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The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure–activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO–Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH• first for VO–Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co–OOH•. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.

It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting.

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Designing atomically dispersed metal catalysts for oxygen reduction reaction (ORR) is a promising approach to achieve efficient energy conversion. Herein, we develop a template-assisted method to synthesize a series of single metal atoms anchored on porous N,S-codoped carbon (NSC) matrix as highly efficient ORR catalysts to investigate the correlation between the structure and their catalytic performance. The structure analysis indicates that an identical synthesis method results in distinguished structural differences between Fe-centered single-atom catalyst (Fe-SAs/NSC) and Co-centered/Ni-centered single-atom catalysts (Co-SAs/NSC and Ni-SAs/NSC) because of the different trends of each metal ion in forming a complex with the N,S-containing precursor during the initial synthesis process. The Fe-SAs/NSC mainly consists of a well-dispersed FeN 4 S 2 center site where S atoms form bonds with the N atoms. The S atoms in Co-SAs/NSC and Ni-SAs/NSC, on the other hand, form metal−S bonds, resulting in CoN 3 S 1 and NiN 3 S 1 center sites. Density functional theory (DFT) reveals that the FeN 4 S 2 center site is more active than the CoN 3 S 1 and NiN 3 S 1 sites, due to the higher charge density, lower energy barriers of the intermediates, and products involved. The experimental results indicate that all three single-atom catalysts could contribute high ORR electrochemical performances, while Fe-SAs/NSC exhibits the highest of all, which is even better than commercial Pt/C. Furthermore, Fe-SAs/NSC also displays high methanol tolerance as compared to commercial Pt/C and high stability up to 5000 cycles. This work provides insights into the rational design of the definitive structure of single-atom catalysts with tunable electrocatalytic activities for efficient energy conversion.

As inspired by natural photosynthesis, semiconductor-based photocatalytic water splitting into hydrogen and oxygen has attracted extensive attention, which provides a promising and clean method to convert solar energy into chemical fuel, for alleviating human's excessive reliance on fossil fuels. [1][2][3] For the water splitting process, the half-reaction of water oxidation to oxygen has been well recognized as the rate-limiting step for its four-electron oxidation process and high activation energy barrier (≈700 mV) for O-O bond formation, [4,5] which thus remains as the main challenge to achieve highly efficient overall water splitting. Although enormous efforts have been dedicated to develop photocatalysts for improved water oxidation performances in the past decades, by far only a few photocatalysts (e.g., WO 3 , BiVO 4 , and Ag 3 PO 4 , etc.) have been proven to be efficient for lightdriven oxygen evolution from water. [5][6][7][8] Worse still, several drawbacks always limit their practical application in oxygen-generating photocatalytic systems, including poor photostability, low charge carrier mobility, and high costs of raw materials. Since the pioneering work reported in 2009 by Wang et al., [9] metal-free graphitic carbon nitride (g-C 3 N 4 ) with a 2D conjugated structure has been intensively investigated for photocatalytic water redox reactions, owing to its earth-abundance, environmental friendliness, chemical stability, and suitable thermodynamical potentials for both hydrogen and oxygen evolution reactions. [10][11][12] In the past ten years, various strategies, including thermodynamic (such as doping with heteroatoms, [13][14][15][16] engineering defects with nitrogen vacancies or carbon vacancies, [17,18] etc.) and kinetic (such as compositing with other semiconductors, [7,[19][20][21][22] morphology design, [23][24][25][26][27] and loading cocatalysts, [28][29][30] etc.) modifications, have emerged to enhance the photocatalytic hydrogen evolution activity of g-C 3 N 4 and a high quantum yield of 34.4% at 400 nm has been achieved. [31] However, only very few results have been reported on g-C 3 N 4 based photocatalysts for water oxidation, and most of them were focused on surface modification by loading cocatalysts, such as cobalt (hydr)oxide and selenide, [32][33][34] etc., onto g-C 3 N 4 . Unfortunately, the photocatalytic oxygen evolution Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C 3 N 4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C 3 N 4 . The resultant boron-doped and nitrogen-deficient g-C 3 N 4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h −1 g −1 , much higher than previously reported g-C 3 N 4 . It is well evidenced that with c...

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Understanding the role of oxidation state of Cu surface and surface-adsorbed intermediate species in electrochemical CO2 reduction is crucial for the development of selective CO2-to-fuel electrocatalysts. In this study, the electrochemical CO2 reduction mechanism over the Cu catalysts with various oxidation states was studied by using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS), in situ soft X-ray absorption spectroscopy (Cu L-edge) and on-line gas chromatography measurements. The atop-adsorbed CO (COatop) intermediate is obtained on the electrodeposited Cu surface which primarily has the oxidation state of Cu(I). COatop is further reduced, followed by the formation of C1 product such as CH4. The residual bridge-adsorbed CO (CObridge) is formed on the as-prepared Cu surface with Cu(0) which inhibits hydrocarbon formation. In contrast, the CV-treated Cu electrode prepared by oxidizing the as-prepared Cu surface contains different amount of Cu(I) and Cu(0) states. The major theme of this work is that in situ SEIRAS results show the coexistence of COatop and CObridge as the reaction intermediates during CO2 reduction and the selectivity of CO2-to-ethylene conversion is further enhanced in the CV-treated Cu electrode. The Cu catalysts modulated by electrochemical method exhibit different oxidation states and reaction intermediates as well as the electrocatalytic properties.