AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Highly efficient two-electron electroreduction of oxygen into hydrogen peroxide over Cu-doped TiO2

Zhiqin Deng1,§, Li Li1,§, Yuchun Ren1, Chaoqun Ma2, Jie Liang1, Kai Dong1, Qian Liu3( ), Yonglan Luo3, Tingshuai Li1, Bo Tang4, Yang Liu5, Shuyan Gao5, Abdullah M. Asiri6, Shihai Yan2( ), Xuping Sun1( )
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, China
Institute for Advanced Study, Chengdu University, Chengdu 610106, China
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China
School of Materials Science and Engineering, Henan Normal University, Xinxiang 453007, China
Chemistry Department, Faculty of Science & Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia

§ Zhiqin Deng and Li Li contributed equally to this work.

Show Author Information

Graphical Abstract

Cu acts as an effective dopant to boost the catalytic activity of TiO2 for 2e– O2 reduction reaction. Such Cu-TiO2 electrocatalyst achieves a high H2O2 selectivity of 91.2% and a large Faradaic efficiency (FE) of 98% in an alkaline medium.

Abstract

Electrosynthesis of hydrogen peroxide (H2O2), as a sustainable alternative to the anthraquinone oxidation method, provides the feasibility of directly generating H2O2. Here, we report Cu-doped TiO2 as an efficient electrocatalyst which exhibits the excellent two-electron oxygen reduction reaction (2e− ORR) performance with respect to the pristine TiO2. The Cu doping results in the distortion of TiO2 lattice and further forms a large number of oxygen vacancies and Ti3+. Such Cu-doped TiO2 exhibits a positive onset potential about 0.79 V and high H2O2 selectivity about 91.2%. Moreover, it also shows a larger H2O2 yield and good stability. Density functional theory (DFT) calculations reveal that Cu dopant not only improves the electrical conductivity of pristine TiO2 but reduces the *OOH adsorption energy of active sites, which is beneficial to promote subsequently 2e− ORR process.

Keywords

Cu-doped TiO2oxygen vacancyTi3+two-electron oxygen reduction reactionhydrogen peroxide

Electronic Supplementary Material

Download File(s)
12274_2021_3995_MOESM1_ESM.pdf (4.3 MB)

References

1

Campos-Martin, J. M.; Blanco-Brieva, G.; Fierro, J. L. G. Hydrogen peroxide synthesis: An outlook beyond the anthraquinone process. Angew. Chem., Int. Ed. 2006, 45, 6962–6984.
Crossref Google Scholar
2

Li, H. B.; Zheng, B.; Pan, Z. Y.; Zong, B. N.; Qiao, M. H. Advances in the slurry reactor technology of the anthraquinone process for H2O2 production. Front. Chem. Sci. Eng. 2018, 12, 124–131.
Crossref Google Scholar
3

Santacesaria, E.; Di Serio, M.; Velotti, R.; Leone, U. Kinetics, mass transfer, and palladium catalyst deactivation in the hydrogenation step of the hydrogen peroxide synthesis via anthraquinone. Ind. Eng. Chem. Res. 1994, 33, 277–284.
Crossref Google Scholar
4

Han, G. H.; Lee, S. H.; Hwang, S. Y.; Lee, K. Y. Advanced development strategy of nano catalyst and DFT calculations for direct synthesis of hydrogen peroxide. Adv. Energy Mater. 2021, 11, 2003121.
Crossref Google Scholar
5

Dittmeyer, R.; Grunwaldt, J. D.; Pashkova, A. A review of catalyst performance and novel reaction engineering concepts in direct synthesis of hydrogen peroxide. Catal. Today 2015, 248, 149–159.
Crossref Google Scholar
6

Jiang, Y. Y.; Ni, P. J.; Chen, C. X.; Lu, Y. Z.; Yang, P.; Kong, B.; Fisher, A.; Wang, X. Selective electrochemical H2O2 production through two-electron oxygen electrochemistry. Adv. Energy Mater. 2018, 8, 1801909.
Crossref Google Scholar
7

Wang, Y. L.; Waterhouse, G. I. N.; Shang, L.; Zhang, T. R. Electrocatalytic oxygen reduction to hydrogen peroxide: From homogeneous to heterogeneous electrocatalysis. Adv. Energy Mater. 2021, 11, 2003323.
Crossref Google Scholar
8

Chen, G. Y.; Liu, J. W.; Li, Q. Q.; Guan, P. F.; Yu, X. F.; Xing, L. S.; Zhang, J.; Che, R. C. A direct H2O2 production based on hollow porous carbon sphere-sulfur nanocrystal composites by confinement effect as oxygen reduction electrocatalysts. Nano Res. 2019, 12, 2614–2622.
Crossref Google Scholar
9

Cai, H. Z.; Chen, B. B.; Zhang, X.; Deng, Y. C.; Xiao, D. Q.; Ma, D.; Shi, C. Highly active sites of low spin FeIIN4 species: The identification and the ORR performance. Nano Res. 2021, 14, 122–130.
Crossref Google Scholar
10

Verdaguer-Casadevall, A.; Deiana, D.; Karamad, M.; Siahrostami, S.; Malacrida, P.; Hansen, T. W.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. Trends in the electrochemical synthesis of H2O2: Enhancing activity and selectivity by electrocatalytic site engineering. Nano Lett. 2014, 14, 1603–1608.
Crossref Google Scholar
11

Jirkovský, J. S.; Panas, I.; Ahlberg, E.; Halasa, M.; Romani, S.; Schiffrin, D. J. Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production. J. Am. Chem. Soc. 2011, 133, 19432–19441.
Crossref Google Scholar
12

Siahrostami, S.; Verdaguer-Casadevall, A.; Karamad, M.; Deiana, D.; Malacrida, P.; Wickman, B.; Escudero-Escribano, M.; Paoli, E. A.; Frydendal, R.; Hansen, T. W. et al. Enabling direct H2O2 production through rational electrocatalyst design. Nat. Mater. 2013, 12, 1137–1143.
Crossref Google Scholar
13

Chang, Q. W.; Zhang, P.; Mostaghimi, A. H. B.; Zhao, X. R.; Denny, S. R.; Lee, J. H.; Gao, H. P.; Zhang, Y.; Xin, H. L.; Siahrostami, S. et al. Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon. Nat. Commun. 2020, 11, 2178.
Crossref Google Scholar
14

Zhang, L. C.; Liang, J.; Yue, L. C.; Xu, Z. Q.; Dong, K.; Liu, Q.; Luo, Y. L.; Li, T. S.; Cheng, X. H.; Cui, G. W. et al. N-doped carbon nanotubes supported CoSe2 nanoparticles: A highly efficient and stable catalyst for H2O2 electrosynthesis in acidic media. Nano Res. 2022, 15, 304–309.
Crossref Google Scholar
15

Wang, M. J.; Zhang, N.; Feng, Y. G.; Hu, Z. W.; Shao, Q.; Huang, X. Q. Partially pyrolyzed binary metal-organic framework nanosheets for efficient electrochemical hydrogen peroxide synthesis. Angew. Chem., Int. Ed. 2020, 59, 14373–14377.
Crossref Google Scholar
16

Dong, K.; Liang, J.; Wang, Y. Y.; Xu, Z. Q.; Liu, Q.; Luo, Y. L.; Li, T. S.; Li, L.; Shi, X. F.; Asiri, A. M. et al. Honeycomb carbon nanofibers: A superhydrophilic O2-entrapping electrocatalyst enables ultrahigh mass activity for the two-electron oxygen reduction reaction. Angew. Chem., Int. Ed. 2021, 60, 10583–10587.
Crossref Google Scholar
17

Tang, C.; Jiao, Y.; Shi, B. Y.; Liu, J. N.; Xie, Z. H.; Chen, X.; Zhang, Q.; Qiao, S. Z. Coordination tunes selectivity: Two-electron oxygen reduction on high-loading molybdenum single-atom catalysts. Angew. Chem., Int. Ed. 2020, 59, 9171–9176.
Crossref Google Scholar
18

Zhang, L. C.; Liang, J.; Yue, L. C.; Dong, K.; Xu, Z. Q.; Li, T. S.; Liu, Q.; Luo, Y. L.; Liu, Y.; Gao, S. Y. et al. CoTe nanoparticle-embedded N-doped hollow carbon polyhedron: An efficient catalyst for H2O2 electrosynthesis in acidic media. J. Mater. Chem. A 2021, 9, 21703–21707.
Crossref Google Scholar
19

Sheng, H. Y.; Hermes, E. D.; Yang, X. H.; Ying, D. W.; Janes, A. N.; Li, W. J.; Schmidt, J. R.; Jin, S. Electrocatalytic production of H2O2 by selective oxygen reduction using earth-abundant cobalt pyrite (CoS2). ACS Catal. 2019, 9, 8433–8442.
Crossref Google Scholar
20

Liang, J.; Wang, Y. Y.; Liu, Q.; Luo, Y. L.; Li, T. S.; Zhao, H. T.; Lu, S. Y.; Zhang, F.; Asiri, A. M.; Liu, F. G. et al. Electrocatalytic hydrogen peroxide production in acidic media enabled by NiS2 nanosheets. J. Mater. Chem. A 2021, 9, 6117–6122.
Crossref Google Scholar
21

Wang, Y. L.; Shi, R.; Shang, L.; Waterhouse, G. I. N.; Zhao, J. Q.; Zhang, Q. H.; Gu, L.; Zhang, T. R. High-efficiency oxygen reduction to hydrogen peroxide catalyzed by Nickel single-atom catalysts with tetradentate N2O2 coordination in a three-phase flow cell. Angew. Chem., Int. Ed. 2020, 59, 13057–13062.
Crossref Google Scholar
22

Deng, Z. Q.; Ma, C. Q.; Yan, S. H.; Dong, K.; Liu, Q.; Luo, Y. L.; Liu, Y.; Du, J.; Sun, X. P.; Zheng, B. Z. One-dimensional conductive metal-organic framework nanorods: A highly selective electrocatalyst for the oxygen reduction to hydrogen peroxide. J. Mater. Chem. A 2021, 9, 20345–20349.
Crossref Google Scholar
23

Roy, P.; Berger, S.; Schmuki, P. TiO2 nanotubes: Synthesis and applications. Angew. Chem., Int. Ed. 2011, 50, 2904–2939.
Crossref Google Scholar
24

Chen, X. B.; Mao, S. S. Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications. Chem. Rev. 2007, 107, 2891–2959.
Crossref Google Scholar
25

Ghanem, M. A.; Al-Mayouf, A. M.; Shaddad, M. N.; Marken, F. Selective formation of hydrogen peroxide by oxygen reduction on TiO2 nanotubes in alkaline media. Electrochim. Acta 2015, 174, 557–562.
Crossref Google Scholar
26

Xu, Z. Q.; Liang, J.; Wang, Y. Y.; Dong, K.; Shi, X. F.; Liu, Q.; Luo, Y. L.; Li, T. S.; Jia, Y.; Asiri, A. M. et al. Enhanced electrochemical H2O2 production via two-electron oxygen reduction enabled by surface-derived amorphous oxygen-deficient TiO2−x. ACS Appl. Mater. Interfaces 2021, 13, 33182–33187.
Crossref Google Scholar
27

Wu, T. W.; Zhu, X. J.; Xing, Z.; Mou, S. Y.; Li, C. B.; Qiao, Y. X.; Liu, Q.; Luo, Y. L.; Shi, X. F.; Zhang, Y. N. et al. Greatly improving electrochemical N2 reduction over TiO2 nanoparticles by iron doping. Angew. Chem., Int. Ed. 2019, 58, 18449–18453.
Crossref Google Scholar
28

Kuang, M.; Wang, Y.; Fang, W.; Tan, H. T.; Chen, M. X.; Yao, J. D.; Liu, C. T.; Xu, J. W.; Zhou, K.; Yan, Q. Y. Efficient nitrate synthesis via ambient nitrogen oxidation with Ru-doped TiO2/RuO2 electrocatalysts. Adv. Mater. 2020, 32, 2002189.
Crossref Google Scholar
29

Koketsu, T.; Ma, J. W.; Morgan, B. J.; Body, M.; Legein, C.; Dachraoui, W.; Giannini, M.; Demortiere, A.; Salanne, M.; Dardoize, F. et al. Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO2. Nat. Mater. 2017, 16, 1142–1148.
Crossref Google Scholar
30

Han, Q.; Wu, C. B.; Jiao, H. M.; Xu, R. Y.; Wang, Y. Z.; Xie, J. J.; Guo, Q.; Tang, J. W. Rational design of high-concentration Ti3+ in porous carbon-doped TiO2 nanosheets for efficient photocatalytic ammonia synthesis. Adv. Mater. 2021, 33, 2008180.
Crossref Google Scholar
31

Colón, G.; Maicu, M.; Hidalgo, M. C.; Navío, J. A. Cu-Doped TiO2 systems with improved photocatalytic activity. Appl. Catal. B: Environ. 2006, 67, 41–51.
Crossref Google Scholar
32

Deng, Z. Q.; Ma, C. Q.; Yan, S. H.; Liang, J.; Dong, K.; Li, T. S.; Wang, Y.; Yue, L. C.; Luo, Y. L.; Liu, Q. et al. Electrocatalytic H2O2 production via two-electron O2 reduction by Mo-doped TiO2 nanocrystallines. Catal. Sci. Technol. 2021, 11, 6970–6974.
Crossref Google Scholar
33

Chen, Q. Y.; Ma, C. Q.; Yan, S. H.; Liang, J.; Dong, K.; Luo, Y. L.; Liu, Q.; Li, T. S.; Wang, Y.; Yue, L. C. et al. Greatly facilitated two-electron electroreduction of oxygen into hydrogen peroxide over TiO2 by Mn doping. ACS Appl. Mater. Interfaces 2021, 13, 46659–46664.
Crossref Google Scholar
34

Wu, T. W.; Zhao, H. T.; Zhu, X. J.; Xing, Z.; Liu, Q.; Liu, T.; Gao, S. Y.; Lu, S. Y.; Chen, G.; Asiri, A. M. et al. Identifying the origin of Ti3+ activity toward enhanced electrocatalytic N2 reduction over TiO2 nanoparticles modulated by mixed-valent copper. Adv. Mater. 2020, 32, 2000299.
Crossref Google Scholar
35

Cao, N.; Quan, Y. L.; Guan, A. X.; Yang, C.; Ji, Y. L.; Zhang, L. J.; Zheng, G. F. Oxygen vacancies enhanced cooperative electrocatalytic reduction of carbon dioxide and nitrite ions to urea. J. Colloid Interface Sci. 2020, 577, 109–114.
Crossref Google Scholar
36

Yuan, J.; Liu, L.; Guo, R. R.; Zeng, S.; Wang, H.; Lu, J. X. Electroreduction of CO2 into ethanol over an active catalyst: Copper supported on titania. Catalysts 2017, 7, 220.
Crossref Google Scholar
37

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 1996, 6, 15–50.
Crossref Google Scholar
38

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169.
Crossref Google Scholar
39

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
40

Tilocca, A.; Selloni, A. DFT-GGA and DFT + U simulations of thin water layers on reduced TiO2 anatase. J. Phys. Chem. C 2012, 116, 9114–9121.
Crossref Google Scholar
41

García-Mota, M.; Vojvodic, A.; Abild-Pedersen, F.; Nørskov, J. K. Electronic origin of the surface reactivity of transition-metal-doped TiO2(110). J. Phys. Chem. C 2013, 117, 460–465.
Crossref Google Scholar
42

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Crossref Google Scholar
43

Aguilar, T.; Navas, J.; Alcántara, R.; Fernández-Lorenzo, C.; Gallardo, J. J.; Blanco, G.; Martín-Calleja, J. A route for the synthesis of Cu-doped TiO2 nanoparticles with a very low band gap. Chem. Phys. Lett. 2013, 571, 49–53.
Crossref Google Scholar
44

Han, Z. S.; Choi, C.; Hong, S.; Wu, T. S.; Soo, Y. L.; Jung, Y.; Qiu, J.; Sun, Z. Y. Activated TiO2 with tuned vacancy for efficient electrochemical nitrogen reduction. Appl. Catal. B: Environ. 2019, 257, 117896.
Crossref Google Scholar
45

Li, L.; Chen, H. J.; Li, L.; Li, B. H.; Wu, Q. B.; Cui, C. H.; Deng, B.; Luo, Y. L.; Liu, Q.; Li, T. S. et al. La-doped TiO2 nanorods toward boosted electrocatalytic N2-to-NH3 conversion at ambient conditions. Chin. J. Catal. 2021, 42, 1755–1762.
Crossref Google Scholar
46

Wang, Y. F.; Chen, Z.; Han, P.; Du, Y. H.; Gu, Z. X.; Xu, X.; Zheng, G. F. Single-atomic Cu with multiple oxygen vacancies on ceria for electrocatalytic CO2 reduction to CH4. ACS Catal. 2018, 8, 7113–7119.
Crossref Google Scholar
47

Jiang, K.; Back, S.; Akey, A. J.; Xia, C.; Hu, Y. F.; Liang, W. T.; Schaak, D.; Stavitski, E.; Nørskov, J. K.; Siahrostami, S. et al. Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination. Nat. Commun. 2019, 10, 3997.
Crossref Google Scholar
48

Zhao, X.; Wang, Y.; Da, Y. L.; Wang, X. X.; Wang, T. T.; Xu, M. Q.; He, X. Y.; Zhou, W.; Li, Y. F.; Coleman, J. N. et al. Selective electrochemical production of hydrogen peroxide at zigzag edges of exfoliated molybdenum telluride nanoflakes. Natl. Sci. Rev. 2020, 7, 1360–1366.
Crossref Google Scholar
Nano Research
Volume 15 Issue 5,
May 2022
Pages 3880-3885
DOI: 10.1007/s12274-021-3995-6
Cite this article:
Deng Z, Li L, Ren Y, et al. Highly efficient two-electron electroreduction of oxygen into hydrogen peroxide over Cu-doped TiO2. Nano Research, 2022, 15(5): 3880-3885. https://doi.org/10.1007/s12274-021-3995-6
Topics:
Catalytic

1728

Views

52

Crossref

49

Web of Science

48

Scopus

1

CSCD

Altmetrics
Received: 04 September 2021
Revised: 22 October 2021
Accepted: 14 November 2021
Published: 11 January 2022
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
Return