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Oxidation of metallic Cu by supercritical CO₂ and control synthesis of amorphous nano-metal catalysts for CO₂ electroreduction.

ABSTRACT: Amorphous nano-metal catalysts often exhibit appealing catalytic properties, because the intrinsic linear scaling relationship can be broken. However, accurate control synthesis of amorphous nano-metal catalysts with desired size and morphology is a challenge. In this work, we discover that Cu(0) could be oxidized to amorphous Cu_xO species by supercritical CO₂. The formation process of the amorphous Cu_xO is elucidated with the aid of machine learning. Based on this finding, a method to prepare Cu nanoparticles with an amorphous shell is proposed by supercritical CO₂ treatment followed by electroreduction. The unique feature of this method is that the size of the particles with amorphous shell can be easily controlled because their size depends on that of the original crystal Cu nanoparticles. Moreover, the thickness of the amorphous shell can be easily controlled by CO₂ pressure and/or treatment time. The obtained amorphous Cu shell exhibits high selectivity for C2+ products with the Faradaic efficiency of 84% and current density of 320 mA cm^-2. Especially, the FE of C2+ oxygenates can reach up to 65.3 %, which is different obviously from the crystalline Cu catalysts.

SUBMITTER: Chen C

PROVIDER: S-EPMC9968285 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Oxidation of metallic Cu by supercritical CO2 and control synthesis of amorphous nano-metal catalysts for CO2 electroreduction.

Chen Chunjun C Yan Xupeng X Wu Yahui Y Zhang Xiudong X Liu Shoujie S Zhang Fanyu F Sun Xiaofu X Zhu Qinggong Q Zheng Lirong L Zhang Jing J Xing Xueqing X Wu Zhonghua Z Han Buxing B

Nature communications 20230225 1

Amorphous nano-metal catalysts often exhibit appealing catalytic properties, because the intrinsic linear scaling relationship can be broken. However, accurate control synthesis of amorphous nano-metal catalysts with desired size and morphology is a challenge. In this work, we discover that Cu(0) could be oxidized to amorphous CuxO species by supercritical CO2. The formation process of the amorphous CuxO is elucidated with the aid of machine learning. Based on th ...[more]

PMID: 36841816

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Project description:To address the challenge of selectivity toward single products in Cu-catalyzed electrochemical CO2 reduction, one strategy is to incorporate a second metal with the goal of tuning catalytic activity via synergy effects. In particular, catalysts based on Cu modified with post-transition metals (Sn or In) are known to reduce CO2 selectively to either CO or HCOO- depending on their composition. However, it remains unclear exactly which factors induce this switch in reaction pathways and whether these two related bimetal combinations follow similar general structure-activity trends. To investigate these questions systematically, Cu-In and Cu-Sn bimetallic catalysts were synthesized across a range of composition ratios and studied in detail. Compositional and morphological control was achieved via a simple electrochemical synthesis approach. A combination of operando and quasi-in situ spectroscopic techniques, including X-ray photoelectron, X-ray absorption, and Raman spectroscopy, was used to observe the dynamic behaviors of the catalysts' surface structure, composition, speciation, and local environment during CO2 electrolysis. The two systems exhibited similar selectivity dependency on their surface composition. Cu-rich catalysts produce mainly CO, while Cu-poor catalysts were found to mainly produce HCOO-. Despite these similarities, the speciation of Sn and In at the surface differed from each other and was found to be strongly dependent on the applied potential and the catalyst composition. For Cu-rich compositions optimized for CO production (Cu85In15 and Cu85Sn15), indium was present predominantly in the reduced metallic form (In0), whereas tin mainly existed as an oxidized species (Sn2/4+). Meanwhile, for the HCOO--selective compositions (Cu25In75 and Cu40Sn60), the indium exclusively exhibited In0 regardless of the applied potential, while the tin was reduced to metallic (Sn0) only at the most negative applied potential, which corresponds to the best HCOO- selectivity. Furthermore, while Cu40Sn60 enhances HCOO- selectivity by inhibiting H2 evolution, Cu25In75 improves the HCOO- selectivity at the expense of CO production. Due to these differences, we contend that identical mechanisms cannot be used to explain the behavior of these two bimetallic systems (Cu-In and Cu-Sn). Operando surface-enhanced Raman spectroscopy measurements provide direct evidence of the local alkalization and its impact on the dynamic transformation of oxidized Cu surface species (Cu2O/CuO) into a mixture of Cu(OH)2 and basic Cu carbonates [Cux(OH)y(CO3)y] rather than metallic Cu under CO2 electrolysis. This study provides unique insights into the origin of the switch in selectivity between CO and HCOO- pathways at Cu bimetallic catalysts and the nature of surface-active sites and key intermediates for both pathways.

Dataset Information

Oxidation of metallic Cu by supercritical CO₂ and control synthesis of amorphous nano-metal catalysts for CO₂ electroreduction.

Publications

Oxidation of metallic Cu by supercritical CO<sub>2</sub> and control synthesis of amorphous nano-metal catalysts for CO<sub>2</sub> electroreduction.

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