锆簇金属有机骨架材料(Zr-MOFs)的合成总结

序号

配体

条件

结构 来源

1

(200 mg), H3TATB (60 mg) and trifluoroacetic

acid in 12 mL of DEF were ultrasonically dissolved

in a Pyrex vial. The mixture was heated at 120 ºC

in an oven for 12 h. After cooling down to room

temperature, white powder crystalline

precipitate was harvested by filtration ·

2

All samples were synthesized via a reflux

method involving the reaction of

2-sulfoterephthalic acid with ZrClin water

under relatively concentrated conditions. For

the sample with no additives during synthesis

(1), monosodium 2-sulfoterephthalic acid (5 g,

mmol) was dissolved in minimal water, and then

passed through DOWEX 50WX8 proton exchange

resin to obtain 2-sulfoterephthalic acid. The

water was then removed by rotary evaporation, (

then 40 mL of fresh ultrapure water was added

to

dissolve the solid. Separately, ZrCl g,

mmol) was dissolved in 15 mL of ultrapure water

(caution, highly exothermic), then the two

solutions were mixed to make a clear, slightly

pink solution with pH < 1. The solution was then

heated to reflux, and after ~3 minutes a white

precipitate formed. Reflux was continued for 16

hours, then the solution was cooled and the

solid was recovered by centrifugation. The

solid was then washed 2x with ultrapure water,

then refluxed for another 16 hours in ultrapure

water to purify.

3

Synthesis of 14 nm UiO-66-N3

(Zr6O4OH4(C8H3O4-N3)6

2-Azido-1,4-benzenedicarboxylic acid (50 mg,

mmol) was dissolved in 1 mL

of N,N Dimethylformamide (DMF). In a separate

vial, zirconyl chloride octahydrate (21 纳米 级别

'

mg, mmol) was dissolved in 3 mL of DMF. The two

solutions were mixed together

in a 10 mL scintillation vial, and acetic acid (300

µl) was added to the reaction mixture.

The solution was heated at 90 ˚C for 18 h to yield

UiO-66-N3 (Zr6O4OH4(C8H3O4-N3)6.

MOF nanoparticles were purified by centrifugation

(15000 rpm, 90 min) followed by

solvent exchange (3 x DMF and 3 x NANOpure H2O)

over a 48 h period. MOF

nanoparticles were suspended in H2O for

characterization and functionalization with

~

4

DUT-67. ZrCl/HfCl(230 mg/320 mg, 1 mmol)

was dissolved in the mixture of DMF mL) and NMP mL) by

sonication for 10 min. 2,5-Thiophenedicarboxylic acid

(Htdc) (110 mg, mmol) was added to resulting solution and

sonicated additional 5 min. After that acetic acid (7 mL, *

117 mmol) was added to the solution and sonicated for 10 min. The resulting mixture was distributed to 10 Pyrex

tubes, which were subsequently tempered at 120 °C for 48

h. The resulted powder was separated by centrifugation and

washed several times with DMF until supernatant solution

became colorless. The powder was filtered and dried under

argon atmosphere

for half an hour. Yield: 224 mg %) for DUT-67(Zr) and 259

mg

%) for DUT-67(Hf).

The single crystals of DUT-67 were obtained using the same

procedure, but 10 mL of acetic acid instead of 7 mL were

added.

5 ZrCl/HfCl(230 mg/320 mg, 1 mmol)

was dissolved in DMF (25 mL) by sonication for 10 min. Htdc

(258 mg, mmol) was added to resulting solution, and the

mixture was sonicated additional 5 min. After that acetic

acid (11 mL, 183 mmol) was added and the mixture was

sonicated for further 10 min. The reaction mixture was .

distributed to 12 Pyrex tubes, which were subsequently

tempered at 120 °C for 72 h. The washing and drying

procedure was the same as applied to DUT-67. Yield: 384

mg %) for DUT-67(Zr) and 453 mg %) for DUT-67(Hf). The

single

crystals of DUT-68(Zr) were obtained using the same

synthetic

protocol, but utilizing larger amount of modulator.

}

A solutionofHeddb (65mg,,ZrCl(60 mg, ,(HOAc)in16mLof

N,N-dimethyl-

formamide(DMF)wassealedina20mLglassvialandheatedat 120 1C

washedwithDMFandacetone,andthendriedinair(yield72mg).

ZrCl(24 mg) was dissolved in 8 mL of

N,N-dimethylformamide (DMF) in a 25 mL pyrex vial,

to which benzoic acid was added. The mixture was

heated in 85 ºC oven for 1 hours and cooled

to the room temperature. Then, HTBPP (20 mg) was

added to the above solution, which was

{

sonicated for a while. The resulting mixture was

heated in 120 ºC oven for 96 hours to yield about

14 mg of dark red crystals (yield: % based on

HTBPP). The crystals obtained were filtered

and washed with DMF. Elemental analyses calcd (%) Chem. Sci., 2015, 6,

3466–3470 | 3467