锆簇金属有机骨架材料(Zr-MOFs)的合成总结

2021年2月27日发(作者：vd)

序

号

1

配体

条件

ZrOCl2.8H2O

(200

mg),

H3TATB

(60

mg)

and

0.6mL

trifluoroacetic

acid

in

12

mL

of

DEF

were

ultrasonically

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

?C

in

an

oven

for

12

h.

After

cooling

down

to

room

temperature,

white

powder

crystalline

precipitate

was

harvested by filtration

结构

PCN-777

来源

Angew.

Chem.

Int.

Ed.

2014,

53, 1

–

7

2

All

samples

were

synthesized

via

a

reflux

method

involving

the

reaction

of

2-sulfoterephthalic

acid

with

ZrCl

4

in

water

under

relatively

concentrated

conditions.

For

the

sample

with

no

additives

during

synthesis (

1

), monosodium 2-sulfoterephthalic acid (5

g,

18.6

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

4

(2.5 g, 10.7 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,

DOI: 10.1021/jacs.5b07267

J.

Am.

Chem.

Soc.

XXXX,

XXX,

XXX

?

< br>XXX

3

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.

Synthesis of 14 nm UiO-66-N3 (Zr6O4OH4(C8H3O4-N3)6

纳米

级别

2-Azido-1,4-benzenedicarboxylic acid (50 mg, 0.24 mmol)

was dissolved in 1 mL

of

N,N

Dimethylformamide

(DMF).

In

a

separate

vial,

zirconyl chloride octahydrate (21

mg, 0.066 mmol) was dissolved in 3 mL of DMF. The two

solutions were mixed together

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

/10.1021/ja503215w | J.

Am. Chem. Soc. 2014, 136, 7261

?

7264

4

DUT-67.

ZrCl

4

/HfCl

4

(230 mg/320 mg, 1 mmol)

was dissolved in the mixture of DMF (12.5 mL) and NMP (12.5

mL) by sonication for 10 min. 2,5-Thiophenedicarboxylic acid

/10.1021/cg301691d

|

Cryst.

Growth

Des.

2013,

13,

1231

?

1237

(H

2

tdc) (110 mg, 0.67 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

fi

ltered and dried under argon atmosphere

for half an hour. Yield: 224 mg (71.5%) for DUT-67(Zr) and 259

mg

(63.9%) 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

4

/HfCl

4

(230 mg/320 mg, 1 mmol)

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

2

tdc

(258 mg, 1.5 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 (53.9%) for DUT-67(Zr) and 453 mg (52.3%) 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

solutionofH

2

eddb

(65mg,0.24mmol),ZrCl

4

(60

mg,

Journalof SolidStateChemistry223(20

15)104

< br>–

108

0.25mmol),2.5mLofacet icacid(HOAc)in16mLof

formamide(DMF)wass ealedina20mLglassvialandheatedat

ultingcolorlesscrystalswerecollectedand

washedwithDMFandacetone,andthendriedina ir(yield72mg).

N

,

N

-dimethyl-

120

1

C

ZrCl

4

(24 mg) was dissolved in 8 mL of

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

to which 1.0g benzoic acid was added. The mixture

was heated in 85 ?

C oven for 1 hours and cooled

to the room temperature. Then, H

6

TBPP (20 mg)

was added to the above solution, which was

sonicated for a while. The resulting mixture was

heated in 120 ?

C oven for 96 hours to yield about

14 mg of dark red crystals (yield: 38.89% based on

Chem.

Sci.,

2015,

6,

3466

–

3470 |

3467

H

6

TBPP). The crystals obtained were filtered

and washed with DMF. Elemental analyses calcd

(%) for

FJI-H6

(After activation and absorbed

small amount of water, the crystal has a formula of

[Zr

6

O

4

(OH)

4

(H

2

TBPP)

3

]

n

·

~20nH

< p>
2

O):

UiO-66a

0.24 g ZrOCl

2

*8H< /p>

2

O was dissolved in 20 ml DMF/ 1.6

ml HAc under 5 min sonication. Terephthalic acid

(0.136 g, 0.82 mmol, 1.1 eq) was added and the

mixture was sonicated for 5 min more and placed

into

120C preheated oven for 1 day. Solution was

decanted/centrifuged, precipitate was washed DMF

4

times and acetone 4 times over 12 hours. The

material was evacuated 12 h at RT followed by 12 h

at

120C (ramp 1C/min).

UiO-66b

0.24 g ZrOCl

2

*8H

2

< p>
O was dissolved in 32 ml DMF/ 3 g

benzoic acid under 5 min sonication. Terephthalic

acid (0.136 g, 0.82 mmol, 1.1 eq) was added and the

mixture was sonicated for 5 min more, distributed

to 4 vials and placed into 120C preheated oven for 1

day. Precipitate was filtered, washed DMF 4 times

and acetone 4 times over 12 hours. The material

was evacuated 12 h at RT followed by 12 h at 120C

(ramp 1C/min). Yield of the activated material

–

0.15 g.

UiO-66f

0.24 g ZrOCl

2

*8H< /p>

2

O was dissolved in 20 ml DMF/ 0.8

ml HCOOH under 5 min sonication. Terephthalic

acid (0.136 g, 0.82 mmol, 1.1 eq) was added and the

mixture was sonicated for 5 min more and placed

into 120C preheated oven for 1 day. Solution was

decanted/centrifuged, precipitate was washed DMF

4 times and acetone 4 times over 12 hours. The

material was evacuated 12 h at RT followed by 12 h

at

120C (ramp 1C/min). Yield of the activated material

–

0.12 g.

UiO-66h

0.528 g ZrOC l

2

*8H

2

O was dissolved in 40 ml DMF/

1.4 ml (10 eq) HCl under 5 min sonication.

Terephthalic acid (0.272 g, 1.64 mmol, 1 eq) was

added and the mixture was sonicated for 5 min

more

and placed into 120C preheated oven for 1 day.

Precipitate was filtered, washed DMF, < /p>

DMF/NEt

3

/H

< br>2

O

(20/0.4/0.4 ml), DMF 2 times and acetone 4 times

over 6 hours. The material was evacuated 4 h at

70C

followed with 15h at 150C (ramp 1C/min). Yield of

the activated material

–

0.36 g.

UiO-67a

0.24 g ZrOCl

< br>2

*8H

2

O was dissolved in 20 ml DMF/ 1.6

ml HAc under 5 min sonication. 4,4′

-

biphenyldicarboxylic acid (0.198 g, 0.82 mmol, 1.1

eq) was added and the mixture was sonicated for 5

min more and placed into 120C preheated oven for

1 day. Solution was decanted/centrifuged,

precipitate was washed DMF 4 times and acetone 4

times over 12 hours. The material was evacuated

19 h at RT followed by 6 h at 100C (ramp 1C/min).

Yield of the activated material

–

0.19 g.

S4