌｋ，２０２０（２）：４１－４２．［３］邓燕群，金颖，于丹妮，等．负离子纤维／竹炭纤维混纺纱及面料开发［Ｊ］．纺织科学与工程学报，２０２２，３９（１）：１３－１６，２１．ＤＯＩ：１０．３９６９／ｊ．ｉｓｓｎ．２０９６－５１８４．２０２２．０１．００３．ＤＥＮＧＹＱ，ＪＩＮＹ，ＹＵＤＮ，ｅｔａｌ．Ｄｅｖｅｌｏｐｍｅｎｔｏｆａｎｉｏｎｉｃｆｉ⁃ｂｅｒ／ｂａｍｂｏｏ⁃ｃａｒｂｏｎｆｉｂｅｒｂｌｅｎｄｅｄｙａｒｎａｎｄｆａｂｒｉｃｓ［Ｊ］．ＪｏｕｒｎａｌｏｆＴｅｘｔｉｌｅＳｃｉｅｎｃｅ＆Ｅｎｇｉｎｅｅｒｉｎｇ，２０２２，３９（１）：１３－１６，２１．［４］ＺＯＵＫＹ，ＬＩＺＸ．ＣｏｎｔｒｏｌｌａｂｌｅｓｙｎｔｈｅｓｅｓｏｆＭＯＦ⁃ｄｅｒｉｖｅｄｍａｔｅｒｉ⁃ａｌｓ［Ｊ］．Ｃｈｅｍｉｓｔｒｙ，２０１８，２４（２５）：６５０６－６５１８．ＤＯＩ：１０．１００２／ｃｈｅｍ．２０１７０５４１５．［５］ＺＨＡＮＧＨＸ，ＧＥＣＨ，ＺＨＵＣＹ，ｅｔａｌ．Ｄｅｏｄｏｒｉｚｉｎｇｐｒｏｐｅｒｔｉｅｓｏｆｐｈｏｔｏｃａｔａｌｙｓｔｔｅｘｔｉｌｅｓａｎｄｉｔｓｅｆｆｅｃｔａｎａｌｙｓｉｓ［Ｃ］．Ｊａｐａｎ：Ｉｎｔｅｒ⁃ｎａｔｉｏｎａｌＣｏｎｆｅｒｅｎｃｅｏｎＳｏｌｉｄＳｔａｔｅＤｅｖｉｃｅｓａｎｄＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅ，２０１２，２５：２４０－２４４．ＤＯＩ：１０．１０１６／ｊ．ｐｈｐｒｏ．２０１２．０３．０７８．［６］冯小倩，徐晴，张立慧，等．金属有机框架材料固定化酶的研究进展［Ｊ］．生物加工过程，２０２２，２０（５）：４９０－４９９．ＤＯＩ：１０．３９６９／ｊ．ｉｓｓｎ．１６７２－３６７８．２０２２．０５．００３．ＦＥＮＧＸＱ，ＸＵＱ，ＺＨＡＮＧＬＨ，ｅｔａｌ．Ｐｒｏｇｒｅｓｓｉｎｅｎｚｙｍｅｉｍ⁃ｍｏｂｉｌｉｚａｔｉｏｎｗｉｔｈｍｅｔａｌ⁃ｏｒｇａｎｉｃｆｒａｍｅｗｏｒｋｓ［Ｊ］．ＣｈｉｎｅｓｅＪｏｕｒｎａｌｏｆＢｉｏｐｒｏｃｅｓｓＥｎｇｉｎｅｅｒｉｎｇ，２０２２，２０（５）：４９０－４９９．［７］ＷＡＮＧＹ，ＣＵＩＲＱ，ＪＩＡＮＧＨＲ，ｅｔａｌ．Ｒｅｍｏｖａｌｏｆｈｙｄｒｏｇｅｎｓｕｌｆｉｄｅａｎｄａｍｍｏｎｉａｕｓｉｎｇａｂｉｏｔｒｉｃｋｌｉｎｇｆｉｌｔｅｒｐａｃｋｅｄｗｉｔｈｍｏｄｉ⁃ｆｉｅｄｃｏｍｐｏｓｉｔｅｆｉｌｌｅｒ［Ｊ］．Ｐｒｏｃｅｓｓｅｓ，２０２２，１０（１０）：２０１６．ＤＯＩ：１０．３３９０／ｐｒ１０１０２０１６．［８］ＬＥＥＪＨ，ＫＩＭＤ，ＳＨＩＮＨ，ｅｔａｌ．ＺｅｏｌｉｔｉｃｉｍｉｄａｚｏｌａｔｅｆｒａｍｅｗｏｒｋＺＩＦ⁃８ｆｉｌｍｓｂｙＺｎＯｔｏＺＩＦ⁃８ｃｏｎｖｅｒｓｉｏｎａｎｄｔｈｅｉｒｕｓａｇｅａｓｓｅｅｄｌａｙｅｒｓｆｏｒｐｒｏｐｙｌｅｎｅ⁃ｓｅｌｅｃｔｉｖｅＺＩＦ⁃８ｍｅｍｂｒａｎｅｓ［Ｊ］．ＪｏｕｒｎａｌｏｆＩｎ⁃ｄｕｓｔｒｉａｌ＆ＥｎｇｉｎｅｅｒｉｎｇＣｈｅｍｉｓｔｒｙ，２０１９，７２：３７４－３７９．ＤＯＩ：１０．１０１６／ｊ．ｊｉｅｃ．２０１８．１２．０３９．［９］ＭＡＹＮ，ＳＵＮＹＸ，ＹＩＮＪ，ｅｔａｌ．ＡＭＯＦｍｅｍｂｒａｎｅｗｉｔｈｕｌｔｒａ⁃ｔｈｉｎＺＩＦ⁃８ｌａｙｅｒｂｏｎｄｅｄｏｎＺＩＦ⁃８ｉｎｓｉｔｕｅｍｂｅｄｄｅｄＰＳｆｓｕｂｓｔｒａｔｅ［Ｊ］．ＪｏｕｒｎａｌｏｆｔｈｅＴａｉｗａｎＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＥｎｇｉｎｅｅｒｓ，２０１９，１０４（９４）：２７３－２８３．ＤＯＩ：１０．１０１６／ｊ．ｊｔｉｃｅ．２０１９．０８．０１２．［１０］ＺＨＡＮＧＨＦ，ＺＨＡＯＭ，ＬＩＮＪ．ＳｔａｂｉｌｉｔｙｏｆＺＩＦ⁃８ｉｎｗａｔｅｒｕｎｄｅｒａｍｂｉｅｎｔｃｏｎｄｉｔｉｏｎｓ［Ｊ］．ＭｉｃｒｏｐｏｒｏｕｓａｎｄＭｅｓｏｐｏｒｏｕｓＭａｔｅｒｉａｌｓ，２０１８，２７９：２０１－２１０．ＤＯＩ：１０．１０１６／ｊ．ｍｉｃｒｏｍｅｓｏ．２０１８．１２．０３５．［１１］郭亚，孙晓婷．竹炭纤维的性能及应用［Ｊ］．成都纺织高等专科学校学报，２０１６，３３（３）：２１９－２２１．ＧＵＯＹ，ＳＵＮＸＴ．Ｐｒｏｐｅｒｔｉｅｓａｎｄａｐｐｌｉｃａｔｉｏｎｓｏｆｂａｍｂｏｏ⁃ｃａｒｂｏｎｆｉｂｅｒ［Ｊ］．ＪｏｕｒｎａｌｏｆＣｈｅｎｇｄｕＴｅｘｔｉｌｅＣｏｌｌｅｇｅ，２０１６，３３（３）：２１９－２２１．［１２］ＧＵＡＮＭ，ＡＮＸＹ，ＬＩＵＨＢ．Ｃｅｌｌｕｌｏｓｅｎａｎｏｆｉｂｅｒ（ＣＮＦ）ａｓａｖｅｒｓａｔｉｌｅｆｉｌｌｅｒｆｏｒｔｈｅｐｒｅｐａｒａｔｉｏｎｏｆｂａｍｂｏｏｐｕｌｐｂａｓｅｄｔｉｓｓｕｅｐａ⁃ｐｅｒｈａｎｄｓｈｅｅｔｓ［Ｊ］．Ｃｅｌｌｕｌｏｓｅ，２０１９，２６（４）：２６１３－２６２４．ＤＯＩ：１０．１００７／ｓ１０５７０－０１８－２２１２－６．［１３］申烨华，张晶晶，赵美玲，等．一种基于双配体制备壳层厚度可控的ＺｎＯ＠ＺＩＦ⁃８传感材料的方法［Ｐ］．中国：１４９３１９０８Ａ，２０２２－０５－３１．ＳＨＥＮＹＨ，ＺＨＡＮＧＪＪ，ＺＨＡＯＭＬ，ｅｔａｌ．ＡｃｏｎｔｒｏｌｌａｂｌｅｓｈｅｌｌｔｈｉｃｋｎｅｓｓｐｒｅｐａｒａｔｉｏｎｍｅｔｈｏｄｂａｓｅｄｏｎｄｕａｌｃｏｏｒｄｉｎａｔｉｏｎｓｙｓｔｅｍＺｎＯ＠ＺＩＦ⁃８Ｍｅｔｈｏｄｏｆｓｅｎｓｉｎｇｍａｔｅｒｉａｌｓ［Ｐ］．Ｃｈｉｎａ：ＣＮ１４９３１９０８Ａ，２０２２－０５－３１．［１４］杨淑蕙．植物纤维化学［Ｍ］．北京：中国轻工业出版社，２００１：６９－７０．ＹＡＮＧＳＨ．Ｐｌａｎｔｆｉｂｅｒｃｈｅｍｉｓｔｒｙ［Ｍ］．Ｂｅｉｊｉｎｇ：ＣｈｉｎａＬｉｇｈｔＩｎ⁃ｄｕｓｔｒｙＰｒｅｓｓ，２００１：６９－７０．［１５］ＷＡＮＧＪ，ＴＡＮＧＢ，ＢＡＩＷ，ｅｔａｌ．Ｄｅｏｄｏｒｉｚｉｎｇｆｏｒｆｉｂｅｒａｎｄｆａｂ⁃ｒｉｃ：ａｄｓｏｒｐｔｉｏｎ，ｃａｔａｌｙｓｉｓ，ｓｏｕｒｃｅｃｏｎｔｒｏｌａｎｄｍａｓｋｉｎｇ［Ｊ］．Ａｄ⁃ｖａｎｃｅｓｉｎＣｏｌｌｏｉｄａｎｄＩｎｔｅｒｆａｃｅＳｃｉｅｎｃｅ，２０２０，２８３：１０２２４３．ＤＯＩ：１０．１０１６／ｊ．ｃｉｓ．２０２０．１０２２４３．（责任编辑㊀李琦）２６。
温度对体内药物代谢的影响研究随着社会的发展和医学科技的进步，药物在治疗疾病中起到了至关重要的作用。
然而，我们常常忽视了一个重要的因素——温度。
事实上，温度不仅会影响环境中药物的稳定性和活性，还可能对人体内药物代谢产生重要影响。
本文将探讨温度对体内药物代谢的影响，并从分子水平、酶活性以及整体生理效应三个方面进行阐述。
一、温度对体内药物代谢的分子机制温度是影响生命活动最为基本的环境因素之一。
在人体内，温度可以调节酶活性和化学反应速率，从而影响药物代谢过程。
具体而言，在适宜的温度下，酶与底物结合更加紧密，反应速率增加；相反，在低温下，酶-底物互作会减弱或中断，导致代谢过程减慢甚至停止。
此外，在高温条件下，蛋白质结构发生变化，并且空间构象发生改变，这也会影响酶活性。
特别是对于一些热敏感的酶，高温可能导致其失活甚至变性，从而使得药物代谢受阻。
二、温度对体内药物代谢中的酶活性调节在体内，药物代谢主要依靠酶的催化作用完成。
温度直接影响着酶催化反应的速率和效果。
首先，温度可以通过影响蛋白质结构来调节酶的催化活性。
由于高温能够使蛋白质发生解离和聚合作用，降低分子间能量并增加反应概率，从而提高酶反应速率。
但是，在过高或过低的温度条件下，蛋白质可能会发生变性，并且失去原有功能。
其次，温度还可以通过改变底物与酶之间的互作力强弱来调节代谢反应速率。
在适宜的温度下，底物分子能够更容易与酶结合形成复合物，加速酶催化反应；而在非理想温度下，则出现与之相反的结果。
此外，在某些情况下，温度还可以影响酶的合成和降解过程，从而间接影响药物代谢。
例如，温度高会促进特定酶的合成，增加其催化作用的数量和效果。
三、温度对体内整体药物代谢的生理效应除了对分子水平和酶活性的影响外，温度还会对整体药物代谢过程产生生理效应。
首先，温度可以改变血液循环情况。
高温会导致末梢血管扩张，血流速度加快，从而使药物更快地输送到目标组织或器官中。
相反，在低温下，血液循环减慢，药物运输速度也会相应减缓。
