Mao Tingjie, Chen Jiadong, Wang Ren, Yang Zhenrui, Han Xiang, Huang Jinglian, Dong Siyuan, Wang Juan, Jin Huile, Wang Shun
Wenzhou Key Lab of Advanced Energy Storage and Conversion, Zhejiang Province Key Lab of Leather Engineering, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China.
Inorg Chem. 2024 Jun 10;63(23):10809-10816. doi: 10.1021/acs.inorgchem.4c01517. Epub 2024 May 30.
Electrochemically converting carbon dioxide (CO) into valuable fuels and renewable chemical feedstocks is considered a highly promising approach to achieve carbon neutrality. In this work, a robust interfacial built-in electric field (BEF) has been successfully designed and created in Bi/BiTe nanowires (NWs). The Bi/BiTe NWs consistently maintain over 90% Faradaic efficiency (FE) within a wide potential range (-0.8 to -1.2 V), with HCOOH selectivity reaching 97.2% at -1.0 V. Moreover, the FE of Bi/BiTe NWs can still reach 94.3% at a current density of 100 mA cm when it is used as a cathode electrocatalyst in a flow-cell system. Detailed experiments confirm that the presence of interfacial BEF between Bi and Bi/BiTe promotes the formation of OHCO intermediates, thus facilitating the production of HCOOH species. DFT calculations show that Bi/BiTe NWs increase the formation energies of H and *COOH while reducing the energy barrier for *OCHO formation, thus achieving a bidirectional optimization of intermediate adsorption. This work provides a feasible scheme for exploring electrocatalytic reaction intermediates by using the BEF strategy.
将二氧化碳(CO₂)电化学转化为有价值的燃料和可再生化学原料被认为是实现碳中和的一种极具前景的方法。在这项工作中,已成功在Bi/Bi₂Te纳米线(NWs)中设计并创建了强大的界面内建电场(BEF)。Bi/Bi₂Te NWs在很宽的电位范围内(-0.8至-1.2 V)始终保持超过90%的法拉第效率(FE),在-1.0 V时HCOOH选择性达到97.2%。此外,当Bi/Bi₂Te NWs在流动池系统中用作阴极电催化剂时,在电流密度为100 mA cm⁻²时其FE仍可达到94.3%。详细实验证实,Bi与Bi/Bi₂Te之间界面BEF的存在促进了OHCO中间体的形成,从而有利于HCOOH物种的产生。密度泛函理论(DFT)计算表明,Bi/Bi₂Te NWs增加了H和COOH的形成能,同时降低了OCHO形成的能垒,从而实现了中间体吸附的双向优化。这项工作为利用BEF策略探索电催化反应中间体提供了一个可行的方案。