Journal Home > Volume 11 , Issue 9

Photocatalytic CO2 reduction driven by green solar energy could be a promising approach for the carbon neutral practice. In this work, a novel defect engineering approach was developed to form the SnxNb1−xO2 solid solution by the heavy substitutional Nb-doping of SnO2 through a robust hydrothermal process. The detailed analysis demonstrated that the heavy substitution of Sn4+ by a higher valence Nb5+ created a more suitable band structure, a better photogenerated charge carrier separation and transfer, and stronger CO2 adsorption due to the presence of abundant acid centers and excess electrons on its surface. Thus, the SnxNb1−xO2 solid solution sample demonstrated a much better photocatalytic CO2 reduction performance compared to the pristine SnO2 sample without the need for sacrificial agent. Its photocatalytic CO2 reduction efficiency reached ~292.47 µmol/(g·h), which was 19 times that of the pristine SnO2 sample. Furthermore, its main photocatalytic CO2 reduction product was a more preferred multi-carbon (C2+) compound of C2H5OH, while that of the pristine SnO2 sample was a one-carbon (C1) compound of CH3OH. This work demonstrated that, the heavy doping of high valence cations in metal oxides to form solid solution may enhance the photocatalytic CO2 reduction and modulate its reduction process, to produce more C2+ products. This material design strategy could be readily applied to various material systems for the exploration of high-performance photocatalysts for the solar-driven CO2 reduction.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Creation of SnxNb1−xO2 solid solution through heavy Nb-doping in SnO2 to boost its photocatalytic CO2 reduction to C2+ products under simulated solar illumination

Show Author's information Shuang GAO( )Haitao GUANHongyang WANGXinhe YANGWeiyi YANGQi LI( )
Key Laboratory of Advanced Technologies of Materials (Ministry of Education), School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China

Abstract

Photocatalytic CO2 reduction driven by green solar energy could be a promising approach for the carbon neutral practice. In this work, a novel defect engineering approach was developed to form the SnxNb1−xO2 solid solution by the heavy substitutional Nb-doping of SnO2 through a robust hydrothermal process. The detailed analysis demonstrated that the heavy substitution of Sn4+ by a higher valence Nb5+ created a more suitable band structure, a better photogenerated charge carrier separation and transfer, and stronger CO2 adsorption due to the presence of abundant acid centers and excess electrons on its surface. Thus, the SnxNb1−xO2 solid solution sample demonstrated a much better photocatalytic CO2 reduction performance compared to the pristine SnO2 sample without the need for sacrificial agent. Its photocatalytic CO2 reduction efficiency reached ~292.47 µmol/(g·h), which was 19 times that of the pristine SnO2 sample. Furthermore, its main photocatalytic CO2 reduction product was a more preferred multi-carbon (C2+) compound of C2H5OH, while that of the pristine SnO2 sample was a one-carbon (C1) compound of CH3OH. This work demonstrated that, the heavy doping of high valence cations in metal oxides to form solid solution may enhance the photocatalytic CO2 reduction and modulate its reduction process, to produce more C2+ products. This material design strategy could be readily applied to various material systems for the exploration of high-performance photocatalysts for the solar-driven CO2 reduction.

Keywords: solid solution, tin oxide, photocatalytic CO2 reduction, heavy Nb-doping, C2+ product

References(58)

[1]
Ye LQ, Deng Y, Wang L, et al. Bismuth-based photocatalysts for solar photocatalytic carbon dioxide conversion. ChemSusChem 2019, 12: 3671–3701.
[2]
Oshima T, Ichibha T, Qin KS, et al. Undoped layered perovskite oxynitride Li2LaTa2O6N for photocatalytic CO2 reduction with visible light. Angew Chem Int Ed Engl 2018, 57: 8154–8158.
[3]
Baran T, Wojtyła S, Dibenedetto A, et al. Zinc sulfide functionalized with ruthenium nanoparticles for photocatalytic reduction of CO2. Appl Catal B: Environ 2015, 178: 170–176.
[4]
Do KH, Kumar DP, Rangappa AP, et al. Indium phosphide quantum dots integrated with cadmium sulfide nanorods for photocatalytic carbon dioxide reduction. ChemCatChem 2020, 12: 4550–4557.
[5]
Hsu HC, Shown I, Wei HY, et al. Graphene oxide as a promising photocatalyst for CO2 to methanol conversion. Nanoscale 2013, 5: 262–268.
[6]
Wang SB, Han X, Zhang YH, et al. Inside-and-out semiconductor engineering for CO2 photoreduction: From recent advances to new trends. Small Struct 2021, 2: 2000061.
[7]
Chen F, Ma ZY, Ye LQ, et al. Macroscopic spontaneous polarization and surface oxygen vacancies collaboratively boosting CO2 photoreduction on BiOIO3 single crystals. Adv Mater 2020, 32: e1908350.
[8]
Liu LZ, Huang HW, Chen ZS, et al. Synergistic polarization engineering on bulk and surface for boosting CO2 photoreduction. Angew Chem Int Ed Engl 2021, 60: 18303–18308.
[9]
Yang MQ, Xu YJ. Photocatalytic conversion of CO2 over graphene-based composites: Current status and future perspective. Nanoscale Horiz 2016, 1: 185–200.
[10]
Zhu ZH, Liu XL, Bao C, et al. How efficient could photocatalytic CO2 reduction with H2O into solar fuels be? Energy Convers Manag 2020, 222: 113236.
[11]
Wang CL, Sun ZX, Zheng Y, et al. Recent progress in visible light photocatalytic conversion of carbon dioxide. J Mater Chem A 2019, 7: 865–887.
[12]
Hao L, Kang L, Huang HW, et al. Surface-halogenation-induced atomic-site activation and local charge separation for superb CO2 photoreduction. Adv Mater 2019, 31: e1900546.
[13]
Wang XH, Lu L, Wang B, et al. Frustrated Lewis pairs accelerating CO2 reduction on oxyhydroxide photocatalysts with surface lattice hydroxyls as a solid-state proton donor. Adv Funct Mater 2018, 28: 1804191.
[14]
Liang SJ, Zhu SY, Chen Y, et al. Rapid template-free synthesis and photocatalytic performance of visible light-activated SnNb2O6 nanosheets. J Mater Chem 2012, 22: 2670–2678.
[15]
Tang LQ, Kuai LB, Li YC, et al. ZnxCd1–xS tunable band structure-directing photocatalytic activity and selectivity of visible-light reduction of CO2 into liquid solar fuels. Nanotechnology 2018, 29: 064003.
[16]
Xiao J, Yang WY, Gao S, et al. Fabrication of ultrafine ZnFe2O4 nanoparticles for efficient photocatalytic reduction CO2 under visible light illumination. J Mater Sci & Technol 2018, 34: 2331–2336.
[17]
Wang JJ, Lin S, Tian N, et al. Nanostructured metal sulfides: Classification, modification strategy, and solar-driven CO2 reduction application. Adv Funct Mater 2021, 31: 2008008.
[18]
Li X, Yu JG, Jaroniec M, et al. Cocatalysts for selective photoreduction of CO2 into solar fuels. Chem Rev 2019, 119: 3962–4179.
[19]
Sadeghzadeh-Attar A. Photocatalytic degradation evaluation of N–Fe codoped aligned TiO2 nanorods based on the effect of annealing temperature. J Adv Ceram 2020, 9: 107–122.
[20]
Qian XZ, Yang WY, Gao S, et al. Highly selective, defect-induced photocatalytic CO2 reduction to acetaldehyde by the Nb-doped TiO2 nanotube array under simulated solar illumination. ACS Appl Mater Interfaces 2020, 12: 55982–55993.
[21]
Lee S, Jeong S, Kim WD, et al. Low-coordinated surface atoms of CuPt alloy cocatalysts on TiO2 for enhanced photocatalytic conversion of CO2. Nanoscale 2016, 8: 10043–10048.
[22]
Ojha N, Bajpai A, Kumar S. Enriched oxygen vacancies of Cu2O/SnS2/SnO2 heterostructure for enhanced photocatalytic reduction of CO2 by water and nitrogen fixation. J Colloid Interface Sci 2021, 585: 764–777.
[23]
Ma ZY, Li PH, Ye LQ, et al. Selectivity reversal of photocatalytic CO2 reduction by Pt loading. Catal Sci Technol 2018, 8: 5129–5132.
[24]
Low JX, Cheng B, Yu JG. Surface modification and enhanced photocatalytic CO2 reduction performance of TiO2: A review. Appl Surf Sci 2017, 392: 658–686.
[25]
Rawool SA, Yadav KK, Polshettiwar V. Defective TiO2 for photocatalytic CO2 conversion to fuels and chemicals. Chem Sci 2021, 12: 4267–4299.
[26]
Yamaguchi D, Tang LG, Scarlett N, et al. The activation and conversion of carbon dioxide on the surface of zirconia-promoted ceria oxides. Chem Eng Sci 2020, 217: 115520.
[27]
Parey V, Abraham BM, Mir SH, et al. High-throughput screening of atomic defects in MXenes for CO2 capture, activation, and dissociation. ACS Appl Mater Interfaces 2021, 13: 35585–35594.
[28]
Yu HJ, Li JY, Zhang YH, et al. Three-in-one oxygen vacancies: Whole visible-spectrum absorption, efficient charge separation, and surface site activation for robust CO2 photoreduction. Angew Chem Int Ed 2019, 58: 3880–3884.
[29]
Karthikeyan C, Arunachalam P, Ramachandran K, et al. Recent advances in semiconductor metal oxides with enhanced methods for solar photocatalytic applications. J Alloys Compd 2020, 828: 154281.
[30]
Kou XY, Xie N, Chen F, et al. Superior acetone gas sensor based on electrospun SnO2 nanofibers by Rh doping. Sens Actuat B: Chem 2018, 256: 861–869.
[31]
DiMarco BN, Sampaio RN, James EM, et al. Efficiency considerations for SnO2-based dye-sensitized solar cells. ACS Appl Mater Interfaces 2020, 12: 23923–23930.
[32]
Cao ML, Cheng WL, Ni XH, et al. Lignin-based multi-channels carbon nanofibers @ SnO2 nanocomposites for high-performance supercapacitors. Electrochimica Acta 2020, 345: 136172.
[33]
Torres JA, da Silva GTST, Barbosa de Freitas Silva FB, et al. Experimental evidence of CO2 photoreduction activity of SnO2 nanoparticles. ChemPhysChem 2020, 21: 2392–2396.
[34]
Ali W, Zhang XL, Zhang XX, et al. Improved visible-light activities of g-C3N4 nanosheets by co-modifying nano-sized SnO2 and Ag for CO2 reduction and 2,4-dichlorophenol degradation. Mater Res Bull 2020, 122: 110676.
[35]
He YM, Zhang LH, Fan MH, et al. Z-scheme SnO2−x/g-C3N4 composite as an efficient photocatalyst for dye degradation and photocatalytic CO2 reduction. Sol Energy Mater Sol Cells 2015, 137: 175–184.
[36]
Li ZJ, Luan P, Zhang XL, et al. Prolonged lifetime and enhanced separation of photogenerated charges of nanosized α-Fe2O3 by coupling SnO2 for efficient visible-light photocatalysis to convert CO2 and degrade acetaldehyde. Nano Res 2017, 10: 2321–2331.
[37]
Hu K, Li ZJ, Chen SY, et al. Synthesis of silicate-bridged heterojunctional SnO2/BiVO4 nanoplates as efficient photocatalysts to convert CO2 and degrade 2,4-dichlorophenol. Part Part Syst Charact 2018, 35: 1700320.
[38]
Khan B, Raziq F, Faheem MB, et al. Electronic and nanostructure engineering of bifunctional MoS2 towards exceptional visible-light photocatalytic CO2 reduction and pollutant degradation. J Hazard Mater 2020, 381: 120972.
[39]
Alper E, Yuksel Orhan OY. CO2 utilization: Developments in conversion processes. Petroleum 2017, 3: 109–126.
[40]
Liu G, Wang LZ, Yang HG et al. Titania-based photocatalysts–crystal growth, doping and heterostructuring. J Mater Chem 2010, 20: 831–843.
[41]
Wang J, Tafen DN, Lewis JP, et al. Origin of photocatalytic activity of nitrogen-doped TiO2 nanobelts. J Am Chem Soc 2009, 131: 12290–12297.
[42]
Karakitsou KE, Verykios XE. Effects of altervalent cation doping of titania on its performance as a photocatalyst for water cleavage. J Phys Chem 1993, 97: 1184–1189.
[43]
Xu ZC, Yang WY, Li Q, et al. Passivated n–p co-doping of niobium and nitrogen into self-organized TiO2 nanotube arrays for enhanced visible light photocatalytic performance. Appl Catal B: Environ 2014, 144: 343–352.
[44]
Xu WL, Russo PA, Schultz T, et al. Niobium-doped titanium dioxide with high dopant contents for enhanced lithium-ion storage. ChemElectroChem 2020, 7: 4016–4023.
[45]
Purkayastha DD, Brahma R, Krishna MG, et al. Effects of metal doping on photoinduced hydrophilicity of SnO2 thin films. Bull Mater Sci 2015, 38: 203–208.
[46]
Toloman D, Popa A, Stefan M, et al. Enhanced photocatalytic activity of Co doped SnO2 nanoparticles by controlling the oxygen vacancy states. Opt Mater 2020, 110: 110472.
[47]
Ma HQ, Yang WY, Gao S, et al. Photoirradiation-induced capacitance enhancement in the h-WO3/Bi2WO6 submicron rod heterostructure under simulated solar illumination and its postillumination capacitance enhancement retainment from a photocatalytic memory effect. ACS Appl Mater Interfaces 2021, 13: 57214–57229.
[48]
Ren XD, Yang D, Yang Z, et al. Solution-processed Nb : SnO2 electron transport layer for efficient planar perovskite solar cells. ACS Appl Mater Interfaces 2017, 9: 24212429.10.1021/acsami.6b13362
[49]
Liu JY, Dai MJ, Wang TS, et al. Enhanced gas sensing properties of SnO2 hollow spheres decorated with CeO2 nanoparticles heterostructure composite materials. ACS Appl Mater Interfaces 2016, 8: 6669–6677.
[50]
Wang ZY, Zhang T, Han TY, et al. Oxygen vacancy engineering for enhanced sensing performances: A case of SnO2 nanoparticles-reduced graphene oxide hybrids for ultrasensitive ppb-level room-temperature NO2 sensing. Sens Actuat B Chem 2018, 266: 812–822.
[51]
Di Giulio M, Serra A, Tepore A, et al. Influence of the deposition parameters on the physical properties of tin oxide thin films. Mater Sci Forum 1996, 203: 143–148.
[52]
Chukwuike VI, Rajalakshmi K, Barik RC. Surface and electrochemical corrosion analysis of niobium oxide film formed in various wet media. Appl Surf Sci Adv 2021, 4: 100079.
[53]
Nefedov VI, Firsov MN, Shaplygin IS. Electronic structures of MRhO2, MRh2O4, RhMO4 and Rh2MO6 on the basis of X-ray spectroscopy and ESCA data. J Electron Spectrosc Relat Phenom 1982, 26: 65–78.
[54]
Matsumoto Y. Energy positions of oxide semiconductors and photocatalysis with iron complex oxides. J Solid State Chem 1996, 126: 227–234.
[55]
Verbruggen SW, Dirckx JJJ, Martens JA, et al. Surface photovoltage measurements: A quick assessment of the photocatalytic activity? Catal Today 2013, 209: 215–220.
[56]
Tröltzsch U, Kanoun O, Tränkler HR. Characterizing aging effects of lithium ion batteries by impedance spectroscopy. Electrochimica Acta 2006, 51: 1664–1672.
[57]
Shkrob IA, Marin TW, He HY, et al. Photoredox reactions and the catalytic cycle for carbon dioxide fixation and methanogenesis on metal oxides. J Phys Chem C 2012, 116: 9450–9460.
[58]
Yin WJ, Wen B, Bandaru S, et al. The effect of excess electron and hole on CO2 adsorption and activation on rutile (110) surface. Sci Rep 2016, 6: 23298.
File
40145_0619_ESM.pdf (371.9 KB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 04 January 2022
Revised: 31 May 2022
Accepted: 03 June 2022
Published: 22 July 2022
Issue date: September 2022

Copyright

© The Author(s) 2022.

Acknowledgements

This study was supported by the National Natural Science Foundation of China (Grant No. 51902271), the Fundamental Research Funds for the Central Universities (Grant Nos. 2682020CX07, 2682020CX08, and 2682021CX116), and Sichuan Science and Technology Program (Grant Nos. 2020YJ0072, 2020YJ0259, and 2021YFH0163). We would like to thank Analysis and Testing Center of Southwest Jiaotong University for the assistance on material characterization.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Return