English

Cobalt-Vanadium Layered Double Hydroxides Nanosheets as High-Performance Electrocatalysts for Urea Oxidation Reaction

• Yaoyu Liu ^1, ,
• Yuchen Wang ^{1, ,} ,
• Biying Liu ^1, ,
• Mahmoud Amer ^2, ,
• Kai Yan ^{1, ,}

• 1.

  School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275, China

• 2.

  Mechanical Engineering Department, Faculty of Engineering, Alexandria University, Alexandria 21544, Egypt

Corresponding author: Yuchen Wang, wangych235@mail.sysu.edu.cn Kai Yan, yank9@mail.sysu.edu.cn

• Received Date: 12 May 2022
  Accepted Date: 09 June 2022
  Revised Date: 06 June 2022
  Available Online: 15 February 2023
• Fund Project:

  the National Natural Science Foundation of China 22078374

  the National Key R & D Program of China 2020YFC1807600

  the Key-Area Research and Development Program of Guangdong Province 2019B110209003

  the Guangdong Basic and Applied Basic Research Foundation 2019B1515120058

  the Scientific and Technological Planning Project of Guangzhou 202206010145

Abstract: Hydrogen is considered as a desirable clean energy source for supporting human life in the future. Electrochemical water splitting is a promising method for generating carbon-free hydrogen. However, the relatively high overpotential of anodic oxygen evolution reaction (OER) is the main obstacle hindering the widespread popularity of water electrocatalysis technology. Recently, urea oxidation reaction (UOR) has gained significant attention as a potential alternative to OER for hydrogen production since the equilibrium potential of UOR is 0.86 V lower than that of OER. Transition metal-based layered double hydroxides (TM-LDHs) have been explored as promising UOR electrocatalysts, with the advantages of diversified metal species, stable two-dimensional layered structure and exchangeability of interlayer anions. To date, most studies have focused on TM-LDHs of late transition metals (e.g., Ni, Co, and Fe). In this work, by combining early and late transition metals, CoV-LDHs nanosheets were fabricated via a simple one-step coprecipitation method as high-performance UOR electrocatalysts. Additionally, cobalt hydroxide (Co(OH)₂), with a similar lamellar structure, was synthesized via the same method. When compared with Co(OH)₂, CoV-LDHs nanosheets exhibited better UOR performance owing to the following advantages: 1) The nanosheet structure of the as-fabricated CoV-LDHs electrocatalyst exposed a high number of active sites for the electrocatalytic conversion of urea. 2) The introduction of V enhanced the wettability of the CoV-LDHs electrocatalyst; thus, increasing its intrinsic electrocatalytic kinetics. 3) The d-electron compensation effect between Co (3d⁷4s²) and V (3d³4s²) was conducive to promoting the adsorption of urea. Therefore, the CoV-LDHs electrocatalyst exhibited a low electrochemical potential (1.52 V vs. the reversible hydrogen electrode, RHE) to achieve a current density of 10 mA∙cm⁻² in 1 mol∙L⁻¹ of potassium hydroxide containing 0.33 mol∙L⁻¹ urea, which was 70 mV less than that of Co(OH)₂. The Tafel slope value of the CoV-LDHs electrocatalyst (99.9 mV∙dec⁻¹) was lower than that of Co(OH)₂ (115.9 mV∙dec⁻¹), indicating faster UOR kinetics over the CoV-LDHs electrocatalyst. Furthermore, the CoV-LDHs electrocatalyst displayed high stability, with a negligible potential increase after a 10-h chronopotentiometry test by maintaining the current density of 10 mA∙cm⁻². In conclusion, the present work not only shows that the d-electron compensation effect between early and late transition metals could adjust the local electronic structure of TM-LDHs to improve the UOR efficiency, but also provides a feasible route to design dedicated nanostructured TM-LDHs as high-performance UOR electrocatalysts.

Key words:
• Urea oxidation
•  /  Layered double hydroxide
•  /  Nanosheet
•  /  d-Electron compensation
•  /  Wettability

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