Strong p-d Orbital Hybridization on Bismuth Nanosheets for High Performing CO2 Electroreduction,Advanced Materials

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Strong p-d Orbital Hybridization on Bismuth Nanosheets for High Performing CO2 Electroreduction
Advanced Materials ( IF 27.4 ) Pub Date : 2023-11-27 , DOI: 10.1002/adma.202309648
Xueying Cao ₁ , Yadong Tian ₁ , Jizhen Ma ₁ , Weijian Guo ₁ , Wenwen Cai ₁ , Jintao Zhang ₁

Affiliation

Single-atom alloys (SAAs) show great potential for a variety of electrocatalytic reactions. However, the atomic orbital hybridization effect of SAAs on the electrochemical reactions is unclear yet. Herein, the in situ confinement of vanadium/molybdenum/tungsten atoms on bismuth nanosheet is shown to create SAAs with rich grain boundaries, respectively. With the detailed analysis of microstructure and composition, the strong p-d orbital hybridization between bismuth and vanadium enables the exceptional electrocatalytic performance for carbon dioxide (CO₂) reduction with the Faradaic efficiency nearly 100% for C1 products in a wide potential range from −0.6 to −1.4 V, and a long-term electrolysis stability for 90 h. In-depth in situ investigations with theoretical computations reveal that the electron delocalization toward vanadium atoms via the p-d orbital hybridization evokes the bismuth active centers for efficient CO₂ activation via the σ-donation of O-to-Bi, thus reduces protonation energy barriers for formate production. With such fundamental understanding, SAA electrocatalyst is employed to fabricated the solar-driven electrolytic cell of CO₂ reduction and 5-hydroxymethylfurfural oxidation, achieving an outstanding 2,5-furandicarboxylic acid yield of 90.5%. This study demonstrates a feasible strategy to rationally design advanced SAA electrocatalysts via the basic principles of p-d orbital hybridization.

中文翻译：

铋纳米片上的强 pd 轨道杂化可实现高性能 CO2 电还原

单原子合金（SAA）在各种电催化反应中表现出巨大的潜力。然而，SAA的原子轨道杂化对电化学反应的影响尚不清楚。在此，钒/钼/钨原子在铋纳米片上的原位限制分别产生了具有丰富晶界的SAA。通过对微观结构和成分的详细分析，铋和钒之间的强pd轨道杂化使得二氧化碳（CO ₂ ）还原具有优异的电催化性能，C1产品在-0.6到宽电位范围内的法拉第效率接近100% -1.4 V，长期电解稳定性90小时。深入的原位研究和理论计算表明，通过pd轨道杂化，电子向钒原子离域，通过O-to-Bi的σ-捐赠，唤起铋活性中心，从而有效激活CO ₂ ，从而降低了质子化能垒甲酸盐生产。有了这样的基础认识，SAA电催化剂被用来制造CO ₂还原和5-羟甲基糠醛氧化的太阳能驱动电解池，实现了高达90.5%的2,5-呋喃二甲酸产率。这项研究展示了一种通过pd轨道杂化的基本原理合理设计先进 SAA 电催化剂的可行策略。

更新日期：2023-11-27

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