Quantitative Unraveling of Exsolved Heteroboundaries for High-Temperature Electrocatalysis

Xiaoxin Zhang; Xiao Xiao; Qiuyue Zhang; Zhou Chen; Chang Jiang; Mingshu Chen; Ning Yan; Shidi Mo; Meng Wu; Jianhui Li; Jijie Huang; Abdullah N Alodhayb; Xianzhu Fu; Min Chen; Xinchun Lv; Yifei Sun

doi:10.1021/jacs.4c11274

Quantitative Unraveling of Exsolved Heteroboundaries for High-Temperature Electrocatalysis

J Am Chem Soc. 2024 Nov 27. doi: 10.1021/jacs.4c11274. Online ahead of print.

Authors

Xiaoxin Zhang¹, Xiao Xiao¹, Qiuyue Zhang², Zhou Chen³, Chang Jiang¹, Mingshu Chen², Ning Yan⁴, Shidi Mo⁵, Meng Wu⁵, Jianhui Li⁶, Jijie Huang⁷, Abdullah N Alodhayb⁸, Xianzhu Fu⁹, Min Chen¹⁰, Xinchun Lv¹¹, Yifei Sun^{1

2

12

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Affiliations

¹ College of Energy, Xiamen University, Xiamen 361005, China.
² State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, China.
³ College of Materials, Key Laboratory of High Performance Ceramic Fibers (Xiamen University), Ministry of Education, Xiamen University, Xiamen 361005, China.
⁴ School of Physics and Technology, Wuhan University, Wuhan 430072, China.
⁵ College of Chemistry and Chemical Engineering, National Engineering Research Center of Chemicals for Electronics Manufacturing (Reconstruction), Xiamen University, Xiamen 361005, China.
⁶ Fujian Key Laboratory of Semiconductor Materials and Applications, CI Center for OSED, and Department of Physics, Xiamen University, Xiamen 361005, China.
⁷ School of Materials, Shenzhen Campus of Sun Yat-sen University, Shenzhen 518107, China.
⁸ Department of Physics and Astronomy, College of Science, King Abdullah Institute for Nanotechnology, King Saud University, Riyadh 11451, Saudi Arabia.
⁹ Shenzhen Key Laboratory of Energy Electrocatalytic Materials, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, China.
¹⁰ School of Materials and Energy, Foshan University, Foshan 528000, China.
¹¹ LUXI Chemical Group Co., Ltd., Liaocheng 252211, China.
¹² Shenzhen Research Institute of Xiamen University, Shenzhen 18057, China.
¹³ Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, China.

PMID: 39601630
DOI: 10.1021/jacs.4c11274

Abstract

The application of perovskite oxide for high-temperature electrocatalysis is hindered by its limited activity. Exsolution is a smart strategy that allows the enrichment of the perovskite's surface with highly reactive phases, yielding heteroboundaries. However, the identification of the exact catalytic role of this complex architecture is still elusive. Here we presented a quantitative analysis of the CO₂ electroreduction reactivity of a series of perovskite thin film platforms (La_0.4Ca_0.4Ti_0.94Ni_0.06O₃, LCTN) boosted by exsolved heteropical nanoparticles (particularly for Ni and NiO). The cross-scale electrochemical characterizations, together with density functional theory (DFT) modelings, have shown clear evidence that the boundary length of the NP/perovskite interface is strictly correlated with the CO₂RR activity. The intrinsic reaction rate per active site at the NiO/LCTN boundary demonstrates a highest turnover frequency (TOF) of 7.05 ± 0.75 × 104 s^-1 at 800 °C, which is 2.5 times and 4 orders of magnitude better than that of Ni/LCTN and LCTN, respectively. The ab initio molecular dynamics (AIMD) proves that the CO₂ absorption at the NiO/LCTN boundary leverages a bidentate carbonate modality with a reduced dissociation energy barrier. Moreover, a multifold enhancement in oxygen exchange rate was confirmed, which correlated to the facilitated oxygen ion hopping between adjacent TiO₆ octahedrons. Further near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) during CO₂ electrolysis on model electrolyzers reveals the crucial role of the NiO/LCTN boundary in stabilizing oxidized carbon intermediates, raising the onset potential threshold of adventitious carbon as well as preventing its build-up.