In situ Raman spectroscopy reveals the structure evolution and lattice oxygen reaction pathway induced by the crystalline-amorphous heterojunction for water oxidation.

Autor:	Dong J; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Qian Z; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Xu P; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Yue MF; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Zhou RY; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Wang Y; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Nan ZA; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Huang S; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Dong Q; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Li JF; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn.; College of Optical and Electronic Technology, China Jiliang University Hangzhou China., Fan FR; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn., Tian ZQ; State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen 361005 China frfan@xmu.edu.cn.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2022 Apr 22; Vol. 13 (19), pp. 5639-5649. Date of Electronic Publication: 2022 Apr 22 (Print Publication: 2022).
DOI:	10.1039/d2sc01043g
Abstrakt:	One of the most successful approaches for balancing the high stability and activity of water oxidation in alkaline solutions is to use amorphous and crystalline heterostructures. However, due to the lack of direct evidence at the molecular level, the nano/micro processes of amorphous and crystalline heterostructure electrocatalysts, including self-reconstruction and reaction pathways, remain unknown. Herein, the Leidenfrost effect assisted electrospray approach combined with phase separation was used for the first time to create amorphous NiO x /crystalline α-Fe 2 O 3 (a-NiO x /α-Fe 2 O 3 ) nanowire arrays. The results of in situ Raman spectroscopy demonstrate that with the increase of the potential at the a-NiO x /α-Fe 2 O 3 interface, a significant accumulation of OH can be observed. Combining with XAS spectra and DFT calculations, we believe that more OH adsorption on the Ni centers can facilitate Ni 2+ deprotonation to achieve the high-valence oxidation of Ni 4+ according to HSAB theory (Fe 3+ serves as a strong Lewis acid). This result promotes the electrocatalysts to follow the lattice oxygen activation mechanism. This work, for the first time, offers direct spectroscopic evidence for deepening the fundamental understanding of the Lewis acid effect of Fe 3+ , and reveals the synergistic effect on water oxidation via the unique amorphous and crystalline heterostructures. Competing Interests: The authors declare no competing financial interest. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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