Tripathi Vijay, Jain Siddarth, Kabra Dinesh, Panchakarla Leela S, Dutta Arnab
Department of Chemistry, Indian Institute of Technology Bombay Mumbai 400076 India
Department of Physics, Indian Institute of Technology Bombay Mumbai 400076 India.
Nanoscale Adv. 2022 Nov 25;5(1):237-246. doi: 10.1039/d2na00724j. eCollection 2022 Dec 20.
Strategically doped metal oxide nanomaterials signify a rapidly growing genre of functional materials with a wide range of practical applications. Copper vanadate (CuV) represents one such highly active system, which has been rarely explored following its doping with an abundant first-row transition metal. Here, we have developed a series of CuV samples with varying cobalt(ii) doping concentrations deploying a relatively simple solid state synthetic procedure. Among the samples, the 10% Co(ii)-doped CuV (Co-CuV) exhibited excellent reactivity for both the H evolution reaction (HER) and glycerol oxidation reaction (GOR) in an alkaline aqueous medium (pH 14.0) during cathodic and anodic scans, respectively. During this dual-active catalysis, surface-immobilized Co-CuV operates at exceptionally low overpotentials of 176 mV and 160 mV for the HER and GOR, respectively, while achieving 10 mA cm current density. The detailed spectroscopic analysis revealed the formation of formate as the major product during the GOR with a faradaic efficiency of >90%. Therefore, this Co-CuV can be included on either side of a two-electrode electrolyzer assembly to trigger a complete biomass-driven H production, establishing an ideal carbon-neutral energy harvest process.
具有战略意义的掺杂金属氧化物纳米材料是一类快速发展的功能材料，具有广泛的实际应用。钒酸铜（CuV）就是这样一种高活性体系，在用丰富的第一行过渡金属对其进行掺杂后，该体系鲜有研究。在此，我们采用相对简单的固态合成方法，制备了一系列钴（II）掺杂浓度不同的CuV样品。在这些样品中，10%钴（II）掺杂的CuV（Co-CuV）在碱性水介质（pH 14.0）中分别在阴极扫描和阳极扫描期间，对析氢反应（HER）和甘油氧化反应（GOR）均表现出优异的反应活性。在这种双活性催化过程中，表面固定的Co-CuV在析氢反应和甘油氧化反应中分别在176 mV和160 mV的极低过电位下运行，同时实现10 mA cm的电流密度。详细的光谱分析表明，在甘油氧化反应过程中，甲酸盐作为主要产物形成，法拉第效率>90%。因此，这种Co-CuV可以包含在双电极电解槽组件的任一侧，以触发完整的生物质驱动制氢过程，建立理想的碳中性能量收集过程。
