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脉冲电沉积法制备的形貌可控有机-无机纳米杂化物作为尿素氧化的双功能电催化剂。

Pulse electrodeposited, morphology controlled organic-inorganic nanohybrids as bifunctional electrocatalysts for urea oxidation.

作者信息

Jadhav Rohit G, Das Apurba K

机构信息

Department of Chemistry and Centre for Advanced Electronics (CAE), Indian Institute of Technology Indore, Indore 453552, India.

出版信息

Nanoscale. 2020 Dec 8;12(46):23596-23606. doi: 10.1039/d0nr07236b.

Abstract

Organic-inorganic nanohybrids with nanoscale architectures and electrocatalytic properties are emerging as a new branch of advanced functional materials. Herein, nanohybrid organic-inorganic nanosheets are grown on carbon paper via a pulse-electrochemical deposition technique. A benzo[2,1,3]selenadiazole-5-carbonyl protected dipeptide BSeFL (BSe = benzoselenadiazole; F = phenylalanine; and L = leucine) cross-linked with Ni2+ ions (Ni-BSeFL) and nickel hydroxide (Ni(OH)2) in a BSeFL/Ni(OH)2 electrode exhibits stable electrocatalytic activity toward urea oxidation. The cross-linked nanosheet morphology of nanohybrids was optimized by controlling the reduction potential during pulse electrodeposition. The BSeFL/Ni(OH)2 (-1.0 V) nanohybrid deposited at -1.0 V provides abundant active sites of Ni3+ with low charge transfer resistance (RCT) and high exchange current density (J0) at the electrocatalytic interface. The nanohybrids with Ni-BSeFL and Ni(OH)2 show low overpotential and superior stability for electrocatalytic urea electro-oxidation. The BSeFL/Ni(OH)2 (-1.0 V) nanohybrid based electrode requires a low potential of 1.30 V (vs. RHE) to acquire a current density of 10 mA cm-2 for the urea oxidation reaction (UOR) in urea containing alkaline solution which is lower than that for water oxidation in alkaline solution (1.49 V vs. RHE). The organic-inorganic nanohybrid BSeFL/Ni(OH)2 (-1.0 V) shows durability over 10 h for oxygen evolution and urea electro-oxidation, thereby confirming the BSeFL/Ni(OH)2 (-1.0 V) nanohybrid-based electrode as an efficient electrocatalyst.

摘要

具有纳米级结构和电催化性能的有机-无机纳米杂化物正成为先进功能材料的一个新分支。在此,通过脉冲电化学沉积技术在碳纸上生长纳米杂化有机-无机纳米片。一种与Ni2+离子(Ni-BSeFL)交联的苯并[2,1,3]硒二唑-5-羰基保护二肽BSeFL(BSe = 苯并硒二唑;F = 苯丙氨酸;L = 亮氨酸)以及氢氧化镍(Ni(OH)2)在BSeFL/Ni(OH)2电极中对尿素氧化表现出稳定的电催化活性。通过控制脉冲电沉积过程中的还原电位来优化纳米杂化物的交联纳米片形态。在-1.0 V下沉积的BSeFL/Ni(OH)2(-1.0 V)纳米杂化物在电催化界面处提供了丰富的Ni3+活性位点,具有低电荷转移电阻(RCT)和高交换电流密度(J0)。具有Ni-BSeFL和Ni(OH)2的纳米杂化物对尿素电氧化显示出低过电位和优异的稳定性。基于BSeFL/Ni(OH)2(-1.0 V)纳米杂化物的电极在含尿素的碱性溶液中进行尿素氧化反应(UOR)时,需要1.30 V(相对于可逆氢电极,RHE)的低电位来获得10 mA cm-2的电流密度,这低于碱性溶液中析氧反应的电位(1.49 V相对于RHE)。有机-无机纳米杂化物BSeFL/Ni(OH)2(-1.0 V)在析氧和尿素电氧化方面表现出超过10小时的耐久性,从而证实基于BSeFL/Ni(OH)2(-1.0 V)纳米杂化物的电极是一种高效的电催化剂。

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