Beyond d Orbits: Steering the Selectivity of Electrochemical CO2 Reduction via Hybridized sp Band of Sulfur‐Incorporated Porous Cd Architectures with Dual Collaborative Sites,Advanced Energy Materials

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Beyond d Orbits: Steering the Selectivity of Electrochemical CO2 Reduction via Hybridized sp Band of Sulfur‐Incorporated Porous Cd Architectures with Dual Collaborative Sites
Advanced Energy Materials ( IF 24.4 ) Pub Date : 2020-10-11 , DOI: 10.1002/aenm.202002499
Yunzhen Wu ₁ , Panlong Zhai ₁ , Shuyan Cao ₁ , Zhuwei Li ₁ , Bo Zhang ₁ , Yanting Zhang ₁ , Xiaowa Nie ₁ , Licheng Sun _{1,

2,

3} , Jungang Hou ₁

Affiliation

Electrochemical CO₂ reduction is regarded as a promising strategy for the sustainable conversion of greenhouse gas. However, it still remains a significant challenge to manipulate the selectivity and activity. Herein, amorphous and porous Cd modified by sulfur (P–Cd|S) is synthesized by a p‐block sulfur dopant. In comparison with unmodified Cd metal, the P–Cd|S architecture exhibits superior activity for selective CO generation, indicating that the sulfur dopant enables a selectivity shift from formic acid to CO. The high selectivity of P–Cd|S is partially ascribed to the local alkalization and suppression of hydrogen evolution as indicated by the finite element analysis. In‐depth mechanistic investigations by operando Raman, Infrared, and X‐ray photoelectron spectroscopy in combination with theory calculations indicate that the covalently hybridized sp band system with dual collaborative sites (Cd^δ⁺ and S^δ⁻) gives rise to a strong interplay with CO₂ molecules and carbonaceous species, leading to the natural elimination of linear correlation among intermediates binding for d‐band metals and the convenient modulation of selectivity toward CO versus HCOOH.

中文翻译：

超越d轨道：通过具有双协作位点的硫掺入多孔Cd架构的杂化sp带控制电化学还原CO2的选择性

电化学CO ₂减少被认为是实现温室气体可持续转化的有前途的战略。然而，操纵选择性和活性仍然是一个重大挑战。在此，通过封端硫掺杂剂合成了被硫（P–Cd | S）改性的非晶态和多孔Cd。与未改性的Cd金属相比，P–Cd | S结构表现出优异的选择性CO生成活性，表明硫掺杂剂能够实现从甲酸到CO的选择性转变。P–Cd | S的高选择性部分归因于如有限元分析所示，局部碱化和抑制了氢气的释放。拉曼（Raman），红外线，^δ⁺和S^δ^-）产生与CO强烈相互作用₂分子和碳质物，从而导致线性相关的中间体d带金属和朝向相对于CO的选择性HCOOH的方便调制结合之间的自然淘汰。

更新日期：2020-12-01

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