Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO₂-to-formate conversion

Abstract

Electrocatalytic CO₂-to-formate conversion is considered an economically viable process. In general, Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO₂ to CO, but seldom do they exhibit excellent selectivity toward formate. In this article, we demonstrate that a heterointerface catalyst ZnO/ZnSnO₃ with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency (FE) of 86% at −0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO₂ to formate than pristine ZnO and ZnSnO₃. In particular, the FEs of the C₁ products (CO + HCOO⁻) exceed 98% over the potential window. The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO₃ heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center, which results in moderate Zn–O hybridization of HCOO* and weakened Zn–C hybridization of competing COOH*, thus greatly boosting the HCOOH generation. Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO₂ reduction.

Keywords

charge redistribution / CO₂ reduction reaction / electrocatalyst / heterointerfaces / selectivity

References

[1] Luderer G, Vrontisi Z, Bertram C, et al. Residual fossil CO₂ emissions in 1.5-2℃ pathways. Nat Clim Change. 2018; 8 (7): 626- 633.

[2] Xu D, Li K, Jia B, et al. Electrocatalytic CO₂ reduction towards industrial applications. Carbon Energy. 2023; 5 (1): e230.

[3] Wang K, Du Y, Li Y, et al. Atomic-level insight of sulfidation-engineered Aurivillius-related Bi₂O₂SiO₃ nanosheets enabling visible light low-concentration CO₂ conversion. Carbon Energy. 2023; 5 (2): e264.

[4] Nguyen DLT, Kim Y, Hwang YJ, Won DH. Progress in development of electrocatalyst for CO₂ conversion to selective CO production. Carbon Energy. 2020; 2 (1): 72- 98.

[5] Niu ZZ, Gao FY, Zhang XL, et al. Hierarchical Ccopper with inherent hydrophobicity mitigates electrode flooding for high-rate CO₂ electroreduction to multicarbon products. J Am Chem Soc. 2021; 143 (21): 8011- 8021.

[6] Zhang M, Wei W, Zhou S, et al. Engineering a conductive network of atomically thin bismuthene with rich defects enables CO₂ reduction to formate with industry-compatible current densities and stability. Energy Environ Sci. 2021; 14 (9): 4998- 5008.

[7] Dong WJ, Navid IA, Xiao Y, Lim JW, Lee JL, Mi Z. CuS-decorated GaN nanowires on silicon photocathodes for converting CO₂ mixture gas to HCOOH. J Am Chem Soc. 2021; 143 (27): 10099- 10107.

[8] Zhu QL, Xu Q. Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage. Energy Environ Sci. 2015; 8 (2): 478- 512.

[9] Chen M, Wan S, Zhong L, et al. Dynamic restructuring of Cu-doped SnS₂ nanoflowers for highly selective electrochemical CO₂ reduction to formate. Angew Chem Int Ed. 2021; 60 (50): 26233- 26237.

[10] Hori Y, Wakebe H, Tsukamoto T, Koga O. Electrocatalytic process of CO selectivity in electrochemical reduction of CO₂ at metal electrodes in aqueous media. Electrochim Acta. 1994; 39 (11-12): 1833- 1839.

[11] Zhang S, Kang P, Meyer TJ. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate. J Am Chem Soc. 2014; 136 (5): 1734- 1737.

[12] Deng W, Zhang L, Li L, et al. Crucial role of surface hydroxyls on the activity and stability in electrochemical CO₂ reduction. J Am Chem Soc. 2019; 141 (7): 2911- 2915.

[13] Zhang Z, Wen G, Luo D, et al. “Two Ships in a Bottle” design for Zn-Ag-O catalyst enabling selective and long-lasting CO₂ electroreduction. J Am Chem Soc. 2021; 143 (18): 6855- 6864.

[14] Geng Z, Kong X, Chen W, et al. Oxygen vacancies in ZnO nanosheets enhance CO₂ electrochemical reduction to CO. Angew Chem Int Ed. 2018; 57 (21): 6054- 6059.

[15] Xiang Q, Li F, Wang J, et al. Heterostructure of ZnO nanosheets/Zn with a highly enhanced edge surface for efficient CO₂ electrochemical reduction to CO. ACS Appl Mater Interfaces. 2021; 13 (9): 10837- 10844.

[16] Li X, He W, Li C, Song B, Liu S. Synergetic surface modulation of ZnO/Pt@ZIF-8 hybrid nanorods for enhanced photocatalytic CO₂ valorization. Appl Catal B. 2021; 287: 119934.

[17] Lee KY, Kim D, Lee J-H, Kim TY, Gupta MK, Kim S-W. Unidirectional high-power generation via stress-induced dipole alignment from ZnSnO₃ nanocubes/polymer hybrid piezoelectric nanogenerator. Adv Funct Mater. 2014; 24 (1): 37- 43.

[18] He Y, Jiang W-J, Zhang Y, Huang L-B, Hu J-S. Pore-structure-directed CO₂ electroreduction to formate on SnO₂/C catalysts. J Mater Chem A. 2019; 7 (31): 18428- 18433.

[19] Chen H, Liang X, Liu Y, Ai X, Asefa T, Zou X. Active site engineering in porous electrocatalysts. Adv Mater. 2020; 32 (44): 2002435.

[20] Zhang J, Shao S, Zhou D, Xu Q, Wang T. ZnO nanowire arrays decorated 3D N-doped reduced graphene oxide nanotube framework for enhanced photocatalytic CO₂ reduction performance. J CO2 Util. 2021; 50: 101584.

[21] Hu C, Chen L, Hu Y, et al. Light-motivated SnO₂/TiO₂ heterojunctions enabling the breakthrough in energy density for lithium-ion batteries. Adv Mater. 2021; 33 (49): 2103558.

[22] Lei F, Sun Y, Liu K, et al. Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting. J Am Chem Soc. 2014; 136 (19): 6826- 6829.

[23] Gu Z, Yang N, Han P, et al. Oxygen vacancy tuning toward efficient electrocatalytic CO₂ reduction to C₂H₄. Small Methods. 2018; 3 (2): 1800449.

[24] Daiyan R, Lovell EC, Huang B, et al. Uncovering atomic-scale stability and reactivity in engineered zinc oxide electrocatalysts for controllable syngas production. Adv Energy Mater. 2020; 10 (28): 2001381.

[25] Li L, Zhao Z-J, Hu C, et al. Tuning oxygen vacancies of oxides to promote electrocatalytic reduction of carbon dioxide. ACS Energy Lett. 2020; 5 (2): 552- 558.

[26] Li H, Xiao N, Wang Y, et al. Promoting the electroreduction of CO₂ with oxygen vacancies on a plasma-activated SnO_x/carbon foam monolithic electrode. J Mater Chem A. 2020; 8 (4): 1779- 1786.

[27] Guo F, Huang X, Chen Z, Sun H, Shi W. Investigation of visible-light-driven photocatalytic tetracycline degradation via carbon dots modified porous ZnSnO₃ cubes: mechanism and degradation pathway. Sep Purif Technol. 2020; 253: 117518.

[28] Peisert H, Kolacyak D, Chassé T. Site-specific charge-transfer screening at organic/metal interfaces. J Phys Chem C. 2009; 113 (44): 19244- 19250.

[29] Salusso D, Borfecchia E, Bordiga S. Combining X-ray diffraction and X-ray absorption spectroscopy to unveil Zn local environment in Zn-doped ZrO₂ catalysts. J Phys Chem C. 2021; 125 (40): 22249- 22261.

[30] Zhang L, Li XX, Lang ZL, et al. Enhanced cuprophilic interactions in crystalline catalysts facilitate the highly selective electroreduction of CO₂ to CH₄. J Am Chem Soc. 2021; 143 (10): 3808- 3816.

[31] Wang Q, Huang X, Zhao ZL, et al. Ultrahigh-loading of Ir single atoms on NiO matrix to dramatically enhance oxygen evolution reaction. J Am Chem Soc. 2020; 142 (16): 7425- 7433.

[32] Li G, Jang H, Liu S, et al. The synergistic effect of Hf-O-Ru bonds and oxygen vacancies in Ru/HfO₂ for enhanced hydrogen evolution. Nat Commun. 2022; 13: 1270.

[33] Ji Y, Chen Z, Wei R, et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu-Pd sites. Nat Catal. 2022; 5 (4): 251- 258.

[34] Jiang X, Jang H, Liu S, et al. The heterostructure of Ru₂P/WO₃/NPC synergistically promotes H₂O dissociation for improved hydrogen. Angew Chem Int Ed. 2021; 60 (8): 4110- 4116.

[35] Li Z, Cao A, Zheng Q, et al. Elucidation of the synergistic effect of dopants and vacancies on promoted selectivity for CO₂ electroreduction to formate. Adv Mater. 2021; 33 (2): 2005113.

[36] Dunwell M, Lu Q, Heyes JM, et al. The central role of bicarbonate in the electrochemical reduction of carbon dioxide on gold. J Am Chem Soc. 2017; 139 (10): 3774- 3783.

[37] Jiao L, Zhu J, Zhang Y, et al. Non-bonding interaction of neighboring Fe and Ni single-atom pairs on MOF-derived N-doped carbon for enhanced CO₂ electroreduction. J Am Chem Soc. 2021; 143 (46): 19417- 19424.

[38] Chen D, Wang Y, Liu D, et al. Surface composition dominates the electrocatalytic reduction of CO₂ on ultrafine CuPd nanoalloys. Carbon Energy. 2020; 2 (3): 443- 451.

[39] Stamenkovic V, Mun BS, Mayrhofer KJJ, et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew Chem. 2006; 118 (18): 2963- 2967.

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