聚合氮化碳的制备、改性及光催化还原二氧化碳性能研究

doi:10.19964/j.issn.1006-4990.2021-0614

摘要/Abstract

摘要：

由过量二氧化碳（CO₂）排放导致的温室效应使得全球气候变暖问题日益紧迫,在“双碳”背景下,如何资源化利用CO₂尤为重要。光催化还原CO₂生成化学品和燃料是有望同时解决能源危机和环境问题的途径。非金属半导体聚合氮化碳（PCN）具有可见光响应、化学稳定性高、易于制备等优点,在光催化领域备受关注,但由传统热聚合方法得到的PCN存在比表面积小、电子-空穴对复合严重、对可见光吸收范围窄等不足之处。介绍了光还原CO₂的反应机理和PCN的结构,总结了PCN的制备方法以及提升其光还原CO₂性能的手段,包括形貌调控、异原子掺杂、缺陷工程和构建异质结等。最后,对目前PCN材料在CO₂光还原反应研究中存在的问题进行了分析,并对未来发展方向进行了展望。

关键词: 光催化, 二氧化碳还原, 聚合氮化碳, 改性

Abstract:

The greenhouse effect caused by excessive carbon dioxide（CO₂） emissions makes global warming increasingly ur-gent,under the background of “double carbon”,how to utilize CO₂ is of particular importance.The photocatalytic reduction of CO₂ to produce chemicals and fuels is a promising way to solve both energy crisis and environmental problems.Non-metal semiconductor,polymeric carbon nitride（PCN） has attracted much attention in the field of photocatalysis due to its visible light response,high chemical stability,easy preparation and low cost.However,PCN prepared by the traditional thermal polymerization method suffers from small specific surface area,serious electron-hole recombination as well as limited visible light response range.The reaction mechanism of CO₂ photoreduction and the structure of PCN were introduced.The preparation methods of PCN and the modification methods for improved photocatalytic performance were summarized,including morpho-logy control,heteroatom doping,defect engineering and heterojunction construction.Finally,the problems existing in the research of PCN materials in CO₂ photoreduction were analyzed,and the future development direction was prospected.

Key words: photocatalysis, carbon dioxide reduction, polymeric carbon nitride, modification

中图分类号:

O643.32

李佳慧,李克艳,宋春山,郭新闻. 聚合氮化碳的制备、改性及光催化还原二氧化碳性能研究[J]. 无机盐工业, 2021, 53(12): 21-28.

LI Jiahui,LI Keyan,SONG Chunshan,GUO Xinwen. Study on preparation,modification and carbon dioxide photocatalytic reduction performance of polymeric carbon nitride[J]. Inorganic Chemicals Industry, 2021, 53(12): 21-28.

图/表 7

表1

图1

图2

图3

图4

图5

图6

参考文献 66

[1]	SONG C F, LIU Q L, QI Y, et al. Absorption-microalgae hybrid CO₂ capture and biotransformation strategy-A review[J]. International Journal of Greenhouse Gas Control, 2019, 88:109-117.
[2]	ZARGARI N, JUNG E, LEE J H, et al. Carbon dioxide hydrogena-tion:Efficient catalysis by an NHC-amidate Pd(Ⅱ) complex[J]. Tetrahedron Letters, 2017, 58:3330-3332.
[3]	RASUL S, ANJUM D, JEDIDI A, et al. A highly selective copper-in-dium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO₂ to CO[J]. Angewandte Chemie:International Edition, 2015, 54:2146-2150.
[4]	ZHAI Q G, XIE S J, FAN W Q, et al. Photocatalytic conversion of carbon dioxide with water into methane:Platinum and copper(Ⅰ) oxi-de co-catalysts with a core-shell structure[J]. Angewandte Chemie:International Edition, 2013, 52:5776-5779.
[5]	DU C, WANG X J, CHEN W, et al. CO₂ transformation to multicar-bon products by photocatalysis and electrocatalysis[J]. Materials To-day Advances, 2020, 6.Doi: 10.1016/j.mtadv.2020.100071.
[6]	PENG W X, NGUYEN T, NGUYEN D, et al. A roadmap towards the development of superior photocatalysts for solar-driven CO₂-to-fu-els production[J]. Renewable & Sustainable Energy Reviews, 2021, 148.Doi: 10.1016/j.rser.2021.111298.
[7]	KARAMIAN E, SHARIFNIA S. On the general mechanism of pho-tocatalytic reduction of CO₂[J]. Journal of CO₂ Utilization, 2016, 16:194-203.
[8]	WANG R R, YANG P J, WANG S B, et al. Regulating morphological and electronic structures of polymeric carbon nitrides by successive copolymerization and stream reforming for photocatalytic CO₂ reduction[J]. Catalysis Science & Technology, 2021, 11:2570-2576.
[9]	BIE C B, ZHU B C, XU F Y, et al. In situ grown monolayer N-doped graphene on CdS hollow spheres with seamless contact for photoca-talytic CO₂ reduction[J]. Advanced Materials, 2019, 31.Doi: 10.1002/adma.201902868.
[10]	LU L, WANG S M, ZHOU C G, et al. Surface chemistry imposes selective reduction of CO₂ to CO over Ta₃N₅/LaTiO₂N photocataly-st[J]. Journal of Materials Chemistry A, 2018, 6:14838-14846.
[11]	XU J X, JI Q J, YAN X M, et al. Ni(acac)₂/Mo-MOF-derived difu-nctional MoNi@MoO₂ cocatalyst to enhance the photocatalytic H₂ evolution activity of g-C₃N₄[J]. Applied Catalysis B:Environmen-tal, 2020, 268.Doi: 10.1016/j.apcatb.2020.118739.
[12]	LI M L, ZHANG L X, FAN X Q, et al. Highly selective CO₂ photo-reduction to CO over g-C₃N₄/Bi₂WO₆ composites under visible light[J]. Journal of Materials Chemistry A, 2015, 3:5189-5196.
[13]	LI X, JIANG H P, MA C C, et al. Local surface plasma resonance effect enhanced Z-scheme ZnO/Au/g-C₃N₄ film photocatalyst for reduction of CO₂ to CO[J]. Applied Catalysis B:Environmental, 2021, 283.Doi: 10.1016/j.apcatb.2020.119638.
[14]	JI Y F, LUO Y. New mechanism for photocatalytic reduction of CO₂ on the anatase TiO₂(101) surface:The essential role of oxygen va-cancy[J]. Journal of the American Chemical Society, 2016, 138:15896-15902.
[15]	FU J W, JIANG K X, QIU X Q, et al. Product selectivity of photoca-talytic CO₂ reduction reactions[J]. Materials Today, 2020, 32:222-243.
[16]	JEONG S, KIM W D, LEE S, et al. Bi₂O₃ as a promoter for Cu/TiO₂ photocatalysts for the selective conversion of carbon dioxide into methane[J]. ChemCatChem, 2016, 8:1641-1645.
[17]	TERRANOVA U, VINES F, de LEEUW N H, et al. Mechanisms of carbon dioxide reduction on strontium titanate perovskites[J]. Journal of Materials Chemistry A, 2020, 8:9392-9398.
[18]	YU L, BA X, QIU M, et al. Visible-light driven CO₂ reduction co-upled with water oxidation on Cl-doped Cu₂O nanorods[J]. Nano Energy, 2019, 60:576-582.
[19]	PANG H, MENG X G, LI P, et al. Cation vacancy-initiated CO₂ photoreduction over ZnS for efficient formate production[J]. ACS Energy Letters, 2019, 4:1387-1393.
[20]	WANG Y L, TIAN Y, YAN L K, et al. DFT study on sulfur-doped g-C₃N₄ nanosheets as a photocatalyst for CO₂ reduction reaction[J]. The Journal of Physical Chemistry C, 2018, 122:7712-7719.
[21]	PARK H, OU H H, COLUSSI A J, et al. Artificial photosynjournal of C₁-C₃ hydrocarbons from water and CO₂ on titanate nanotubes decorated with nanoparticle elemental copper and CdS quantum- dots[J]. The Journal of Physical Chemistry A, 2015, 119:4658-4666.
[22]	ARORA A K, JASWAL V S, SINGH K, et al. Applications of metal/mixed metal oxides as photocatalyst:A review[J]. Oriental Journal of Chemistry, 2016, 32:2035-2042.
[23]	CUI Y J, DING Z X, FU X Z, et al. Construction of conjugated car-bon nitride nanoarchitectures in solution at low temperatures for photoredox catalysis[J]. Angewandte Chemie:International Edi-tion, 2012, 51:11814-11818.
[24]	RONO N, KIBET J K, MARTINCIGH B S, et al. A review of the current status of graphitic carbon nitride[J]. Critical Reviews in Solid State and Materials Sciences, 2021, 46:189-217.
[25]	FINA F, CALLEAR S K, CARINS G M, et al. Structural investiga-tion of graphitic carbon nitride via XRD and neutron diffraction[J]. Chemistry of Materials, 2015, 27:2612-2618.
[26]	KESSLER F K, ZHENG Y, SCHWARZ D, et al. Functional carbon nitride materials-design strategies for electrochemical devices[J]. Nature Reviews Materials, 2017, 2.Doi: 10.1038/natrevma-ts.2017.30.
[27]	LIN L, YU Z, WANG X C. Crystalline carbon nitride semiconduc-tors for photocatalytic water splitting[J]. Angewandte Chemie:In-ternational Edition, 2019, 58:6164-6175.
[28]	WANG Y H, LIU L Z, MA T Y, et al. 2D graphitic carbon nitride for energy conversion and storage[J]. Advanced Functional Materials, 2021, 31.Doi: 10.1002/adfm.202102540.
[29]	张金水, 王博, 王心晨. 石墨相氮化碳的化学合成及应用[J]. 物理化学学报, 2013, 29(9):1865-1876.
[30]	YE S, WANG R, WU M Z, et al. A review on g-C₃N₄ for photocata-lytic water splitting and CO₂ reduction[J]. Applied Surface Science, 2015, 358:15-27.
[31]	Ong W J, TAN L L, YUN H N, et al. Graphitic carbon nitride (g-C₃N₄)-based photocatalysts for artificial photosynjournal and envi-ronmental remediation:Are we a step closer to achieving sustainability?[J]. Chemical Reviews, 2016, 116:7159-7329.
[32]	SUDHAIK A, RAIZADA P, SHANDILYA P, et al. Review on fab-rication of graphitic carbon nitride based efficient nanocomposites for photodegradation of aqueous phase organic pollutants[J]. Jour-nal of Industrial and Engineering Chemistry, 2018, 67:28-51.
[33]	罗磊. 形貌可控g-C₃N₄的制备及其可见光催化性能研究[D]. 大连:大连理工大学, 2006.
[34]	WANG Y X, WANG H, CHEN F Y, et al. Facile synjournal of oxygen doped carbon nitride hollow microsphere for photocatalysis[J]. Applied Catalysis B:Environmental, 2017, 206:417-425.
[35]	XIA P F, ANTONIETTI M, ZHU B C, et al. Designing defective crystalline carbon nitride to enable selective CO₂ photoreduction in the gas phase[J]. Advanced Functional Materials, 2019, 29.Doi: 10.1002/adfm.201900093.
[36]	郑云, 王心晨. 超分子自组装法制备氮化碳聚合物光催化剂[J]. 中国材料进展, 2017, 36(1):25-32,39.
[37]	GU Q, LIAO Y S, YIN L S, et al. Template-free synjournal of porous graphitic carbon nitride microspheres for enhanced photocatalytic hydrogen generation with high stability[J]. Applied Catalysis B:Environmental, 2015, 165:503-510.
[38]	YU W W, ZHANG T, ZHAO Z K. Garland-like intercalated carbon nitride prepared by an oxalic acid-mediated assembly strategy for highly-efficient visible-light-driven photoredox catalysis[J]. App-lied Catalysis B:Environmental, 2020, 278.Doi: 10.1016/j.apcatb.2020.119342.
[39]	BAI X J, LI J, CAO C B. Synjournal of hollow carbon nitride micro-spheres by an electrodeposition method[J]. Applied Surface Sci-ence, 2010, 256:2327-2331.
[40]	ZHANG X L, ZHENG C, GUO S S, et al. Turn-on fluorescence sen-sor for intracellular imaging of glutathione using g-C₃N₄ nano-sheet-MnO₂ sandwich nanocomposite[J]. Analytical Chemistry, 2014, 86:3426-3434.
[41]	LIN B, YANG G D, WANG L Z. Stacking-layer-number depen-dence of water adsorption in 3D ordered close-packed g-C₃N₄ nanosphere arrays for photocatalytic hydrogen evolution[J]. Angewandte Chemie:International Edition, 2019, 58:4587-4591.
[42]	PAN J Q, DONG Z J, JIANG Z Y, et al. MoS₂ quantum dots modi-fied black Ti³+-TiO₂/g-C₃N₄ hollow nanosphere heterojunction to-ward photocatalytic hydrogen production enhancement[J]. Solar RRL, 2019, 3.Doi: 10.1002/solr.201970123.
[43]	ZHANG M Y, SUN Y, CHANG X, et al. Template-free synjournal of one-dimensional g-C₃N₄ chain nanostructures for efficient photo-catalytic hydrogen evolution[J]. Frontiers in Chemistry, 2021, 9. Doi: 10.3389/fchem.2021.652762.
[44]	KUMAR S, SURENDAR T, KUMAR B, et al. Synjournal of highly efficient and recyclable visible-light responsive mesoporous g-C₃N₄ photocatalyst via facile template-free sonochemical route[J]. RSC Advances, 2014, 4:8132-8137.
[45]	FU J W, ZHU B C, JIANG C J, et al. Hierarchical porous O-dopedg-C₃N₄ with enhanced photocatalytic CO₂ reduction activity[J]. Small, 2017, 13.Doi: 10.1002/smll.201603938.
[46]	TANG J Y, KONG X Y, NG B J, et al. Midgap-state-mediated two-step photoexcitation in nitrogen defect-modified g-C₃N₄ atomic layers for superior photocatalytic CO₂ reduction[J]. Catalysis Sci-ence & Technology, 2019, 9:2335-2343.
[47]	STARUKH H, PRAUS P. Doping of graphitic carbon nitride with non-metal elements and its applications in photocatalysis[J]. Cat-alysts, 2020, 10.Doi: 10.3390/catal10101119.
[48]	WANG K, LI Q, LIU B S, et al. Sulfur-doped g-C₃N₄ with enhanced photocatalytic CO₂-reduction performance[J]. Applied Catalysis B:Environmental, 2015, 176-177:44-52.
[49]	LI K Y, LIANG Y, YANG H, et al. New insight into the mechanism of enhanced photo-fenton reaction efficiency for Fe-doped semi-conductors:A case study of Fe/g-C₃N₄[J]. Catalysis Today, 2021, 371:58-63.
[50]	JI S Y, YANG Y L, ZHOU Z W, et al. Photocatalysis-fenton of Fe-doped g-C₃N₄ catalyst and its excellent degradation performance towards RhB[J]. Journal of Water Process Engineering, 2021, 40.Doi: 10.1016/j.jwpe.2020.101804.
[51]	GAO J K, WANG J P, QIAN X F, et al. One-pot synjournal of copper-doped graphitic carbon nitride nanosheet by heating Cu-melamine supramolecular network and its enhanced visible-light-driven pho-tocatalysis[J]. Journal of Solid State Chemistry, 2015, 228:60-64.
[52]	DOU H L, CHEN L, ZHENG S H, et al. Band structure engineering of graphitic carbon nitride via Cu²+/Cu⁺ doping for enhanced visible light photoactivity[J]. Materials Chemistry and Physics, 2018, 214:482-488.
[53]	LIU B Y, NIE X Q, TANG Y, et al. Objective findings on the K-do-ped g-C₃N₄ photocatalysts:The presence and influence of organic byproducts on K-doped g-C₃N₄ photocatalysis[J]. Langmuir, 2021, 37:4859-4868.
[54]	ZHANG M, BAI X J, LIU D, et al. Enhanced catalytic activity of po-tassium-doped graphitic carbon nitride induced by lower valence position[J]. Applied Catalysis B:Environmental, 2015, 164:77-81.
[55]	WANG Z T, XU J L, ZHOU H, et al. Facile synjournal of Zn(Ⅱ)-do-ped g-C₃N₄ and their enhanced photocatalytic activity under visible light irradiation[J]. Rare Metals, 2019, 38:459-467.
[56]	LI N X, LI Y, JIANG R M, et al. Photocatalytic coupling of methane and CO₂ into C₂-hydrocarbons over Zn doped g-C₃N₄ catalysts[J]. Applied Surface Science, 2019, 498.Doi: 10.1016/j.apsusc.2019.143861.
[57]	章富. 石墨相氮化碳的改性及其光催化制氢性能的研究[D]. 合肥:中国科学技术大学, 2021.
[58]	TANG J Y, ZHOU W G, GUO R T, et al. Enhancement of photoca-talytic performance in CO₂ reduction over Mg/g-C₃N₄ catalysts un-der visible light irradiation[J]. Catalysis Communications, 2018, 107:92-95.
[59]	WANG X N, WU L, WANG Z W, et al. C/N vacancy co-enhanced visible-light-driven hydrogen evolution of g-C₃N₄ nanosheets through controlled He⁺ ion irradiation[J]. Solar RRL, 2019, 3. Doi: 10.1002/solr.201800298.
[60]	WU H Z, LIU L M, ZHAO S J. The role of the defect on the adsorp-tion and dissociation of water on graphitic carbon nitride[J]. App-lied Surface Science, 2015, 358:363-369.
[61]	SHI H N, LONG S, HOU J G, et al. Defects promote ultrafast charge separation in graphitic carbon nitride for enhanced visiblelight-driven CO₂ reduction activity[J]. Chemistry:A European Journal, 2019, 25:5028-5035.
[62]	SONG X H, ZHANG X Y, LI X, et al. Enhanced light utilization efficiency and fast charge transfer for excellent CO₂ photoreduc-tion activity by constructing defect structures in carbon nitride[J]. Journal of Colloid and Interface Science, 2020, 578:574-583.
[63]	FAN Y Y, CHEN H M, CUI D F, et al. NiCo₂O₄/g-C₃N₄ heterojunc-tion photocatalyst for efficient H₂ generation[J]. Energy Technolo-gy, 2021, 9.Doi: 10.1002/ente.202000973.
[64]	ZHAO S C, LI K Y, DU J, et al. Facile construction of a hollow In₂S₃/polymeric carbon nitride heterojunction for efficient visible-light-driven CO₂ reduction[J]. ACS Sustainable Chemistry & En-gineering, 2021, 9:5942-5951.
[65]	JIANG Z F, WAN W M, LI H M, et al. A hierarchical Z-scheme α-Fe₂O₃/g-C₃N₄ hybrid for enhanced photocatalytic CO₂ reduction[J]. Advanced Materials, 2018, 30.Doi: 10.1002/adma.201706108.
[66]	SHI H N, DU J, HOU J G, et al. Solar-driven CO₂ conversion over Co²⁺ doped 0D/2D TiO₂/g-C₃N₄ heterostructure：Insights into the role of Co²⁺ and cocatalyst[J]. Journal of CO₂ Utilization, 2020, 38:16-23.

还原半反应	标准电势/V（相对于标准氢电极,pH=0）
CO₂（g）+e^-→CO₂^-	-1.90
CO₂（g）+2H⁺+2e^-→HCO₂H（l）	-0.20
CO₂（g）+2H⁺+2e^-→CO（g）+H₂O（l）	-0.12
2H⁺+2e^-→H₂（g）	0.00
CO₂（g）+6H⁺+6e^-→CH₃OH（l）+H₂O（l）	0.03
CO₂（g）+4H⁺+4e^-→HCHO（l）+H₂O（l）	0.07
2CO₂（g）+9H₂O（l）+12e^-→C₂H₅OH（l）+12OH^-	0.08
3CO₂（g）+13H₂O（l）+18e^-→C₃H₇OH（l）+18OH^-	0.09
CO₂（g）+8H⁺+8e^-→CH₄（g）+2H₂O（l）	0.17

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会