Citation: Lv Lin, Zhang Liyang, He Xuebing, Yuan Hong, Ouyang Shuxin, Zhang Tierui. Energy-Efficient Hydrogen Production via Electrochemical Methanol Oxidation Using a Bifunctional Nickel Nanoparticle-Embedded Carbon Prism-Like Microrod Electrode[J]. Acta Physico-Chimica Sinica, ;2021, 37(7): 200707. doi: 10.3866/PKU.WHXB202007079 shu

Energy-Efficient Hydrogen Production via Electrochemical Methanol Oxidation Using a Bifunctional Nickel Nanoparticle-Embedded Carbon Prism-Like Microrod Electrode

Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China

Corresponding author: Ouyang Shuxin, oysx@mail.ccnu.edu.cn
Received Date: 28 July 2020
Revised Date: 22 August 2020
Accepted Date: 4 September 2020
Available Online: 14 September 2020
Fund Project: the China Postdoctoral Science Foundation 2019M660184the National Natural Science Foundation of China 21972052the Natural Science Foundation of Hubei Province, China 2020CFB446This work was supported by the China Postdoctoral Science Foundation (2019M660184), the Natural Science Foundation of Hubei Province, China (2020CFB446), and the National Natural Science Foundation of China (21972052). S.O. thanks the financial support from the "Guizi Scholar" Program of Central China Normal University, China

With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm⁻² toward hydrogen evolution in 1.0 mol∙L⁻¹ KOH aqueous solution with 0.5 mol∙L⁻¹ methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm⁻² at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation.
- Bifunctionality,
- Hydrogen evolution,
- Methanol oxidation,
- Nickel nanoparticles,
- Electrolyzer
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