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非晶态 Cox-Fe-B 催化剂中 Co 和 Fe 的协同作用对高效氧析出反应的影响。

Synergistic Activity of Co and Fe in Amorphous Cox-Fe-B Catalyst for Efficient Oxygen Evolution Reaction.

机构信息

TU-NIMS International Collaboration Laboratory, School of Materials Science and Engineering, Tianjin University , Tianjin 300072, P. R. China.

Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 30072, P. R. China.

出版信息

ACS Appl Mater Interfaces. 2017 Nov 22;9(46):40333-40343. doi: 10.1021/acsami.7b13939. Epub 2017 Nov 13.

Abstract

Water splitting has been greatly limited by the sluggish kinetics of the oxygen evolution reaction (OER). High-oxidation-state metal species are required as the favorable active sites in OER. Here, amorphous Cox-Fe-B (x is the molar ratio of Co/Fe), Co-B, and Fe-B compounds were successfully synthesized as the oxygen evolution electrocatalysts. The calculation of turnover frequency (TOF) indicates that both the Co and Fe sites are active for OER. Cyclic voltammetry, X-ray photoelectron spectroscopy, and long-term stability curves were used to demonstrate that Fe can stabilize Co in a higher oxidation level and meanwhile promote the generation of OOH-like species (the key intermediates for OER). The reduced impedance for Co2-Fe-B (compared with that for Fe-B and Co-B) obtained from the electrochemical impedance spectra confirms the enhanced conductivity for the Co2-Fe-B. This optimal sample on Cu substrate shows a low overpotential of 0.298 V at the current density of 10 mA cm with a decreased overpotential of 42 mV compared to that of Co-B. The Co2-Fe-B catalyst also exhibits a small Tafel slope of 62.6 mV/dec and good stability. The enhanced performance could be attributed to the synergistic effect of the increased population of high-oxidation-state metal-OOH species and the promoted conductivity of the catalyst. A solar-to-hydrogen energy conversion efficiency of 4.2% and a Faradaic efficiency of 97.2% can be achieved by connecting the HER and as-prepared OER electrodes to a crystalline silicon solar cell.

摘要

水分解受到氧气析出反应 (OER) 缓慢动力学的极大限制。OER 需要高氧化态金属物种作为有利的活性位点。在此,成功合成了非晶态 Cox-Fe-B(x 是 Co/Fe 的摩尔比)、Co-B 和 Fe-B 化合物作为析氧电催化剂。转换频率(TOF)的计算表明 Co 和 Fe 位点都对 OER 具有活性。循环伏安法、X 射线光电子能谱和长期稳定性曲线表明,Fe 可以稳定 Co 处于较高的氧化态,同时促进 OOH 样物质(OER 的关键中间体)的生成。电化学阻抗谱得到的 Co2-Fe-B 的还原阻抗(与 Fe-B 和 Co-B 相比)证实了 Co2-Fe-B 的导电性增强。在 Cu 基底上的最佳样品在电流密度为 10 mA cm 时的过电位仅为 0.298 V,与 Co-B 相比,过电位降低了 42 mV。Co2-Fe-B 催化剂还表现出较小的塔菲尔斜率 62.6 mV/dec 和良好的稳定性。增强的性能可归因于高氧化态金属-OOH 物种的增加和催化剂导电性的提高的协同效应。通过将 HER 和制备的 OER 电极连接到晶体硅太阳能电池,可以实现 4.2%的太阳能到氢气的能量转换效率和 97.2%的法拉第效率。

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