Manifesting p-d Orbital Hybridization Through Strategic D-Band Engineering: A Pathway to Boosted Bifunctional HER/OER Electrochemical Performance in Self-Templated Co-SnO2 Grown Over Co-SnS2 Nanosheets.

IF 10.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL
Manash P Nath, Tanmoy Kalita, Suvankar Deka, Manju Kumari Jaiswal, Abhishek Borborah, Dhruba Jyoti Kalita, Lakshi Saikia, Biswajit Choudhury
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Abstract

In this study, Co-doped SnO2 is synthesized atop the hexagonal CoS template (CoSS) via direct air calcination of as-synthesized Co-doped SnS2 (CoS) nanosheets. The structural evolution facilitated the emergence of Co2+ and Co3+ states, complemented by surface-adsorbed sulfur oxyanions (SO4 2-, HSO3 -, SO3 2-). CoSS deposited over carbon cloth (CoSS/CC) exhibited superior bifunctional HER and OER, demonstrating higher stability and efficiency than their CoS/CC counterparts. Notably, CoSS/CC||CoSS/CC shows the overall water splitting at a minimum cell voltage of 1.5 V, significantly lower than CoS/CC||CoS/CC. Mechanistically, the Co3+ states serve as catalytically active sites that enhance OER, while the synergistic interaction between Co3+ and the sulfur oxyanions promotes HER activities. Density functional theory (DFT) calculations revealed an upshifted d-band centre (ɛd) and enhanced metal-oxygen covalency (Δ) in CoSS, with superior charge transfer and p-d hybridization. ATR-FTIR, Raman, and XPS investigations confirmed surface reconstruction of CoSS/CC electrodes with enhanced electrical conductivity. It is related that a highly strained system of VO-CoSS has more unfilled electronic states near the Fermi level (ɛF) to facilitate a stable interaction with HER/OER intermediates. Overall, this study underscores the superior bifunctional electrocatalytic efficiency of CoSS/CC over CoS/CC, establishing it as a promising candidate for efficient overall water splitting.

通过战略性d波段工程实现p-d轨道杂化:在Co-SnS2纳米片上生长的自模板Co-SnO2提高双功能HER/OER电化学性能的途径
在本研究中,通过直接空气煅烧合成的共掺杂SnS2 (CoS)纳米片,在六边形CoS模板(CoSS)上合成了共掺杂SnO2。结构演化促进了Co2+和Co3+态的出现,并辅以表面吸附的硫氧离子(SO4 2-, HSO3 -, so32 -)。在碳布上沉积的CoSS (CoSS/CC)表现出优异的双功能HER和OER,表现出比co /CC更高的稳定性和效率。值得注意的是,CoSS/CC||CoSS/CC在最小电池电压为1.5 V时显示出整体的水分裂,显著低于CoS/CC||CoS/CC。机制上,Co3+态作为催化活性位点增强OER,而Co3+与硫氧离子之间的协同作用促进HER活性。密度泛函理论(DFT)计算表明,CoSS的d波段中心(d)上移,金属-氧共价(Δ)增强,具有优越的电荷转移和p-d杂化。ATR-FTIR, Raman和XPS研究证实了CoSS/CC电极的表面重建具有增强的导电性。高应变的VO-CoSS系统在费米能级附近有更多的未填充电子态,以促进与HER/OER中间体的稳定相互作用。总的来说,本研究强调了CoSS/CC比CoS/CC更优越的双功能电催化效率,确立了它作为高效整体水分解的有希望的候选材料。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Small Methods
Small Methods Materials Science-General Materials Science
CiteScore
17.40
自引率
1.60%
发文量
347
期刊介绍: Small Methods is a multidisciplinary journal that publishes groundbreaking research on methods relevant to nano- and microscale research. It welcomes contributions from the fields of materials science, biomedical science, chemistry, and physics, showcasing the latest advancements in experimental techniques. With a notable 2022 Impact Factor of 12.4 (Journal Citation Reports, Clarivate Analytics, 2023), Small Methods is recognized for its significant impact on the scientific community. The online ISSN for Small Methods is 2366-9608.
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