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揭示ZIF-9与硼碳氮化物在还原氧化石墨烯上的良好协同作用,作为碱性介质中析氢和析氧反应的双功能电催化剂。

Unveiling the Favorable Synergy of ZIF-9 and Borocarbonitride on rGO as a Bifunctional Electrocatalyst for Hydrogen and Oxygen Evolution Reactions in Alkaline Media.

作者信息

Daniel Shantharaja, Kim Hyun Chul, Podilapu Atchutha Rao

机构信息

Department of Future Automotive Engineering, Green Car Technology Research Center, Hydrogen Energy Human Resources Development Group, Kongju National University, 1223-24 (7-211), Cheonan-daero, Seobuk-gu, Cheonan-si, Chungnam 31080, Republic of Korea.

Gitam (Deemed-to-be) University, Visaakhapatnam 530045, India.

出版信息

Langmuir. 2025 Jul 30. doi: 10.1021/acs.langmuir.5c02189.

Abstract

Exploitation of the reaction of hydrogen with oxygen as an energy source requires energy storage and conversion devices, such as metal-air batteries and fuel cells, which, in turn, require the development of low-cost materials with high electrocatalytic performance for hydrogen/oxygen evolution reactions (HER/OER).o develop highly efficient, bifunctional HER/OER electrocatalysts, the imidazole-substituted benzimidazole precursor 3 was used to synthesize a cobalt(II)-MOF (ZIF-9). Synthesized ZIF-9 was used as a sacrificial precursor, where the pyrolysis temperature and Co doping of the benzimidazole framework were tuned. Composites of ZIF-9 with boron carbon nitride (BCN) and graphene oxide (rGO) on carbon cloth (CC), denoted as ZIF-9 + BCN + rGO/CC, were prepared by varying the amounts of BCN and rGO in a ratio of 1:1, respectively, immobilized on the electrode surfaces. The nanocomposite catalysts were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, and Raman spectroscopy. The efficacy of the composite electrocatalysts as the working electrode for electrochemical water electrolysis via hydrogen and oxygen evolution reactions was evaluated by using spectroscopic and analytical techniques. The composite catalyst ZIF-9 + BCN + rGO/CC exhibited impressive performance, indicated by the overpotential, onset potential, and Tafel values in 1 M KOH electrolyte at a scan rate of 5 mV and overpotential of 10 mA cm. ZIF-9 + BCN + rGO/CC afforded η values of less than -222 mV (HER) and 374 mV (OER). The Tafel values were 39 mV/dec (HER) and 73 mV/dec (OER). The ZIF-9 + BCN + rGO/CC catalyst showed remarkable stability for approximately 50 h and was durable in basic media for both the hydrogen and oxygen evolution reactions. ZIF-9 + BCN + rGO/CC as a cathode and anode catalyst exhibited excellent performance in terms of overall electrocatalysis, superior to that of state-of-the-art catalysts.

摘要

将氢与氧的反应用作能源需要能量存储和转换装置,如金属空气电池和燃料电池,这反过来又需要开发用于析氢/析氧反应(HER/OER)的具有高电催化性能的低成本材料。为了开发高效的双功能HER/OER电催化剂,咪唑取代的苯并咪唑前体3被用于合成钴(II)-金属有机框架(ZIF-9)。合成的ZIF-9用作牺牲前体,其中对苯并咪唑框架的热解温度和钴掺杂进行了调整。通过以1:1的比例分别改变BCN和rGO的量,制备了ZIF-9与硼碳氮化物(BCN)和氧化石墨烯(rGO)在碳布(CC)上的复合材料,记为ZIF-9 + BCN + rGO/CC,并将其固定在电极表面。使用傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱、X射线衍射、热重分析、布鲁诺尔-埃米特-泰勒分析和拉曼光谱对纳米复合催化剂进行了表征。通过光谱和分析技术评估了复合电催化剂作为通过析氢和析氧反应进行电化学水分解的工作电极的效能。复合催化剂ZIF-9 + BCN + rGO/CC表现出令人印象深刻的性能,在1 M KOH电解液中,扫描速率为5 mV且过电位为10 mA cm时,其过电位、起始电位和塔菲尔值表明了这一点。ZIF-9 + BCN + rGO/CC的η值小于-222 mV(HER)和374 mV(OER)。塔菲尔值分别为39 mV/dec(HER)和73 mV/dec(OER)。ZIF-9 + BCN + rGO/CC催化剂在约50小时内表现出显著的稳定性,并且在碱性介质中对于析氢和析氧反应都很耐用。ZIF-9 + BCN + rGO/CC作为阴极和阳极催化剂在整体电催化方面表现出优异的性能,优于现有催化剂。

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