构筑富含阳离子缺陷的贫P-Ni2P和富P-CoP3异质结用于增强尿素/肼电催化氧化反应

doi:10.3866/PKU.WHXB202306054

Abstract

Abstract:

Handling hydrazine/urea wastewater through electrochemical oxidation technology (HzOR/UOR) holds significant importance for sewage disposal and nitrogen recycling, as the presence of hydrazine/urea leads to severe environmental issues. On the other hand, hydrazine/urea could potentially serve as a new type of fuel. However, at present, this remains a considerable challenge. The development of a low-cost, highly efficient, and stable electrocatalyst stands as a prerequisite for achieving this goal. In this study, a novel Ni₂P/CoP₃-Zn^vac bimetallic phosphide catalyst is designed and constructed using a hydrothermal-alkali etching-phosphating three-step method. This catalyst integrates P-rich CoP₃, P-poor metallic Ni₂P, and abundant Zn²⁺ cation vacancies into a single structure for HzOR/UOR. Copious P in CoP₃ provides a wealth of negative electrons, which aids in the adsorption of positive reactive intermediates. Meanwhile, P-poor metallic Ni₂P exhibits excellent electrical conductivity, ensuring rapid reaction dynamics. Both physical and electrochemical experiments confirm the successful creation of the Ni₂P/CoP₃-Zn^vac heterojunction, along with the distinctive electron structure of Ni₂P and CoP₃. Electron paramagnetic resonance (EPR) results validate the presence of cation vacancies, which significantly enhance the density of active sites. Consequently, this innovative Ni₂P/CoP₃-Zn^vac heterojunction catalyst displays remarkable electrocatalytic activity, achieving a potential of −47 mV/1.311 V to attain 10 mA∙cm⁻² for HzOR and UOR, respectively. The Tafel slopes of 54.3 and 37.24 mV∙dec⁻¹ for HzOR and UOR are significantly smaller than those of single-phased Ni₂P and CoP₃, as well as the two-phased phosphide without alkali etching. Building upon the excellent HzOR/UOR performance of the Ni₂P/CoP₃-Zn^vac heterojunction, a two-electrode cell for direct hydrazine fuel cells (DHzFC) and direct urea-hydrogen peroxide fuel cells (DUHPFC) is assembled with a Ni₂P/CoP₃-Zn^vac anode. This configuration demonstrates a maximum power density of 229.01 mW∙cm⁻² for DHzFC and 16.22 mW∙cm⁻² for DUHPFC. Moreover, both DHzFC and DUHPFC exhibit exceptional stability for up to 24 h. A homemade aqueous Zn-Hz battery, equipped with a Ni₂P/CoP₃-Zn^vac cathode, further demonstrates its practicality for energy conversion. This work underscores a promising avenue for developing cost-effective and highly stable solutions for UOR and HzOR.

Key words: Ni₂P/CoP₃ heterojunction, Cation vacancy, Alkaline etching, Hydrazine oxidation reaction, Urea oxidation reaction

Wenjuan Tan, Yong Ye, Xiujuan Sun, Bei Liu, Jiajia Zhou, Hailong Liao, Xiulin Wu, Rui Ding, Enhui Liu, Ping Gao. Building P-Poor Ni₂P and P-Rich CoP₃ Heterojunction Structure with Cation Vacancy for Enhanced Electrocatalytic Hydrazine and Urea Oxidation[J]. Acta Phys. -Chim. Sin. 2024, 40(6), 2306054. doi: 10.3866/PKU.WHXB202306054

Figures/Tables 8

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Building P-Poor Ni₂P and P-Rich CoP₃ Heterojunction Structure with Cation Vacancy for Enhanced Electrocatalytic Hydrazine and Urea Oxidation

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