Murugesan Panneerselvam, Marcelo Albuquerque, Iuri Soter Viana Segtovich, Frederico W. Tavares, Luciano T. Costa
{"title":"研究二氧化碳电还原机制:通过氢气进化反应、可行性和选择性考虑,对二氧化碳转化的富土二亚胺锰催化剂进行 DFT 深入研究","authors":"Murugesan Panneerselvam, Marcelo Albuquerque, Iuri Soter Viana Segtovich, Frederico W. Tavares, Luciano T. Costa","doi":"10.1007/s11705-024-2502-5","DOIUrl":null,"url":null,"abstract":"<div><p>This study investigates the detailed mechanism of CO<sub>2</sub> conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)<sub>3</sub>Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO<sub>2</sub> reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO<sub>2</sub> reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO<sub>2</sub> fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO<sub>2</sub> reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO<sub>2</sub> conversion to CO over H<sub>2</sub> evolution due to the higher energy barrier in forming the Mn-H<sub>2</sub> species during H<sub>2</sub> production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO<sub>2</sub> reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO<sub>2</sub> reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)<sub>3</sub>Br] toward CO production over HCOO<sup>−</sup> and H<sub>2</sub> formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":571,"journal":{"name":"Frontiers of Chemical Science and Engineering","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Investigating CO2 electro-reduction mechanisms: DFT insight into earth-abundant Mn diimine catalysts for CO2 conversions over hydrogen evolution reaction, feasibility, and selectivity considerations\",\"authors\":\"Murugesan Panneerselvam, Marcelo Albuquerque, Iuri Soter Viana Segtovich, Frederico W. Tavares, Luciano T. Costa\",\"doi\":\"10.1007/s11705-024-2502-5\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>This study investigates the detailed mechanism of CO<sub>2</sub> conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)<sub>3</sub>Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO<sub>2</sub> reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO<sub>2</sub> reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO<sub>2</sub> fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO<sub>2</sub> reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO<sub>2</sub> conversion to CO over H<sub>2</sub> evolution due to the higher energy barrier in forming the Mn-H<sub>2</sub> species during H<sub>2</sub> production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO<sub>2</sub> reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO<sub>2</sub> reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)<sub>3</sub>Br] toward CO production over HCOO<sup>−</sup> and H<sub>2</sub> formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":571,\"journal\":{\"name\":\"Frontiers of Chemical Science and Engineering\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Frontiers of Chemical Science and Engineering\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11705-024-2502-5\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Frontiers of Chemical Science and Engineering","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s11705-024-2502-5","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0
摘要
本研究利用 Christoph Steinlechner 及其同事合成的二(I)亚胺锰电催化剂 [Mn(pyrox)(CO)3Br],研究了将 CO2 转化为 CO 的详细机理。利用密度泛函理论计算,我们深入探讨了二氧化碳还原与竞争性氢进化反应的电催化途径。我们的分析揭示了二亚胺氮配位在提高锰中心电子密度方面的重要作用,从而在热力学上有利于二氧化碳还原和氢进化反应。此外,我们还观察到三乙醇胺(TEOA)稳定了过渡态,有助于二氧化碳的固定和还原。影响反应速率的关键步骤包括在二氧化碳还原过程中断开 MnC(O)-OH 键,以及在氢演化反应中裂解 MnH-H-TEOA 键。我们解释了二氧化碳转化为一氧化碳比氢气进化更优先的原因,因为在产生氢气的过程中形成 Mn-H2 物种的能量障碍更高。我们的研究结果表明,可以通过调整 Mn 中心的电子密度来提高二氧化碳还原反应的活性和选择性。此外,我们还分析了潜在的竞争反应,重点是二氧化碳还原的电催化过程,并通过对氧化还原电势和吉布斯自由能的密度泛函理论计算,评估了 "质子化优先 "和 "还原优先 "的途径。分析表明,"还原优先 "途径在 CO 生成中占主导地位,尤其是在高电势条件下。此外,我们的研究还强调了[Mn(pyrox)(CO)3Br]对 CO 生成的选择性,而不是对 HCOO- 和 H2 生成的选择性,这为今后的研究提出了途径,即通过使用更大的基集和探索更多的功能化配体来扩展这些发现。
Investigating CO2 electro-reduction mechanisms: DFT insight into earth-abundant Mn diimine catalysts for CO2 conversions over hydrogen evolution reaction, feasibility, and selectivity considerations
This study investigates the detailed mechanism of CO2 conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)3Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO2 reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO2 reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO2 fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO2 reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO2 conversion to CO over H2 evolution due to the higher energy barrier in forming the Mn-H2 species during H2 production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO2 reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO2 reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)3Br] toward CO production over HCOO− and H2 formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.
期刊介绍:
Frontiers of Chemical Science and Engineering presents the latest developments in chemical science and engineering, emphasizing emerging and multidisciplinary fields and international trends in research and development. The journal promotes communication and exchange between scientists all over the world. The contents include original reviews, research papers and short communications. Coverage includes catalysis and reaction engineering, clean energy, functional material, nanotechnology and nanoscience, biomaterials and biotechnology, particle technology and multiphase processing, separation science and technology, sustainable technologies and green processing.