{"title":"在多孔掺氮碳纳米纤维上整合 Cu+/Cu0 位点,稳定高效地将二氧化碳电还原为多碳产品","authors":"","doi":"10.1016/j.jechem.2024.09.059","DOIUrl":null,"url":null,"abstract":"<div><div>The Cu<sup>+</sup>/Cu<sup>0</sup> sites of copper-based catalysts are crucial for enhancing the production of multicarbon (C<sub>2+</sub>) products from electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR). However, the unstable Cu<sup>+</sup> and insufficient Cu<sup>+</sup>/Cu<sup>0</sup> active sites lead to their limited selectivity and stability for C<sub>2+</sub> production. Herein, we embedded copper oxide (CuO<em><sub>x</sub></em>) particles into porous nitrogen-doped carbon nanofibers (CuO<em><sub>x</sub></em>@PCNF) by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu<sub>2</sub>O particles. The porous nitrogen-doped carbon nanofibers protected and dispersed Cu<sup>+</sup> species, and its microporous structure enhanced the interaction between CuO<em><sub>x</sub></em> and reactants during eCO<sub>2</sub>RR. The obtained CuO<em><sub>x</sub></em>@PCNF created more effective and stable Cu<sup>+</sup>/Cu<sup>0</sup> active sites. It showed a high Faradaic efficiency of 62.5% for C<sub>2+</sub> products in H-cell, which was 2 times higher than that of bare CuO<em><sub>x</sub></em> (∼31.1%). Furthermore, it achieved a maximum Faradaic efficiency of 80.7% for C<sub>2+</sub> products in flow cell. In situ characterization and density functional theory (DFT) calculation confirmed that the N-doped carbon layer protected Cu<sup>+</sup> from electrochemical reduction and lowered the energy barrier for the dimerization of *CO. Stable and exposed Cu<sup>+</sup>/Cu<sup>0</sup> active sites enhanced the enrichment of *CO and promoted the C–C coupling reaction on the catalyst surface, which facilitated the formation of C<sub>2+</sub> products.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1000,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Integrating Cu+/Cu0 sites on porous nitrogen-doped carbon nanofibers for stable and efficient CO2 electroreduction to multicarbon products\",\"authors\":\"\",\"doi\":\"10.1016/j.jechem.2024.09.059\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The Cu<sup>+</sup>/Cu<sup>0</sup> sites of copper-based catalysts are crucial for enhancing the production of multicarbon (C<sub>2+</sub>) products from electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR). However, the unstable Cu<sup>+</sup> and insufficient Cu<sup>+</sup>/Cu<sup>0</sup> active sites lead to their limited selectivity and stability for C<sub>2+</sub> production. Herein, we embedded copper oxide (CuO<em><sub>x</sub></em>) particles into porous nitrogen-doped carbon nanofibers (CuO<em><sub>x</sub></em>@PCNF) by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu<sub>2</sub>O particles. The porous nitrogen-doped carbon nanofibers protected and dispersed Cu<sup>+</sup> species, and its microporous structure enhanced the interaction between CuO<em><sub>x</sub></em> and reactants during eCO<sub>2</sub>RR. The obtained CuO<em><sub>x</sub></em>@PCNF created more effective and stable Cu<sup>+</sup>/Cu<sup>0</sup> active sites. It showed a high Faradaic efficiency of 62.5% for C<sub>2+</sub> products in H-cell, which was 2 times higher than that of bare CuO<em><sub>x</sub></em> (∼31.1%). Furthermore, it achieved a maximum Faradaic efficiency of 80.7% for C<sub>2+</sub> products in flow cell. In situ characterization and density functional theory (DFT) calculation confirmed that the N-doped carbon layer protected Cu<sup>+</sup> from electrochemical reduction and lowered the energy barrier for the dimerization of *CO. Stable and exposed Cu<sup>+</sup>/Cu<sup>0</sup> active sites enhanced the enrichment of *CO and promoted the C–C coupling reaction on the catalyst surface, which facilitated the formation of C<sub>2+</sub> products.</div></div>\",\"PeriodicalId\":15728,\"journal\":{\"name\":\"Journal of Energy Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2024-10-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Energy Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2095495624006958\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"Energy\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495624006958","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
Integrating Cu+/Cu0 sites on porous nitrogen-doped carbon nanofibers for stable and efficient CO2 electroreduction to multicarbon products
The Cu+/Cu0 sites of copper-based catalysts are crucial for enhancing the production of multicarbon (C2+) products from electrochemical CO2 reduction reaction (eCO2RR). However, the unstable Cu+ and insufficient Cu+/Cu0 active sites lead to their limited selectivity and stability for C2+ production. Herein, we embedded copper oxide (CuOx) particles into porous nitrogen-doped carbon nanofibers (CuOx@PCNF) by pyrolysis of the electrospun fiber film containing ZIF-8 and Cu2O particles. The porous nitrogen-doped carbon nanofibers protected and dispersed Cu+ species, and its microporous structure enhanced the interaction between CuOx and reactants during eCO2RR. The obtained CuOx@PCNF created more effective and stable Cu+/Cu0 active sites. It showed a high Faradaic efficiency of 62.5% for C2+ products in H-cell, which was 2 times higher than that of bare CuOx (∼31.1%). Furthermore, it achieved a maximum Faradaic efficiency of 80.7% for C2+ products in flow cell. In situ characterization and density functional theory (DFT) calculation confirmed that the N-doped carbon layer protected Cu+ from electrochemical reduction and lowered the energy barrier for the dimerization of *CO. Stable and exposed Cu+/Cu0 active sites enhanced the enrichment of *CO and promoted the C–C coupling reaction on the catalyst surface, which facilitated the formation of C2+ products.
期刊介绍:
The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies.
This journal focuses on original research papers covering various topics within energy chemistry worldwide, including:
Optimized utilization of fossil energy
Hydrogen energy
Conversion and storage of electrochemical energy
Capture, storage, and chemical conversion of carbon dioxide
Materials and nanotechnologies for energy conversion and storage
Chemistry in biomass conversion
Chemistry in the utilization of solar energy