基于氧化亚铜光电极的制备及其光电化学性能的研究进展

doi:10.16085/j.issn.1000-6613.2017-0668

摘要/Abstract

摘要： 氧化亚铜（Cu₂O）因具有合适的带隙、光响应好、价格低廉等优点，在光电化学（PEC）分解水和还原CO₂等领域引起广泛关注，是最重要的PEC光电极材料之一。本文回顾了近年来基于Cu₂O光电极的制备方法，如电化学法、物理沉积法、滴涂法、热氧化法、化学浴沉积法等，同时对不同的制备方法进行了比较。本文对基于其他过渡金属氧化物半导体材料来制备PEC光电极也具有一定的参考价值。另外，由于Cu₂O材料本身在电解液中易发生光腐蚀，光稳定性差，使得Cu₂O光电极在PEC上的应用受到很大限制。本文综述了表面修饰、半导体复合等改性手段来提高Cu₂O光电极的光稳定性，改善其PEC性能。最后指出Cu₂O光电极未来的研究重点在于探索新的电极制备方法、开拓新的改性手段以及多种改性手段的综合运用，从而进一步提高其PEC性能和应用前景。

关键词: 氧化亚铜, 光电极, 光电化学, 改性, 太阳能

Abstract: As one of the most important photoelectrode materials, cuprous oxide (Cu₂O) has attracted much attention in photoelectrochemical (PEC)water splitting and CO₂ reduction due to its advantages of suitable bandgap, well photoresponse and low cost. This review summarizes the latest progress on the preparation methods of Cu₂O photoelectrodes, such as electrochemistry, PVD, dip-coating, thermal oxidation and chemical bath deposition. The summarized methods are compared in details. Notably, this review provides valuable reference to designing and constructing PEC photoelectrodes based on other transition metal oxide semiconductors. In addition, the practical application of Cu₂O photoelectrodes is confined by its poor stability due to its self-photocorrosion in electrolyte solutions. This review outlines commonly used modification methods to enhance photostability and PEC performance of Cu₂O photoelectrodes, including surface modification, fabrication of semiconductor composites, etc. In the end, this review points out that the future research directions of Cu₂O photoelectrode should aim at exploring novel methods to fabricate Cu₂O photoelectrodes, inventing novel modification methods and integrating multiple modification methods in order to further enhance the PEC performance and application prospect of Cu₂O photoelectrodes.

Key words: cuprous oxide, photoelectrode, photoelectrochemical, modification, solar energy

中图分类号:

O643
O614

付星晨, 颜德健, 刘冀锴. 基于氧化亚铜光电极的制备及其光电化学性能的研究进展[J]. 化工进展, 2018, 37(01): 140-148.

FU Xingchen, YAN Dejian, LIU Jikai. Research progress of fabrication and photoelectrochemical properties based on Cu₂O photoelectrodes[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 140-148.

参考文献

[1] PARACCHINO A,LAPORTE V,SIVULA K,et al.Highly active oxide photocathode for photoelectrochemical water reduction[J]. Nature Materials,2011,10(6):456-461.
[2] HARA M,KONDO T,KOMODA M,et al.Cu₂O as a photocatalyst for overall water splitting under visible light irradiation[J].Chemical Communications,1998(3):357-358.
[3] IKEDA S,TAKATA T,KONDO T,et al.Mechano-catalytic overall water splitting[J].Chemical Communications,1998(20):2185-2186.
[4] YANG H,YANG J O,YANG A D,et al.Electrochemical synthesis and photocatalytic property of cuprous oxide nanoparticles[J].Materials Research Bulletin,2006,41(7):1310-1318.
[5] AKIMOTO K,ISHIZUKA S,YANAGITA M,et al.Thin film deposition of Cu₂O and application for solar cells[J].Solar Energy,2006,80(6):715-722.
[6] SHISHIYANU S T,SHISHIYANU T S,LUPAN O I.Novel NO₂ gas sensor based on cuprous oxide thin films[J]. Sensors and Actuators B:Chemical,2006,113(1):468-476.
[7] JAYARAMULU K,SURESH V M,MAJI T K.Stabilization of Cu₂O nanoparticles on a 2D metal-organic framework for catalytic Huisgen 1,3-dipolar cycloaddition reaction[J].Dalton Transactions,2015,44:83-86.
[8] KIM J,KWON Y,LEE H.Metal ion-assisted reshaping of Cu₂O nanocrystals for catalytic applications[J].Journal of Materials Chemistry A,2013,1:14183-14188.
[9] 宫慧勇,蒋晶晶,刘韶泽,等.纳米氧化亚铜的形貌控制合成及光催化降解有机染料的研究进展[J].化工进展,2015,34(11):3915-3925. GONG H Y,JIANG J J,LIU S Z,et al.Research progress in controllable synthesis of Cu₂O with different morphologies and their property for photodegrading organic dye[J].Chemical Industry and Engineering Progress,2015,34(11):3915-3925.
[10] 康园丽,王桂赟,刘宗园,等.含铜半导体氧化物的光催化应用进展[J].化工进展,2012,31(1):69-73. KANG Y L,WANG G Y,LIU Z Y,et al.Photocatalytic research progress of Cu-based semiconductor oxides[J].Chemical Industry and Engineering Progress,2012,31(1):69-73.
[11] CHANG X X,WANG T,ZHANG P,et al.Stable aqueous photoelectrochemical CO₂ reduction by a Cu₂O dark cathode with improved selectivity for carbonaceous products[J].Angewandte Chemie,2016,55(31):8840-8845.
[12] THERESE G H A,KAMATH P V.Electrochemical synthesis of metal oxides and hydroxides[J].Chemistry of Materials,2000,12(5):1195-1204.
[13] HU C,NIAN J,TENG S.Electrodeposited p-type Cu₂O as photocatalyst for H₂ evolution from water reduction in the presence of WO₃[J].Solar Energy Materials & Solar Cells,2008,92(9):1071-1076.
[14] YANG C,TRAN P D,BOIX P P,et al.Engineering a Cu₂O/NiO/Cu₂MoS₄ hybrid photocathode for H₂ generation in water[J].Nanoscale,2014,6:6506-6510.
[15] MCSHANE C M,CHOI K.Photocurrent enhancement of n-type Cu₂O electrodes achieved by controlling dendritic branching growth[J].Journal of the American Chemical Society,2009,131(7):2561-2569.
[16] WANG P,WU H,TANG Y,et al.Electrodeposited Cu₂O as photoelectrodes with controllable conductivity type for solar energy conversion[J].The Journal of Physical Chemistry C,2015,119(47):26275-26282.
[17] YU L,XIONG L,YU Y.Cu₂O homojunction solar cells:F-doped n-type thin film and highly improved efficiency[J].The Journal of Physical Chemistry C,2015,119(40):22803-22811.
[18] YANG Y,XU D,WU Q,et al.Cu₂O/CuO bilayered composite as a high-efficiency photocathode for photoelectrochemical hydrogen evolution reaction[J].Scientific Reports,2016,6:35158.
[19] TILLEY S D,SCHREIER M,AZEVEDO J,et al.Ruthenium oxide hydrogen evolution catalysis on composite cuprous oxide water-splitting photocathodes[J].Advanced Functional Materials,2014,24(3):303-311.
[20] PARACCHINO A,BRAUER J C,MOSER J,et al.Synthesis and characterization of high-photoactivity electrodeposited Cu₂O solar absorber by photoelectrochemistry and ultrafast spectroscopy[J].The Journal of Physical Chemistry C,2012,116(13):7341-7350.
[21] QI H,WOLFE J,FICHOU D,et al.Cu₂O photocathode for low bias photoelectrochemical water splitting enabled by NiFe-layered double hydroxide Co-catalyst[J].Scientific Reports,2016,6:30882.
[22] MUSSELMAN B K P,WISNET A,IZA D C,et al.Strong efficiency improvements in ultra-low-cost inorganic nanowire solar cells[J].Advanced Energy Materials,2010,22(35):E254-E258.
[23] HO-KIMURA S,MONIZ S J A,TANG J,et al.A method for synthesis of renewable Cu₂O junction composite electrodes and their photoelectrochemical properties[J]. ACS Sustainable Chemistry & Engineering,2015,3(4):710-717.
[24] SIRIPALA W,IVANOVSKAYA A,JARAMILLO T F,et al.A Cu₂O/TiO₂ heterojunction thin film cathode for photoelectrocatalysis[J]. Solar Energy Materials & Solar Cell,2003,77(3):229-237.
[25] WU L L,TSUI L,SWAMI N,et al.Photoelectrochemical stability of electrodeposited Cu₂O films[J].The Journal of Physical Chemistry C,2010,114(26):11551-11556.
[26] HAN K,TAO M.Electrochemically deposited p-n homojunction cuprous oxide solar cells[J].Solar Energy Materials & Solar Cells,2009,93(1):153-157.
[27] KATAYAMA J,ITO K,MATSUOKA M,et al.Performance of Cu₂O/ZnO solar cell prepared by two-step electrodeposition[J]. Journal of Applied Electrochemistry,2004,34(7):687-692.
[28] CUI J B,GIBSON U J.A simple two-step electrodeposition of Cu₂O/ZnO nanopillar solar cells[J].The Journal of Physical Chemistry C,2010,114(14):6408-6412.
[29] WANG P,TANG Y M,WEN X M,et al.Enhanced visible light-induced charge separation and charge transport in Cu₂O-based photocathodes by urea treatment[J].ACS Applied Materials & Interfaces,2015,7(36):19887-19893.
[30] HOU J G,CHENG H J,TAKEDA O,et al.Three-dimensional bimetal-graphene-semiconductor coaxial nanowire arrays to harness charge flow for the photochemical reduction of carbon dioxide[J].Angewandte Chemie,2015,54(29):8480-8484.
[31] LUO J S,STEIER L,SON M,et al.Cu₂O nanowire photocathodes for efficient and durable solar water splitting[J]. Nano Letters,2016,16(3):1848-1857.
[32] ZHANG Z H,DUA R,ZHANG L B,et al.Carbon-layer-protected cuprous oxide nanowire arrays for efficient water reduction[J].ACS Nano,2013,7(2):1709-1717.
[33] SHARMA D,UPADHYAY S,SATSANGI V R,et al.Improved photoelectrochemical water splitting performance of Cu₂O/SrTiO₃ heterojunction photoelectrode[J].The Journal of Physical Chemistry C,2014,118(44):25320-25329.
[34] YANG Z,CHIANG C K,CHANG H-T.Synthesis of fluorescent and photovoltaic Cu₂O nanocubes[J].Nanotechnology,2008,19(2).DOI:10.1088/0957-4484/19102/025604.
[35] ZHAO Y F,YANG Z Y,ZHANG Y X,et al.Cu₂O decorated with cocatalyst MoS₂ for solar hydrogen production with enhanced efficiency under visible light[J].The Journal of Physical Chemistry C,2014,118(26):14238-14245.
[36] AN X Q,LI K,TANG J W.Cu₂O/reduced graphene oxide composites for the photocatalytic conversion of CO₂[J].ChemSusChem,2014,7(4):1086-1093.
[37] DUCHENE J S,WILLIAMS B P,JOHNSTON-PECK A C,et al.Elucidating the sole contribution from electromagnetic near-fields in Plasmon-enhanced Cu₂O photocathodes[J].Advanced Energy Materials,2016,6:1501250.
[38] MINAMI T,TANAKA H,SHIMAKAWA T,et al.High-efficiency oxide heterojunction solar cells using Cu₂O sheets[J]. Japanese Journal of Applied Physics,2004,43:L917-L919.
[39] WANG L X,ZHAO F,HAN Q,et al.Spontaneous formation of Cu₂O-g-C₃N₄ core-shell nanowires for photocurrent and humidity responses[J].Nanoscale,2015,7:9694-9702.
[40] LIN C,LAI Y,MERSCH D,et al.Cu₂O|NiO_x nanocomposite as an inexpensive photocathode in photoelectrochemical water splitting[J].Chemical Science,2012,3:3482-3487.
[41] LI C L,LI Y B,DELAUNAY J.A novel method to synthesize highly photoactive Cu₂O microcrystalline films for use in photoelectrochemical cells[J]. ACS Applied Materials & Interfaces, 2014,6(1):480-486.
[42] YU L,LI G J,ZHANG X S,et al.Enhanced activity and stability of carbon-decorated cuprous oxide mesoporous nanorods for CO₂ reduction in artificial photosynthesis[J].ACS Catalysis,2016,6:6444-6454.
[43] JIN Z X,HU Z F,YU J C,et al.Room temperature synthesis of highly active Cu/Cu₂O photocathode for photoelectrochemical water splitting[J].Journal of Materials Chemistry A,2016,4:13736-13741.
[44] KECSENOVITY E,ENDRÖDI B,TÓTH P S,et al.Enhanced photoelechemical performance of cuprous oxide/graphene nanohybrids[J].Journal of the American Chemical Society,2017,139:6682-6692.
[45] FU K,HUANG J Z,YAO N N,et al.Hybrid nanostructure of TiO₂ nanorods arrays/Cu₂O with a CH₃NH₃PbI₃ interlayers for enhanced photocatalytic activity and photoelechemical performance[J].RSC Advances,2016,6:57695-57700.
[46] SHYAMAL S,HAJRA P,MANDAL H,et al.Benign role of Bi on electrodeposited Cu₂O semiconductor towards photo-assisted H₂ generation from water[J].Journal of Materials Chemistry A,2016,4:9244-9252.
[47] MAHMOUD M A,QIAN W,EI-SAYED M A.Following charge separation on the nanoscale in Cu₂O-Au nanoframe hollow nanoparticles[J].Nano Letters,2011,11(8):3285-3289.
[48] HACIALIOGLU S,MENG F,JIN S.Facile and mild solution synthesis of Cu₂O nanowires and nanotubes driven by screw dislocations[J].Chemical Communication,2012,48:1174-1176.
[49] JONGH P E D,VANMAEKELBERGH D,KELLY J J.Cu₂O:electrodeposition and Characterization[J].Chemistry of Materials,1999,11(12):3512-3517.
[50] ENGEL C J,POLSON T A,SPADO J R,et al.Photoelectrochemistry of porous p-Cu₂O films[J].Journal of the Electrochemical Society, 2008,155(3):F37-F42.
[51] GERISCHER H.On the stability of semiconductor electrodes against photodecomposition[J].Journal of the Electroanalytical Chemistry,1997,82(1/2):133-143.
[52] MORALES-GUIO C G,TILLEY S D,VRUBEL H,et al.Hydrogen evolution from a copper(I) oxide photocathode coated with an amorphous molybdenum sulphide catalyst[J]. Nature Communications,2014,5:3059.
[53] DUBALE A A,PAN C,TAMIRAT A G,et al.Heterostructured Cu₂O/CuO decorated with nickel as a highly efficient photocathode for photoelectrochemical water reduction[J].Journal of Materials Chemistry A,2015,3(23):12482-12499.
[54] HUANG Q,KANG F,LIU H,et al.Highly aligned Cu₂O/CuO/TiO₂ core/shell nanowire arrays as photocathodes for water photoelectrolysis[J].Journal of Materials Chemistry A,2013,1(7):2418-2425.
[55] JIANG T F,XIE T F,YANG W H,et al.Photoelectrochemical and photovoltaic properties of p-n Cu₂O homojunction films and their photocatalytic performance[J].The Journal of Physical Chemistry C,2013,117(9):4619-4624.
[56] SCHREIER M,LUO J S,GAO P,et al.Covalent immobilization of a molecular catalyst on Cu₂O photocathodes for CO₂ reduction[J].Journal of the American Chemical Society,2016,138(6):1938-1946.
[57] BORNOZ P,ABDI F F,TILLEY S D,et al.A bismuth vanadate-cuprous oxide tandem cell for overall solar water splitting[J].The Journal of Physical Chemistry C,2014,118(30):16959-16966.
[58] MORALES-GUIO C G,LIARDET L,MAYER M T,et al. Photoelectrochemical hydrogen production in alkaline solutions using Cu₂O coated with earth-abundant hydrogen evolution catalysts[J]. Angewandte Chemie International Edition,2015,54(2):664-667.