In-Situ-Grown Cu Dendrites Plasmonically Enhance Electrocatalytic Hydrogen Evolution on Facet-Engineered Cu2 O

Hao Zhang; Jiefeng Diao; Yonghui Liu; Han Zhao; Bryan K Y Ng; Zhiyuan Ding; Zhenyu Guo; Huanxin Li; Jun Jia; Chang Yu; Fang Xie; Graeme Henkelman; Maria-Magdalena Titirici; John Robertson; Peter Nellist; Chunying Duan; Yuzheng Guo; D Jason Riley; Jieshan Qiu

doi:10.1002/adma.202305742

In-Situ-Grown Cu Dendrites Plasmonically Enhance Electrocatalytic Hydrogen Evolution on Facet-Engineered Cu₂ O

Adv Mater. 2023 Oct;35(42):e2305742. doi: 10.1002/adma.202305742. Epub 2023 Sep 12.

Authors

Hao Zhang^{1

2}, Jiefeng Diao³, Yonghui Liu⁴, Han Zhao⁵, Bryan K Y Ng⁶, Zhiyuan Ding⁷, Zhenyu Guo⁸, Huanxin Li⁹, Jun Jia⁴, Chang Yu¹⁰, Fang Xie¹, Graeme Henkelman³, Maria-Magdalena Titirici⁸, John Robertson^{4

9}, Peter Nellist⁷, Chunying Duan¹¹, Yuzheng Guo⁴, D Jason Riley¹, Jieshan Qiu¹⁰

Affiliations

¹ Department of Materials and London Center for Nanotechnology, Imperial College London, London, SW7 2AZ, UK.
² Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
³ Department of Chemistry and the Oden Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, TX, 78712, USA.
⁴ School of Electrical Engineering and Automation, Wuhan University, Wuhan, 430072, P. R. China.
⁵ Department of Chemistry, University of Zurich, Winterthurerstrasse 190, Zurich, CH-8057, Switzerland.
⁶ Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, OX1 3QR, UK.
⁷ Department of Materials, University of Oxford, Oxford, OX1 3PH, UK.
⁸ Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, UK.
⁹ Department of Engineering, University of Cambridge, Cambridge, CB2 1PZ, UK.
¹⁰ State Key Lab of Fine Chemicals, School of Chemical Engineering, Liaoning Key Lab for Energy Materials and Chemical Engineering, Dalian University of Technology, Dalian, 116024, P. R. China.
¹¹ School of Chemistry, Dalian University of Technology, Dalian, Liaoning, 116024, P. R. China.

PMID: 37667462
DOI: 10.1002/adma.202305742

Abstract

Herein, facet-engineered Cu₂ O nanostructures are synthesized by wet chemical methods for electrocatalytic HER, and it is found that the octahedral Cu₂ O nanostructures with exposed crystal planes of (111) (O-Cu₂ O) has the best hydrogen evolution performance. Operando Raman spectroscopy and ex-situ characterization techniques showed that Cu₂ O is reduced during HER, in which Cu dendrites are grown on the surface of the Cu₂ O nanostructures, resulting in the better HER performance of O-Cu₂ O after HER (O-Cu₂ O-A) compared with that of the as-prepared O-Cu₂ O. Under illumination, the onset potential of O-Cu₂ O-A is ca. 52 mV positive than that of O-Cu₂ O, which is induced by the plasmon-activated electrochemical system consisting of Cu₂ O and the in-situ generated Cu dendrites. Incident photon-to-current efficiency (IPCE) measurements and the simulated UV-Vis spectrum demonstrate the hot electron injection (HEI) from Cu dendrites to Cu₂ O. Ab initio nonadiabatic molecular dynamics (NAMD) simulations revealed the transfer of photogenerated electrons (27 fs) from Cu dendrites to Cu₂ O nanostructures is faster than electron relaxation (170 fs), enhancing its surface plasmons activity, and the HEI of Cu dendrites increases the charge density of Cu₂ O. These make the energy level of the catalyst be closer to that of H⁺ /H₂ , evidenced by the plasmon-enhanced HER electrocatalytic activity.

Keywords: copper dendrites; copper oxide; engineered facets; hot-electron injection; hydrogen evolution.

Abstract

Grants and funding