Zengxi Wei

Filling the oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting

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. Co3O4 has been developed as a highly efficient OER electrocatalyst, but it has almost no activity for HER. In a previous study, it has been demonstrated that the formation of oxygen vacancies (VO) in Co3O4 can significantly enhance the OER activity. However, the stability of VO needs to be considered, especially under the highly oxidizing conditions of the OER process. It is a big challenge to stabilize the VO in Co3O4 while reserving the excellent activity. Filling the oxygen vacancies with heteroatoms in the VO-rich Co3O4 may be a smart strategy to stabilize the VO by compensating the coordination numbers and obtain an even surprising activity due to the modification of electronic properties by heteroatoms. Herein, we successfully transformed VO-rich Co3O4 into an HER-OER electrocatalyst by filling the in situ formed VO in Co3O4 with phosphorus (P-Co3O4) by treating Co3O4 with Ar plasma in the presence of a P precursor. The relatively lower coordination numbers in VO-Co3O4 than those in pristine Co3O4 were evidenced by X-ray adsorption spectroscopy, indicating that the oxygen vacancies were created after Ar plasma etching. On the other hand, the relatively higher coordination numbers in P-Co3O4 than those in VO-Co3O4 and nearly same coordination number as that in pristine Co3O4 strongly suggest the efficient filling of P in the vacancies by treatment with Ar plasma in the presence of a P precursor. The Co–O bonds in Co3O4 consist of octahedral Co3+(Oh)–O and tetrahedral Co2+(Td)–O (Oh, octahedral coordination by six oxygen atoms and Td, tetrahedral coordination by four oxygen atoms). More Co3+(Oh)–O are broken when oxygen vacancies are formed in VO-Co3O4, and more electrons enter the octahedral Co 3d orbital than those entering the tetrahedral Co 3d orbital. Then, with the filling of P in the vacancy site, electrons are transferred out of the Co 3d states, and more Co2+(Td) than Co3+(Oh) are left in P-Co3O4. These results suggest that the favored catalytic ability of P-Co3O4 is dominated by the Co2+(Td) site. P-Co3O4 shows superior electrocatalytic activities for HER and OER (among the best non-precious metal catalysts). Owing to its superior efficiency, P-Co3O4 can directly catalyze overall water splitting with excellent performance. The theoretical calculations illustrated that the improved electrical conductivity and intermediate binding by P-filling contributed significantly to the enhanced HER and OER activity of Co3O4.

Metal‐Free Carbon Materials for CO2 Electrochemical Reduction

The rapid increase of the CO2 concentration in the Earths atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO2 conversion, electrochemical reduction of CO2 (CO2 RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal-free electrocatalysts for the CO2 RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high-temperature stability, and environmental friendliness. They exhibit remarkable CO2 RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal-free catalysts for the CO2 RR are highlighted. Recent advances regarding the identification of active sites for the CO2 RR and the pathway of reduction of CO2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom-doped carbon materials as metal-free electrocatalysts for the CO2 RR are included.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries

Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future.

Research progress on vanadium-based cathode materials for sodium ion batteries

Sodium ion batteries (SIBs) have attracted increasing attention as one of the most promising candidates for cost-effective, high-energy rechargeable batteries. Owing to their high theoretical capacity and energy density, and rich electrochemical interaction with Na+ (V2+–V5+), a large number of vanadium(V)-based cathode materials, including vanadium oxides (e.g., V2O5 and VO2), vanadium bronzes (e.g., NaxVO2, NaV3O8, NaV6O15 and δ-NH4V4O10), V-based phosphates (e.g., Na3V2(PO4)3, VOPO4, NaVOPO4, Na7V3(P2O7)4 and Na2(VO)P2O7) and F-containing V-based polyanions (e.g., NaVPO4F, Na3V2(PO4)2F3 and Na3(VOx)2(PO4)2F3−2x), have been explored for SIBs. In this review, we mainly summarize the basic structures, modified/optimized structures, synthetic methods and morphology control of V-based cathode materials for SIBs. Additionally, major drawbacks, emerging challenges and some perspectives on the development of V-based cathode materials for SIBs are also discussed.

Chevrel Phase Mo6T8 (T = S, Se) as Electrodes for Advanced Energy Storage

With the large-scale applications of electric vehicles in recent years, future batteries are required to be higher in power and possess higher energy densities, be more environmental friendly, and have longer cycling life, lower cost, and greater safety than current batteries. Therefore, to develop alternative electrode materials for advanced batteries is an important research direction. Recently, the Chevrel phase Mo6 T8 (T = S, Se) has attracted increasing attention as electrode candidate for advanced batteries, including monovalent (e.g., lithium and sodium) and multivalent (e.g., magnesium, zinc and aluminum) ion batteries. Benefiting from its unique open crystal structure, the Chevrel phase Mo6 T8 cannot only ensure rapid ion transport, but also retain the structure stability during electrochemical reactions. Although the history of the research on Mo6 T8 as electrodes for advanced batteries is short, there has been significant progress on the design and fabrication of Mo6 T8 for various advanced batteries as above mentioned. An overview of the recent progress on Mo6 T8 electrodes applied in advanced batteries is provided, including synthesis methods and diverse structures for Mo6 T8 , and electrochemical mechanism and performance of Mo6 T8 . Additionally, a briefly conclusion on the significant progress, obvious drawbacks, emerging challenges and some perspectives on the research of Mo6 T8 for advanced batteries in the near future is provided.

Fe-doped phosphorene for the nitrogen reduction reaction

The nitrogen-to-ammonia conversion is one of the most important and challenging processes in chemistry. We have employed spin-polarized density functional theory to propose Fe-doped monolayer phosphorene (Fe–P) as a new catalyst for the N2 reduction reaction at room temperature. Our results show that single-atom Fe is the active site, cooperating with P to activate the inert N–N triple bond and reduce N2 to NH3via three reliable pathways. Our findings provide a new avenue for single atom catalytic nitrogen fixation under ambient conditions.

Strong Electronic Interaction in Dual-Cation-Incorporated NiSe2 Nanosheets with Lattice Distortion for Highly Efficient Overall Water Splitting

Exploring highly efficient and low-cost electrocatalysts for electrochemical water splitting is of importance for the conversion of intermediate energy. Herein, the synthesis of dual-cation (Fe, Co)-incorporated NiSe2 nanosheets (Fe, Co-NiSe2 ) and systematical investigation of their electrocatalytic performance for water splitting as a function of the composition are reported. The dual-cation incorporation can distort the lattice and induce stronger electronic interaction, leading to increased active site exposure and optimized adsorption energy of reaction intermediates compared to single-cation-doped or pure NiSe2 . As a result, the obtained Fe0.09 Co0.13 -NiSe2 porous nanosheet electrode shows an optimized catalytic activity with a low overpotential of 251 mV for oxygen evolution reaction and 92 mV for hydrogen evolution reaction (both at 10 mA cm-2 in 1 m KOH). When used as bifunctional electrodes for overall water splitting, the current density of 10 mA cm-2 is achieved at a low cell voltage of 1.52 V. This work highlights the importance of dual-cation doping in enhancing the electrocatalyst performance of transition metal dichalcogenides.