Abstract
Herein, we report a special pulse potential method to increase methanol production and keep the CuxO/TiO2 nanotube array (TNT) catalyst active during photoelectrocatalysis reduction of CO2. The CuO/TNT catalyst was prepared via electrodeposition of copper on anodized titanium oxide followed by heat treatment. The variation of valence of copper in the photoelectrocatalytic reduction process was studied intensively by high-resolution transmission electron microscopy, XPS, and AES characterizations. Results show that the photocatalytically active CuO is apt to be reduced to elementary Cu during photoelectrocatalysis process, leading to rapid decay of photocatalytic activity. While for the case of pulse potential regime, another photocatalytically active oxide, Cu2O, will be produced on the surface during anodic pulse, which can effectively maintain the photocatalytic activity of catalyst. CV study indicates that the oxidation of Cu is prior to the oxidation of methanol, so the methanol oxidation hardly ever happens during anodic pulse stage. The catalyst applied in pulse potential regime provided a much larger photocurrent than that in constant potential regime over an extended period of time. As a result, the yield of methanol produced in optimized pulse potential condition is greatly increased, nearly twice that in constant potential regime.
Similar content being viewed by others
References
D’Alessandro DM, Smit B, Long JR (2010) Carbon dioxide capture: prospects for new materials. Angew Chem 49(35):6058–6082
Tu W, Zhou Y, Zou Z (2014) Photocatalytic conversion of CO2 into renewable hydrocarbon fuels: state-of-the-art accomplishment, challenges, and prospects. Adv Mater 26(27):4607–4626
Fang B, Xing Y, Bonakdarpour A, Zhang S, Wilkinson DP (2015) Hierarchical CuO–TiO2 hollow microspheres for highly efficient photodriven reduction of CO2 to CH4. ACS Sustain Chem Eng 3:2381–2388
Nguyen VH, Wu JCS (2018) Recent developments in the design of photoreactors for solar energy conversion from water splitting and CO2 reduction. Appl Catal A 550:122–141
Han E, Hu F, Zhang S, Luan B, Li P, Sun H, Wang S (2018) Worm-like FeS2/TiO2 nanotubes for photoelectrocatalytic reduction of CO2 to methanol under visible light. Energ Fuel 32:4357–4363
Li H, Lei Y, Huang Y, Fang Y, Xu Y, Zhu L, Li X (2011) Photocatalytic reduction of carbon dioxide to methanol by Cu2O/SiC nanocrystallite under visible light irradiation. J Nat Gas Chem 20:145–150
Huang J, Fu G, Shi C, Wang X, Zhai M, Gu C (2014) Novel porous CuO microrods: synthesis, characterization, and their photocatalysis property. J Phys Chem Solids 75:1011–1016
Shao Q, Wang LY, Wang XJ, Yang MC, Ge SS, Yang XK, Wang JX (2013) Hydrothermal synthesis and photocatalytic property of porous CuO hollow microspheres via PS latex as templates. Solid State Sci 20:29–35
Kim H, Bae S, Jeon D, Ryu J (2018) Fully solution-processable Cu2O–BiVO4 photoelectrochemical cells for bias-free solar water splitting. Green Chem 20:3732–3742
Wang K, Zhang WZ, Lou FP, Wei T, Qian ZM, Guo WH (2018) Preparation of electrospun heterostructured hollow SnO2/CuO nanofibers and their enhanced visible light photocatalytic performance. J Solid State Electr 22:2413–2423
Pozan GS, Isleyen M, Gokcen S (2013) Transition metal coated TiO2 nanoparticles: synthesis, characterization and their photocatalytic activity. Appl Catal B140-141(Complete):537–545
Scuderi V, Amiard G, Sanz R, Boninelli S, Impellizzeri G, Privitera V (2017) TiO2 coated CuO nanowire array: ultrathin p–n heterojunction to modulate cationic/anionic dye photo-degradation in water. Appl Surf Sci 416:885–890
Hu Q, Huang J, Li G, Chen J, Zhang Z, Deng Z, Jiang Y, Guo W, Cao Y (2016) Effective water splitting using CuOx/TiO2 composite films: role of Cu species and content in hydrogen generation. Appl Surf Sci 369:201–206
Santamaria M, Conigliaro G, Di Franco F (2014) Photoelectrochemical evidence of Cu2O/TiO2 nanotubes hetero-junctions formation and their physicochemical characterization. Electrochim Acta 144:315–323
Xq S, Li J, Zq Z, Yu M, Yuan L (2015) Cu(II) porphyrins modified TiO2 photocatalysts: accumulated patterns of Cu(II) porphyrin molecules on the surface of TiO2 and influence on photocatalytic activity. J Alloy Compd 626:252–259
Shaislamov U, Krishnamoorthy K, Kim SJ, Abidov A, Allabergenov B, Kim S, Choi S, Suresh R, Ahmed WM, Lee HJ (2016) Highly stable hierarchical p-CuO/ZnO nanorod/nanobranch photoelectrode for efficient solar energy conversion. Int J Hydrog Energy 41:2253–2262
Wang WN, Wu F, Myung Y, Niedzwiedzki DM, Im HS, Park J, Banerjee P, Biswas P (2015) Surface engineered CuO nanowires with ZnO islands for CO2 photoreduction. ACS Appl Mater Inter 7:5685–5692
Wang JC, Zhang L, Fang WX, Ren J, Li YY, Yao HC, Wang JS, Li ZJ (2015) Enhanced photoreduction CO2 activity over direct Z-scheme alpha-Fe2O3/Cu2O heterostructures under visible light irradiation. ACS Appl Mater Inter 7:8631–8639
Huang Q, Kang F, Liu H, Li Q, Xiao X (2013) Highly aligned Cu2O/CuO/TiO2 core/shell nanowire arrays as photocathodes for water photoelectrolysis. J Mater Chem A 1:2418–2425
Paracchino A, Laporte V, Sivula K, Grätzel M, Thimsen E (2011) Highly active oxide photocathode for photoelectrochemical water reduction. Nat Mater 10:456–461
Li Y, Yun X, Chen H, Zhang W, Li Y (2016) Facet-selective charge carrier transport, deactivation mechanism and stabilization of a Cu2O photo-electro-catalyst. Phys Chem Chem Phys 18(10):7023–7026
Habisreutinger SN, Schmidt ML, Stolarczyk JK (2013) Photocatalytic reduction of CO2 on TiO2 and other semiconductors. Angew Chem Int Edit 52:7372–7408
Radecka M, Wnuk A, Trenczek-Zajac A, Schneider K, Zakrzewska K (2015) TiO2/SnO2 nanotubes for hydrogen generation by photoelectrochemical water splitting. Int J Hydrog Energy 40:841–851
Li P, Zhang J, Wang H, Jing H, Xu J, Sui X, Hu H, Yin H (2014) The photoelectric catalytic reduction of CO2 to methanol on CdSeTe NSs/TiO2 NTs. Catal Sci Technol 4:1070–1077
Zhang L, Cao H, Pen Q, Wu L, Hou G, Tang Y, Zheng G (2018) Embedded CuO nanoparticles@TiO2-nanotube arrays for photoelectrocatalytic reduction of CO2 to methanol. Electrochim Acta 283:1507–1513
Cao H, Huang K, Wu L, Hou G, Tang Y, Zheng G (2016) Enhanced catalytic performance of Pt/TNTs composite electrode by reductive doping of TNTs. Appl Surf Sci 364:257–263
Miao H, Hu X, Fan J, Li C, Sun Q, Hao Y, Zhang G, Bai J, Hou X (2015) Hydrothermal synthesis of TiO2 nanostructure films and their photoelectrochemical properties. Appl Surf Sci 358:418–424
Xiao M, Musselman KP, Duley WW, Zhou NY (2016) Resistive switching memory of TiO2 nanowire networks grown on Ti foil by a single hydrothermal method. Nano-micro Lett 9:15
Babu B, Mallikarjuna K, Reddy CV, Park J (2016) Facile synthesis of Cu@TiO2 core shell nanowires for efficient photocatalysis. Mater Lett 176:265–269
Ai Z, Zhang L, Lee S, Ho W (2012) Interfacial hydrothermal synthesis of Cu@Cu2O core–shell microspheres with enhanced visible-light-driven photocatalytic activity. J Phys Chem C 113:20896–20902
Zhou C, Cheng J, Hou K, Zhu Z, Zheng Y (2017) Preparation of CuWO4@Cu2O film on copper mesh by anodization for oil/water separation and aqueous pollutant degradation. Chem Eng J 307:803–811
Zhou J, Guo L, Guo X, Mao J, Zhang S (2010) Selective hydrogenolysis of glycerol to propanediols on supported Cu-containing bimetallic catalysts. Green Chem 12:1835
Zhao J, Li Y, Zhu Y, Wang Y, Wang C (2016) Enhanced CO2 photoreduction activity of black TiO2-coated Cu nanoparticles under visible light irradiation: role of metallic Cu. Appl Catal A 510:34–41
Kim MH, Ebner JR, Friedman RM, Vannice MA (2002) Determination of metal dispersion and surface composition in supported Cu–Pt Catalysts. J Catal 208:381–392
Fox EB, Velu S, Engelhard MH, Chin YH, Miller JT, Kropf J, Song C (2008) Characterization of CeO2-supported Cu–Pd bimetallic catalyst for the oxygen-assisted water–gas shift reaction. J Catal 260:358–370
Macak JM, Gong BG, Hueppe M, Schmuki P (2007) Filling of TiO2 nanotubes by self-doping and electrodeposition. Adv Mater 19:3027–3031
Liu J, Shi H, Shen Q, Guo C, Zhao G (2017) Efficiently photoelectrocatalyze CO2 to methanol using Ru(II)-pyridyl complex covalently bonded on TiO2 nanotube arrays. Appl Catal B 210:368–378
Li P, Xu J, Jing H, Wu C, Peng H, Lu J, Yin H (2014) Wedged N-doped CuO with more negative conductive band and lower overpotential for high efficiency photoelectric converting CO2 to methanol. Appl Catal B 156-157(Complete):134–140
Lemos SG, Oliveira RTS, Santos MC, Nascente PAP, Bulhões LOS, Pereira EC (2007) Electrocatalysis of methanol, ethanol and formic acid using a Ru/Pt metallic bilayer. J Power Sources 163:695–701
Wang Y, Sheng ZM, Yang H, Jiang SP, Li CM (2010) Electrocatalysis of carbon black- or activated carbon nanotubes-supported Pd–Ag towards methanol oxidation in alkaline media. Int J Hydrog Energy 35:10087–10093
Hu Y, Shao Q, Wu P, Zhang H, Cai C (2012) Synthesis of hollow mesoporous Pt–Ni nanosphere for highly active electrocatalysis toward the methanol oxidation reaction. Electrochem Commun 18:96–99
Hu Y, Wu P, Zhang H, Cai C (2012) Synthesis of graphene-supported hollow Pt–Ni nanocatalysts for highly active electrocatalysis toward the methanol oxidation reaction. Electrochim Acta 85:314–321
Feng JJ, Chen LX, Ma X, Yuan J, Chen JR, Wang AJ, Xu QQ (2017) Bimetallic AuPt alloy nanodendrites/reduced graphene oxide: one-pot ionic liquid-assisted synthesis and excellent electrocatalysis towards hydrogen evolution and methanol oxidation reactions. Int J Hydrog Energy 42:1120–1129
Yang F, Cheng K, Wu T, Zhang Y, Yin J, Wang G, Cao D (2013) Dendritic palladium decorated with gold by potential pulse electrodeposition: enhanced electrocatalytic activity for H2O2 electroreduction and electrooxidation. Electrochim Acta 99:54–61
Cao H, Fan Z, Hou G, Tang Y, Zheng G (2014) Ball-flower-shaped Ni nanoparticles on Cu modified TiO2 nanotube arrays for electrocatalytic oxidation of methanol. Electrochim Acta 125:275–281
Funding
This work was supported by the Natural Science Foundation of Zhejiang Province (No. LY17B030009 and No. LQ16E020002).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Dedicated to the memory of Ivo Alexandre Hümmelgen
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Zhang, L., Cao, H., Lu, Y. et al. High-efficiency and sustainable photoelectric conversion of CO2 to methanol over CuxO/TNTs catalyst by pulse potential method. J Solid State Electrochem 24, 447–459 (2020). https://doi.org/10.1007/s10008-019-04439-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10008-019-04439-7