石墨相氮化碳光催化剂研究进展

doi:10.16085/j.issn.1000-6613.2016.07.018

摘要/Abstract

摘要： 石墨相氮化碳(g-C₃N₄)作为一种可见光响应的半导体聚合物光催化剂,具有廉价易得、化学稳定性好、无毒无害以及合适的禁带宽度和能带位置等优点,但也存在只能吸收波长小于475nm的光且光生载流子复合严重等问题,需要对其进行改性来提高光催化能力。本文在介绍g-C₃N₄的结构、特性和制备方法的基础上,着重评述了g-C₃N₄在形貌调控、半导体复合、元素掺杂、分子掺杂和染料敏化等改性手段方面的研究进展以及在降解有机污染物、分解水制氢、还原CO₂和有机合成等方面的应用。最后指出g-C₃N₄未来的研究方向在于用多种手段共同改性g-C₃N₄、拓展g-C₃N₄在光催化领域的应用和深入进行机理研究等方面。

关键词: 石墨相氮化碳, 催化剂, 太阳能, 制氢, 聚合物

Abstract: As a visible light responding polymer and semiconductor photocatalyst, graphitic carbon nitride (g-C₃N₄)has the advantages of cheap and readily available, chemically stable, non-toxic and harmless, as well as having suitable band gap and band position etc. However, g-C₃N₄ can only absorb light shorter than 460nm and its photogenerated carriers recombine severely, which has restricted its application. Modification of g-C₃N₄ is an effective means to improve its photocatalytic ability. This article outlines the structure, properties and preparation methods of g-C₃N₄, then focuses on the research progress of g-C₃N₄, including morphology controlling, compounding with semiconductors, element doping, molecular doping and dye-sensitized. It also discusses the applications of g-C₃N₄ in pollutants removal, hydrogen evolution, CO₂ reduction and other aspects of organic synthesis. The prospects for the development of g-C₃N₄ based photocatalysts are also discussed, and the research direction of graphitic carbon nitride are proposed as multiple modification, application and mechanism exploration.

Key words: graphitic carbon nitride, catalyst, solar energy, hydrogen production, polymers

中图分类号:

O643
O649

郭雅容, 陈志鸿, 刘琼, 张正国, 方晓明. 石墨相氮化碳光催化剂研究进展[J]. 化工进展, 2016, 35(07): 2063-2070.

GUO Yarong, CHEN Zhihong, LIU Qiong, ZHANG Zhengguo, FANG Xiaoming. Research progress of graphitic carbon nitride in photocatalysis[J]. Chemical Industry and Engineering Progree, 2016, 35(07): 2063-2070.

参考文献

[1] 李家德,方稳,周晚琴,等.银基半导体光催化剂研究进展[J]. 化工进展,2015,34(1):113-118.
[2] 黄颖,闫常峰,郭常青,等.半导体Z反应光解水制氢的光能转换效率及研究进展[J]. 化工进展,2014,33(12):3221- 3229,3245.
[3] FUJISHIMA A,HONDA K. Electrochemical photolysis of water at a semiconductor electrode [J]. Nature,1972,238(5358):37-38.
[4] ZHANG F,YAMAKATA A,MAEDA K,et al. Cobalt-modified porous single-crystalline LaTiO₂N for highly efficient water oxidation under visible light[J]. Journal of the American Chemical Society,2012,134(20):8348-8351.
[5] YANG J H,YAN H J,XU Z,et al. Roles of cocatalysts in semiconductor-based photocatalytic hydrogen production[J]. Philosophical Transactions of the Royal Society A (Mathematical,Physical & Engineering Sciences),2013,371(1996):0430 (15 pp.).
[6] CHEN S,QI Y,HISATOMI T,et al. Efficient visible-light-driven z-scheme overall water splitting using a MgTa₂O_6-xN_y/TaONheterostructure photocatalyst for H-2 evolution [J]. Angewandte Chemie-International Edition,2015,54(29):8498-8501.
[7] WANG X C,MAEDA K,THOMAS A,et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light[J]. Nature Materials,2009,8(1):76-80.
[8] LIEBIG J. About some nitrogen compounds[J]. Ann. Pharm,1834,10(10).
[9] YAN H-Y,WEI Q,ZHENG B-B,et al. Low-compressibility and hard material carbon nitride imide C₂N₂(NH):first principles calculations[J]. Journal of Solid State Chemistry,2011,184(3):572-577.
[10] THOMAS A,FISCHER A,GOETTMANN F,et al. Graphitic carbon nitride materials:variation of structure and morphology and their use as metal-free catalysts[J]. Journal of Materials Chemistry,2008,18(41):4893-4908.
[11] 范乾靖,刘建军,于迎春,等.新型非金属光催化剂-石墨型氮化碳的研究进展[J].化工进展,2014,33(5):1185-1194.
[12] YAN S C,LV S B,LI Z S,et al. Organic-inorganic composite photocatalyst of g-C₃N₄ and TaON with improved visible light photocatalytic activities[J]. Dalton Transactions,2010,39(6):1488-1491.
[13] GROENEWOLT M,ANTONIETTI M. Synthesis of g-C₃N₄ nanoparticles in mesoporous silica host matrices[J]. Advanced Materials,2005,17(14):1789-1792.
[14] YANGANG W,FEI W,YUANHUI Z,et al. Simple synthesis of ordered cubic mesoporous graphitic carbon nitride by chemical vapor deposition method using melamine[J]. Materials Letters,2014,136:271-273.
[15] MONTIGAUD H,TANGUY B,DEMAZEAU G,et al. Solvothermal synthesis of the graphitic form of C₃N₄ as macroscopic sample[J]. Diamond and Related Materials,1999,8(819):1707-1710.
[16] QIXUN G,YI X,XINJUN W,et al. Characterization of well-crystallized graphitic carbon nitride nanocrystallites via a benzene-thermal route at low temperatures[J]. Chemical Physics Letters,2003,380(1/2):84-87.
[17] ZIMMERMAN J L,WILLIAMS R,KHABASHESKU V N,et al. Synthesis of spherical carbon nitride nanostructures [J]. Nano Letters,2001,1(12):731-734.
[18] WANG X,MAEDA K,CHEN X,et al. Polymer semiconductors for artificial photosynthesis:hydrogen evolution by mesoporous graphitic carbon nitride with visible light[J]. Journal of the American Chemical Society,2009,131(5):1680-1681.
[19] LIU J,HUANG J,ZHOU H,et al. Uniform graphitic carbon nitride nanorod for efficient photocatalytic hydrogen evolution and sustained photoenzymatic catalysis[J]. ACS Applied Materials & Interfaces,2014,6(11):8434-8440.
[20] HO W,ZHANG Z,LIN W,et al. Copolymerization with 2,4,6-triaminopyrimidine for the rolling-up the layer structure,tunable electronic properties,and photocatalysis of g-C₃N₄[J]. ACS Applied Materials & Interfaces,2015,7(9):5497-505.
[21] LIN Z,ZHENG J,LIN G,et al. Negative ion laser desorption/ionization time-of-flight mass spectrometric analysis of small molecules using graphitic carbon nitride nanosheet matrix[J]. Anal. Chem.,2015,87(15):8005-8012.
[22] ZHANG J,WANG Y,JIN J,et al. Efficient visible-light photocatalytic hydrogen evolution and enhanced photostability of core/shell CdS/g-C₃N₄ nanowires[J]. ACS Applied Materials & Interfaces,2013,5(20):10317-10324.
[23] ZHANG M,BAI X,LIU D,et al. Enhanced catalytic activity of potassium-doped graphitic carbon nitride induced by lower valence position[J]. Applied Catalysis B:Environmental,2015,164:77-81.
[24] MENG Y,SHEN J,CHEN D,et al. Photodegradation performance of methylene blue aqueous solution on Ag/g-C₃N₄ catalyst[J]. Rare Metals,2011,30(s1):276-279.
[25] WANG Y,WANG Y,CHEN Y,et al. Synthesis of Ti-doped graphitic carbon nitride with improved photocatalytic activity under visible light [J]. Materials Letters,2015,139:70-72.
[26] SONG X,TAO H,CHEN L,et al. Synthesis of Fe/g-C₃N₄ composites with improved visible light photocatalytic activity[J]. Materials Letters,2014,116:265-267.
[27] CHANG C,FU Y,HU M,et al. Photodegradation of bisphenol A by highly stable palladium-doped mesoporous graphite carbon nitride (Pd/mpg-C₃N₄) under simulated solar light irradiation[J]. Applied Catalysis B:Environmental,2013,142/143:553-560.
[28] XU D,LI X,LIU J,et al. Synthesis and photocatalytic performance of europium-doped graphitic carbon nitride [J]. Journal of Rare Earths,2013,31(11):1085-1091.
[29] YUE B,LI Q,IWAI H,et al. Hydrogen production using zinc-doped carbon nitride catalyst irradiated with visible light[J]. Science and Technology of Advanced Materials,2011,12(3):034401.
[30] CHEN J,HONG Z,CHEN Y,et al. One-step synthesis of sulfur-doped and nitrogen-deficient g-C₃N₄ photocatalyst for enhanced hydrogen evolution under visible light[J]. Materials Letters,2015,145:129-132.
[31] LI J,SHEN B,HONG Z,et al. A facile approach to synthesize novel oxygen-doped g-C₃N₄ with superior visible-light photoreactivity[J]. Chemical Communications,2012,48(98):12017-12019.
[32] WANG H,ZHANG X,XIE J,et al. Structural distortion in graphitic-C₃N₄ realizing an efficient photoreactivity[J]. Nanoscale,2015,7(12):5152-5156.
[33] ZHANG G,ZHANG M,YE X,et al. Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution[J]. Advanced Materials,2014,26(5):805-809.
[34] ZHOU Y,ZHANG L,LIU J,et al. Brand new P-doped g-C₃N₄:enhanced photocatalytic activity for H2evolution and Rhodamine B degradation under visible light[J]. J. Mater. Chem. A,2015,3(7):3862-3867.
[35] LI Y,WU S,HUANG L,et al. Synthesis of carbon-doped g-C₃N₄ composites with enhanced visible-light photocatalytic activity[J]. Materials Letters,2014,137:281-284.
[36] ZHANG J,CHEN X,TAKANABE K,et al. Synthesis of a carbon nitride structure for visible-light catalysis by copolymerization[J]. Angewandte Chemie,2010,49(2):441-444.
[37] ZHANG G,WANG X. A facile synthesis of covalent carbon nitride photocatalysts by co-polymerization of urea and phenylurea for hydrogen evolution [J]. Journal of Catalysis,2013,307:246-253.
[38] ZHENG H-R,ZHANG J-S,WANG X-C,et al. Modification of carbon nitride photocatalysts by copolymerization with diaminomaleonitrile[J]. Acta Physico-Chimica Sinica,2012,28(10):2336-2342.
[39] GUO Y,KONG F,WANG C,et al. Molecule-induced gradient electronic potential distribution on a polymeric photocatalyst surface and improved photocatalytic performance[J]. Journal of Materials Chemistry A,2013,1(16):5142.
[40] CHU S,WANG Y,GUO Y,et al. Band structure engineering of carbon nitride:in search of a polymer photocatalyst with high photooxidation property[J]. ACS Catalysis,2013,3(5):912-919.
[41] CHEN Y,ZHANG J,ZHANG M,et al. Molecular and textural engineering of conjugated carbon nitride catalysts for selective oxidation of alcohols with visible light[J]. Chemical Science,2013,4(8):3244.
[42] ZHANG J,ZHANG G,CHEN X,et al. Co-monomer control of carbon nitride semiconductors to optimize hydrogen evolution with visible light[J]. Angewandte Chemie,2012,51(13):3183- 3187.
[43] TAKANABE K,KAMATA K,WANG X,et al. Photocatalytic hydrogen evolution on dye-sensitized mesoporous carbon nitride photocatalyst with magnesium phthalocyanine[J]. Physical Chemistry Chemical Physics,2010,12(40):13020-13025.
[44] MIN S,LU G. Enhanced electron transfer from the excited eosin Y to mpg-C₃N₄ for highly efficient hydrogen evolution under 550 nm irradiation [J]. Journal of Physical Chemistry C,2012,116(37):19644-19652.
[45] MAO J,PENG T,ZHANG X,et al. Effect of graphitic carbon nitride microstructures on the activity and selectivity of photocatalytic CO₂ reduction under visible light[J]. Catalysis Science & Technology,2013,3(5):1253-1260.
[46] CAO S-W,LIU X-F,YUAN Y-P,et al. Solar-to-fuels conversion over In₂O₃/g-C₃N₄ hybrid photocatalysts[J]. Applied Catalysis B-Environmental,2014,147:940-946.
[47] LI X-H,BAAR M,BLECHERT S,et al. Facilitating room-temperature Suzuki coupling reaction with light:Mott-Schottky photocatalyst for C-C-coupling[J]. Scientific Reports,2013,3(6):1743.
[48] DAI X,XIE M,MENG S,et al. Coupled systems for selective oxidation of aromatic alcohols to aldehydes and reduction of nitrobenzene into aniline using CdS/g-C₃N₄photocatalyst under visible light irradiation[J]. Applied Catalysis B-Environmental,2014,158:382-390.
[49] HONG J,XIA X,WANG Y,et al. Mesoporous carbon nitride with in situ sulfur doping for enhanced photocatalytic hydrogen evolution from water under visible light[J]. Journal of Materials Chemistry,2012,22(30):15006-15012.