Atmosphere Induces Tunable Oxygen Vacancies to Stabilize Single-Atom Copper in Ceria for Robust Electrocatalytic CO2 Reduction to CH4.

Electrochemical carbon dioxide reduction (ECO2RR) shows great potential to create high-value carbon-based chemicals, while designing advanced catalysts at the atomic level remains challenging. The ECO2RR performance is largely dependent on the catalyst microelectronic structure that can be effectively modulated through surface defect engineering. Here, we provide an atmosphere-assisted low-temperature calcination strategy to prepare a series of single-atomic Cu/ceria catalysts with varied oxygen vacancy concentrations for robust electrolytic reduction of CO2 to methane. The obtained Cu/ceria catalyst under H2 environment (Cu/ceria-H2) exhibits a methane Faraday efficiency (FECH4) of 70.03% with a turnover frequency (TOFCH4) of 9946.7 h-1 at an industrial-scale current density of 150 mA cm-2 in a flow cell. Detailed studies indicate the copious oxygen vacancies in the Cu/ceria-H2 are conducive to regulating the surface microelectronic structure with stabilized Cu+ active center. Furthermore, density functional theory calculations and operando ATR-SEIRAS demonstrate that the Cu/ceria-H2 can markedly enhance the activation of CO2, facilitate the adsorption of pivotal intermediates *COOH and *CO, thus ultimately enabling the high selectivity for CH4 production. This study presents deep insights into designing effective electrocatalysts for CO2 to CH4 conversion by controlling the surface microstructure via the reaction atmosphere.

Regulating the Electronic Structure of Bismuth Nanosheets by Titanium Doping to Boost CO2 Electroreduction and Zn-CO2 Batteries.

The electrochemical carbon dioxide reduction reaction (E-CO2 RR) to formate is a promising strategy for mitigating greenhouse gas emissions and addressing the global energy crisis. Developing low-cost and environmentally friendly electrocatalysts with high selectivity and industrial current densities for formate production is an ideal but challenging goal in the field of electrocatalysis. Herein, novel titanium-doped bismuth nanosheets (TiBi NSs) with enhanced E-CO2 RR performance are synthesized through one-step electrochemical reduction of bismuth titanate (Bi4 Ti3 O12 ). We comprehensively evaluated TiBi NSs using in situ Raman spectra, finite element method, and density functional theory. The results indicate that the ultrathin nanosheet structure of TiBi NSs can accelerate mass transfer, while the electron-rich properties can accelerate the production of *CO2 - and enhance the adsorption strength of *OCHO intermediate. The TiBi NSs deliver a high formate Faradaic efficiency (FEformate ) of 96.3% and a formate production rate of 4032 µmol h-1  cm-2 at -1.01 V versus RHE. An ultra-high current density of -338.3 mA cm-2 is achieved at -1.25 versus RHE, and simultaneously FEformate still reaches more than 90%. Furthermore, the rechargeable Zn-CO2 battery using TiBi NSs as a cathode catalyst achieves a maximum power density of 1.05 mW cm-2 and excellent charging/discharging stability of 27 h.

The effect of cation mixing controlled by thermal treatment duration on the electrochemical stability of lithium transition-metal oxides.

Lithium cathode materials have been considered as promising candidates for energy storage applications because of their high power/energy densities, low cost, and low toxicity. However, the Li/Ni cation mixing limits their application as practical electrode materials. The cation mixing of lithium transition-metal oxides, which was first considered only as the origin of performance degeneration, has recently been reconsidered as a way to stabilize the structure of active materials. Here we find that as the duration of the post-synthesis thermal treatment (at 500 °C) of LiNi1/3Co1/3Mn1/3O2 (NCM) was increased, the Li/Ni molar ratio in the final product was found to decrease, and this was attributed to the reduction in nickel occupying lithium sites; the cation mixing subtly changed; and those subtle variations remarkably influence their cycling performance. The cathode material with appropriate cation mixing exhibits a much slower voltage decay and capacity fade during long-term cycling. Combining X-ray diffraction, Rietveld analysis, the Fourier transform infrared technique, field-emission scanning electron microscopy, and electrochemical measurements, we demonstrate that an optimal degree of Ni2+ occupancy in the lithium layer enhances the electrochemical performance of layered NMC materials and that this occurs through a "pillaring" effect. The results provide new insights into "cation mixing" as a new concept for material design utilization of layered cathodes for lithium-ion batteries, thereby promoting their further application in lithium-ion batteries with new functions and properties.

Three-Phase-Heterojunction Cu/Cu2O-Sb2O3 Catalyst Enables Efficient CO2 Electroreduction to CO and High-Performance Aqueous Zn-CO2 Battery.

Zn-CO2 batteries are excellent candidates for both electrical energy output and CO2 utilization, whereas the main challenge is to design electrocatalysts for electrocatalytic CO2 reduction reactions with high selectivity and low cost. Herein, the three-phase heterojunction Cu-based electrocatalyst (Cu/Cu2O-Sb2O3-15) is synthesized and evaluated for highly selective CO2 reduction to CO, which shows the highest faradaic efficiency of 96.3% at -1.3 V versus reversible hydrogen electrode, exceeding the previously reported best values for Cu-based materials. In situ spectroscopy and theoretical analysis indicate that the Sb incorporation into the three-phase heterojunction Cu/Cu2O-Sb2O3-15 nanomaterial promotes the formation of key *COOH intermediates compared with the normal Cu/Cu2O composites. Furthermore, the rechargeable aqueous Zn-CO2 battery assembled with Cu/Cu2O-Sb2O3-15 as the cathode harvests a peak power density of 3.01 mW cm-2 as well as outstanding cycling stability of 417 cycles. This research provides fresh perspectives for designing advanced cathodic electrocatalysts for rechargeable Zn-CO2 batteries with high-efficient electricity output together with CO2 utilization.

Cobalt-Doped NiS2 Micro/Nanostructures with Complete Solid Solubility as High-Performance Cathode Materials for Actual High-Specific-Energy Thermal Batteries.

Transition-metal sulfides are key cathode materials for thermal batteries used in military applications. However, it is still a big challenge to prepare sulfides with good electronic conductivity and thermal stability. Herein, we rapidly synthesized a Co-doped NiS2 micro/nanostructure using a hydrothermal method. We found that the specific capacity of the Ni1-xCoxS2 micro/nanostructure increases with the amount of Co doping. Under a current density of 100 mA cm-2, the specific capacity of Ni0.5Co0.5S2 was about 1565.2 As g-1 (434.8 mAh g-1) with a cutoff voltage of 1.5 V. Owing to the small polarization impedance (5 mΩ), the pulse voltage reaches about 1.74 V under a pulse current of 2.5 A cm-2, 30 ms. Additionally, the discharge mechanism was proposed by analyzing the discharge product according to the anionic redox chemistry. Furthermore, a 3.9 kg full thermal battery is assembled based on the synthesized Ni0.5Co0.5S2 cathode materials. Notably, the full thermal battery discharges at a current density of 100 mA cm-2, with an operating time of about 4000 s, enabling a high specific energy density of around 142.5 Wh kg-1. In summary, this work presents an effective cathode material for thermal battery with high specific energy and long operating life.