Dataset Information

Electrocatalytic CO₂ reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes.

ABSTRACT: Electrocatalytic reduction of CO₂ into alcohols of high economic value offers a promising route to realize resourceful CO₂ utilization. In this study, we choose three model bicentric copper complexes based on the expanded and fluorinated porphyrin structure, but different spatial and coordination geometry, to unravel their structure-property-performance correlation in catalyzing electrochemical CO₂ reduction reactions. We show that the complexes with higher intramolecular tension and coordination asymmetry manifests a lower electrochemical stability and thus more active Cu centers, which can be reduced during electrolysis to form Cu clusters accompanied by partially-reduced or fragmented ligands. We demonstrate the hybrid structure of Cu cluster and partially reduced O-containing hexaphyrin ligand is highly potent in converting CO₂ into alcohols, up to 32.5% ethanol and 18.3% n-propanol in Faradaic efficiencies that have been rarely reported. More importantly, we uncover an interplay between the inorganic and organic phases to synergistically produce alcohols, of which the intermediates are stabilized by a confined space to afford extra O-Cu bonding. This study underlines the exploitation of structure-dependent electrochemical property to steer the CO₂ reduction pathway, as well as a potential generic tactic to target alcohol synthesis by constructing organic/inorganic Cu hybrids.

SUBMITTER: Yang B

PROVIDER: S-EPMC9433389 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Electrocatalytic CO2 reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes.

Yang Baiyu B Chen Ling L Xue Songlin S Sun Hao H Feng Kun K Chen Yufeng Y Zhang Xiang X Xiao Long L Qin Yongze Y Zhong Jun J Deng Zhao Z Jiao Yan Y Peng Yang Y

Nature communications 20220831 1

Electrocatalytic reduction of CO2 into alcohols of high economic value offers a promising route to realize resourceful CO2 utilization. In this study, we choose three model bicentric copper complexes based on the expanded and fluorinated porphyrin structure, but different spatial and coordination geometry, to unravel their structure-property-performance correlation in catalyzing electrochemical CO2 reduction reactions. We show that the complexes with higher intra ...[more]

PMID: 36045126

Similar Datasets

Project description:The development of efficient catalysts is one of the main challenges in CO2 conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu+1 were studied to convert CO2 via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO2 reduction to reduce the kinetic barrier and enhance C-C coupling to obtain C2+ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·gcat-1·h-1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C1 products like formate and methanol. During CO2 hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·gcat-1·h-1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu1+/Cu0 interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu0 and crystalline ZnO prevailed under CO2 hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu0 catalyst surface in the TC process than in the Cu1+ present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu1+ + Cu0 species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C2+ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO2 conversion products.

Dataset Information

Electrocatalytic CO₂ reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes.

Publications

Electrocatalytic CO<sub>2</sub> reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets