Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO<sub>2</sub> electroreduction using tailored Cu/ZnO precatalysts

Varandili, Seyedeh Behnaz; Stoian, Dragos; Vávra, Jan; Rossi, Kevin; Pankhurst, James R.; Guntern, Yannick T.; López, Núria; Buonsanti, Raffaella

doi:10.1039/d1sc04271h

Cited by 49 publications

(48 citation statements)

References 49 publications

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“…Hence, the enriched ZnO surface increases the local CO concentration, allowing a higher formation of the key CO-adsorbed intermediate (*CO) at the Cu +1 /Cu 0 interface that, subsequently, is transformed by dimerization reactions (namely, *CO–*CO or *CHx–*CO) into C 2+ products like ethanol. 42 , 52 , 53 These findings agree with a recent work on ZnO@Cu-derived and Cu@ZnO-derived catalysts that showed selectivity for ethanol and methane, respectively. Experimental results and DFT simulations show that a higher Zn content increases the local CO concentration and enables a tandem conversion mechanism, determining the selectivity shift from CH 4 to ethanol.…”

Section: Resultssupporting

confidence: 91%

“…Experimental results and DFT simulations show that a higher Zn content increases the local CO concentration and enables a tandem conversion mechanism, determining the selectivity shift from CH 4 to ethanol. 52 Similarly, it was found an enhanced ethanol selectivity at the terraces of a Cu–Ag bimetallic system, via a *CHx–*CO coupling pathway, because of the CO-enriched environment generated by Ag nanospheres. 53 …”

Section: Resultsmentioning

confidence: 93%

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CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

Guzmán

Salomone

Bensaid

et al. 2021

ACS Appl. Mater. Interfaces

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The development of efficient catalysts is one of the main challenges in CO 2 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 CO 2 via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO 2 reduction to reduce the kinetic barrier and enhance C–C coupling to obtain C 2+ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·g cat –1 ·h –1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C 1 products like formate and methanol. During CO 2 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·g cat –1 ·h –1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu 1+ /Cu 0 interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu 0 and crystalline ZnO prevailed under CO 2 hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu 0 catalyst surface in the TC process than in the Cu 1+ 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 Cu 1+ + Cu 0 species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C 2+ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO 2 conversion products.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 93%

CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

Guzmán

Salomone

Bensaid

et al. 2021

ACS Appl. Mater. Interfaces

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“…We further performed stability tests (Figure S25), which showed a decrease in the C 2 + products selectivity, accompanied by a gradual increase in the H 2 selectivity. This is probably caused by the fact that some Zn elements leach into the electrolyte, [8,23] leading to a decrease in the proportion of Zn elements on the catalyst surface, which was also confirmed by our results of XPS after the reaction (Figure S21).…”

Section: Methodssupporting

confidence: 78%

“…Among all Cu‐based bimetallic catalysts investigated, CuZn nanoparticles (NPs) catalyst have been considered as alternatives of precious CuAu and CuAg catalysts because of its eco‐friendly and cost‐efficient [7] . For example, Cu x Zn y catalysts facilitate the formation of C 2 products through promoting the dimerization of two neighboring *CO intermediates on the surface of Cu [7d, 8] …”

Section: Figurementioning

confidence: 99%

Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

et al. 2022

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The electrochemical CO 2 reduction (CO 2 ER) to multi-carbon chemical feedstocks over Cu-based catalysts is of considerable attraction but suffers with the ambiguous nature of active sites, which hinder the rational design of catalysts and large-scale industrialization. This paper describes a large-scale simulation to obtain realistic CuZn nanoparticle models and the atom-level structure of active sites for C 2 + products on CuZn catalysts in CO 2 ER, combining neural network based global optimization and density functional theory calculations. Upon analyzing over 2000 surface sites through high throughput tests based on NN potential, two kinds of active sites are identified, balanced CuÀ Zn sites and Zn-heavy CuÀ Zn sites, both facilitating CÀ C coupling, which are verified by subsequent calculational and experimental investigations. This work provides a paradigm for the design of high-performance Cu-based catalysts and may offer a general strategy to identify accurately the atomic structures of active sites in complex catalytic systems.

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“…Our incomplete understanding of these processes hinders the design of novel CO 2 RR catalysts. There, the restructuring of the catalyst due to alloying processes, 23 different reduction rates for CuO x and ZnO species and their different stability contribute to the time dependencies of the activity and selectivity under reaction conditions. 13 Therefore, it is imperative to monitor the presence of the desired bimetallic motifs under catalysts' working conditions by using suitable operando techniques, such as X-ray absorption spectroscopy (XAS).…”

Section: Introductionmentioning

confidence: 99%

Tracking heterogeneous structural motifs and the redox behaviour of copper–zinc nanocatalysts for the electrocatalytic CO₂ reduction using operando time resolved spectroscopy and machine learning

Rüscher

Herzog

Timoshenko

et al. 2022

Catal. Sci. Technol.

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Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO₂ electroreduction using tailored Cu/ZnO precatalysts

Abstract: Understanding the catalyst compositional and structural features that control selectivity is of the uttermost importance to target desired products in chemical reactions. In this joint experimental-computational work, we leverage tailored...

Cited by 49 publications

References 49 publications

CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

Tracking heterogeneous structural motifs and the redox behaviour of copper–zinc nanocatalysts for the electrocatalytic CO₂ reduction using operando time resolved spectroscopy and machine learning

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Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO2 electroreduction using tailored Cu/ZnO precatalysts

Abstract: Understanding the catalyst compositional and structural features that control selectivity is of the uttermost importance to target desired products in chemical reactions. In this joint experimental-computational work, we leverage tailored...

Cited by 49 publications

References 49 publications

CO2 Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

CO2 Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

Tracking heterogeneous structural motifs and the redox behaviour of copper–zinc nanocatalysts for the electrocatalytic CO2 reduction using operando time resolved spectroscopy and machine learning

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Product

Resources

About

Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO₂ electroreduction using tailored Cu/ZnO precatalysts

CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

CO₂ Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes

Tracking heterogeneous structural motifs and the redox behaviour of copper–zinc nanocatalysts for the electrocatalytic CO₂ reduction using operando time resolved spectroscopy and machine learning