共价有机框架材料在光催化领域中的应用

doi:10.7503/cjcu20200409

摘要/Abstract

摘要：

共价有机框架(COFs)材料是有机构筑基元通过共价键连接而形成的晶态有机多孔材料. COFs具有孔道结构规整、及比表面积高等特点, 被广泛地应用于气体储存与分离、催化、传感、储能及光电转化等领域. 将具有可调吸光能力的有机构筑基元引入到COFs中, 可使其展现出强大的光催化潜力. 近年来, COFs在光催化领域中发展迅猛. 本文总结了COFs在光催化产氢、光催化二氧化碳还原、光催化有机反应以及光催化污染物降解等方面的研究进展, 并展望了其在光催化领域的应用前景.

关键词: 共价有机框架材料, 光催化, 光解水产氢, 二氧化碳还原, 有机反应, 污染物降解

Abstract:

Covalent organic frameworks(COFs) are crystalline porous organic materials, which are built from organic building blocks through covalent bonds. COFs have the characteristics of well-defined pore structure and high specific surface area. COFs have been widely used in gas storage and separation, catalysis, sensing, energy storage, photoelectric conversion and many other fields. Introducing organic building blocks with adjustable light absorption into COFs provide COF with a great potential in photocatalysis. In recent years, COFs have developed rapidly in the field of photocatalysis. This paper summarizes the recent progress of COFs in the fields of photocatalytic hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic organic reactions, and photocatalytic degradation of pollutants, and looks forward to its further prospects in the field of photocatalysis.

Key words: Covalent organic frameworks, Photocatalysis, Photocatalytic hydrogen evolution, Carbon dioxide reduction, Organic reaction, Degradation of pollutants

中图分类号:

O643

TrendMD:

李丽, 李鹏飞, 王博. 共价有机框架材料在光催化领域中的应用. 高等学校化学学报, 2020, 41(9): 1917.

LI Li, LI Pengfei, WANG Bo. Photocatalytic Application of Covalent Organic Frameworks. Chem. J. Chinese Universities, 2020, 41(9): 1917.

图/表 14

参考文献 80

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COFs	co?Catalyst	Sacrificial donor	Solvent	Light irradiation	HER/ (μmol·h^-1·g^-1)	AQE	Ref.
TFPT?COF	Pt	10%(volume raction) TEOA	Water	>420 nm	1970	2.2%—3.9% (500 nm)	[33]
N₀?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	23	0.001% (450 nm)	[34]
N₁?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	90	0.077% (450 nm)	[34]
N₂?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	438	0.19%(450 nm)	[34]
N₃?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	1703	0.44%(450 nm)	[34]
PTP?COF	Pt	1%(volume raction) TEOA	PBS solution	AM 1.5	83.83	―	[35]
A?TEBPY?COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	98	―	[36]
A?TENPY?COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	22	―	[36]
A?TEPPY? COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	6	―	[36]
TP?EDDA?COF	Pt	10%(volume raction) TEOA	Water	>395 nm	30	―	[37]
TP?BDDA?COF	Pt	10%(volume raction) TEOA	Water	>395 nm	324	1.8%(520 nm)	[37]
S?COF	Pt	0.1 mol/L Ascorbic acid	Water	>420 nm	4440	―	[38]
FS?COF	Pt	0.1 mol/L Ascorbic acid	Water	>420 nm	10100	―	[38]
FS?COF?WS5F	Pt/WS5F	0.1 mol/L Ascorbic acid	Water	>420 nm	16300	2.2%(600 nm)	[38]
TpPa?COF	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	1560	―	[39]
TpPa?COF?(CH₃)₂	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	8330	―	[39]
TpPa?COF?NO₂	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	220	―	[39]
sp²c?COF_ERDN	Pt	10%(volume fraction) TEOA	Water	>420 nm	2120	0.48%(495 nm)	[40]
CN?COF	Pt	10%(volume fraction) TEOA	Water	>420 nm	10100	20.7%(425 nm)	[41]
NH₂?Uio?66/TpPa?1?COF	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	23410	―	[42]
CdS?COF(90:10)	Pt	10%(volume fraction) Lactic acid	Water	>420 nm	3678	4.2%(420 nm)	[43]
Pt?PVP?TP?COF	Pt?PVP	0.054 mol/L Ascorbic acid	Water	>420 nm	8420	0.4%(475 nm)	[44]
N₂?COF	Co	1%(volume fraction) TEOA	Water/ACN (volume ratio1:4)	AM 1.5	782	0.16%(400 nm)	[45]
TpDTz?COF	Ni	10%(volume fraction) TEOA	Water	AM 1.5	941	―	[46]

COFs	co?Catalyst	Sacrificial donor	Solvent	Light irradiation	HER/ (μmol·h^-1·g^-1)	AQE	Ref.
TFPT?COF	Pt	10%(volume raction) TEOA	Water	>420 nm	1970	2.2%—3.9% (500 nm)	[33]
N₀?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	23	0.001% (450 nm)	[34]
N₁?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	90	0.077% (450 nm)	[34]
N₂?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	438	0.19%(450 nm)	[34]
N₃?COF	Pt	1%(volume raction) TEOA	PBS solution	>420 nm	1703	0.44%(450 nm)	[34]
PTP?COF	Pt	1%(volume raction) TEOA	PBS solution	AM 1.5	83.83	―	[35]
A?TEBPY?COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	98	―	[36]
A?TENPY?COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	22	―	[36]
A?TEPPY? COF	Pt	10%(volume raction) TEOA	Water	AM 1.5	6	―	[36]
TP?EDDA?COF	Pt	10%(volume raction) TEOA	Water	>395 nm	30	―	[37]
TP?BDDA?COF	Pt	10%(volume raction) TEOA	Water	>395 nm	324	1.8%(520 nm)	[37]
S?COF	Pt	0.1 mol/L Ascorbic acid	Water	>420 nm	4440	―	[38]
FS?COF	Pt	0.1 mol/L Ascorbic acid	Water	>420 nm	10100	―	[38]
FS?COF?WS5F	Pt/WS5F	0.1 mol/L Ascorbic acid	Water	>420 nm	16300	2.2%(600 nm)	[38]
TpPa?COF	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	1560	―	[39]
TpPa?COF?(CH₃)₂	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	8330	―	[39]
TpPa?COF?NO₂	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	220	―	[39]
sp²c?COF_ERDN	Pt	10%(volume fraction) TEOA	Water	>420 nm	2120	0.48%(495 nm)	[40]
CN?COF	Pt	10%(volume fraction) TEOA	Water	>420 nm	10100	20.7%(425 nm)	[41]
NH₂?Uio?66/TpPa?1?COF	Pt	100 mg Sodium ascorbate	PBS solution	>420 nm	23410	―	[42]
CdS?COF(90:10)	Pt	10%(volume fraction) Lactic acid	Water	>420 nm	3678	4.2%(420 nm)	[43]
Pt?PVP?TP?COF	Pt?PVP	0.054 mol/L Ascorbic acid	Water	>420 nm	8420	0.4%(475 nm)	[44]
N₂?COF	Co	1%(volume fraction) TEOA	Water/ACN (volume ratio1:4)	AM 1.5	782	0.16%(400 nm)	[45]
TpDTz?COF	Ni	10%(volume fraction) TEOA	Water	AM 1.5	941	―	[46]

COFs	Co?catalyst	Condition	Light irradiation/nm	Product (selectivity)	Activity/ (μmol·h^-1·g^-1)	TON/TOF^*	Ref.
Re?CTF?py	Re	Solid?gas system	200—1100	CO	353.05	4.8/—	[50]
Re?COF	Re	TEOA/MeCN(volume ratio 0.2:3)	>420	CO(98%)	750	48/—	[51]
Ni?TpBpy COF	Ni/ Ru(bpy)₃Cl₂	TEOA/MeCN/H₂O (volume ratio 1:3:1)	>420	CO(96%)	811.4	13.62/—	[52]
DQTP?COF?Co	Co/Ru(bpy)₃Cl₂	TEOA/MeCN(volume ratio 1:4)	>420	CO	1020	—/0.55 h^-1	[53]
DQTP?COF?Zn	Zn/Ru(bpy)₃Cl₂	TEOA/MeCN(volume ratio 1:4)	>420	HCOOH(90%)	152.5	—/0.08 h^-1	[53]
TTCOF?Zn	—	H₂O	420—800	CO(100%)	0.2055	—/—	[54]
COF?367?Co NSs	Ru(bpy)₃Cl₂	Ascorbic acid/0.1 mol/L KHCO₃	>420	CO(78%)	10162	—/—	[55]
ACOF?1	—	H₂O	420—800	CH₃OH	0.36	—/—	[56]
N₃?COF	—	H₂O	420—800	CH₃OH	0.57	—/—	[56]
CT?COF	—	H₂O	>420	CO(98%)	102.7	—/—	[57]
COF?318/TiO₂	—	Solid?gas system	380—800	CO	69.67	—/—	[58]

COFs	Co?catalyst	Condition	Light irradiation/nm	Product (selectivity)	Activity/ (μmol·h^-1·g^-1)	TON/TOF^*	Ref.
Re?CTF?py	Re	Solid?gas system	200—1100	CO	353.05	4.8/—	[50]
Re?COF	Re	TEOA/MeCN(volume ratio 0.2:3)	>420	CO(98%)	750	48/—	[51]
Ni?TpBpy COF	Ni/ Ru(bpy)₃Cl₂	TEOA/MeCN/H₂O (volume ratio 1:3:1)	>420	CO(96%)	811.4	13.62/—	[52]
DQTP?COF?Co	Co/Ru(bpy)₃Cl₂	TEOA/MeCN(volume ratio 1:4)	>420	CO	1020	—/0.55 h^-1	[53]
DQTP?COF?Zn	Zn/Ru(bpy)₃Cl₂	TEOA/MeCN(volume ratio 1:4)	>420	HCOOH(90%)	152.5	—/0.08 h^-1	[53]
TTCOF?Zn	—	H₂O	420—800	CO(100%)	0.2055	—/—	[54]
COF?367?Co NSs	Ru(bpy)₃Cl₂	Ascorbic acid/0.1 mol/L KHCO₃	>420	CO(78%)	10162	—/—	[55]
ACOF?1	—	H₂O	420—800	CH₃OH	0.36	—/—	[56]
N₃?COF	—	H₂O	420—800	CH₃OH	0.57	—/—	[56]
CT?COF	—	H₂O	>420	CO(98%)	102.7	—/—	[57]
COF?318/TiO₂	—	Solid?gas system	380—800	CO	69.67	—/—	[58]

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