Single-atom site engineering has emerged as an effective strategy for enhancing the selectivity of multicarbon products in electrochemical CO₂ reduction reaction (CO₂RR), yet the synergistic roles of interfacial microenvironment regulation and key intermediate evolution remain poorly understood. Herein, Ag single-atom-modified porous CuO nanosheets (Ag₁-p-CuO) were constructed, and the mechanism by which Ag₁ atoms regulate the evolution of interfacial intermediates and water structure to promote ethylene formation, was systematically investigated through in situ shell-isolated nanoparticle enhanced Raman spectroscopy and advanced constant-potential density functional theory calculations. The atomically dispersed 0.2 % Ag species on porous CuO enabled a maximum C₂H₄ Faradaic efficiency of 54% and C₂₊ Faradaic efficiency of 78%. In situ Raman spectra reveal that, Ag₁ decoration enriches CO coverage at defective Cu step sites and reorganizes the interfacial water layer near the surface. The resulting Ag₁-Cu interface enhances cation-H₂O dissociation, establishing a local proton-donating environment that directs C–C bond formation toward a favorable asymmetric CO–CHO coupling pathway while lowering the hydrogenation barrier of the key ethylene precursor *CH₂CHO, thereby markedly improving ethylene selectivity. This work provides new insights into single-atom catalysis mediated interfacial microenvironment and intermediate behavior for promoting multicarbon product formation in CO₂RR.

Efficient electroreduction of CO₂ into CO and other chemicals turns greenhouse gases into fuels and value-added chemicals, holding great promise for a closed carbon cycle and the alleviation of climate changes. However, there are still challenges in the large-scale application of CO₂ electroreduction due to the sluggish kinetics. Herein we develop a self-assembly strategy to synthesize a highly efficient CO₂ reduction electrocatalyst with atomically dispersed Ni-N₄ active centers anchored on polymer-derived mesh-like N-doped carbon nanofibers (Ni-N₄/NC). The Ni-N₄/NC exhibits high selectivity for CO₂ reduction reaction with CO Faradaic efficiency (CO FE) above 90% over a wide potential range from −0.6 to −1.0 V vs. RHE. The catalyst reaches a maximum CO FE up to 98.4% at −0.8 V with a TOF of 1.28 x 10⁵ h^–1 and Tafel slope of 113 mV·dec^–1. The catalyst also exhibits remarkable stability, with little change in current density and CO FE over a 10-hour durability test at –0.8 V vs. RHE. This method provides a new route for the synthesis of highly efficient CO₂ reduction electrocatalyst.

Developing highly efficient oxygen evolution reaction (OER) catalyst for the acidic corrosive operating conditions is a challenging task. Herein, we report the synthesis of uniform RuO₂ clusters with ~ 2 nm in size via electrochemical leaching of Sr from SrRuO₃ ceramic in acid. The RuO₂ clusters exhibit ultrahigh OER activity with overpotential of ~ 160 mV at 10 mA·cm_geo⁻² in 1.0 M HClO₄ solution for 30-h testing. The extended X-ray absorption fine structure measurement reveals enlarged Jahn-Teller distortion of Ru-O octahedra in the RuO₂ clusters compared to its bulk counterpart. Density function theory calculations show that the enhanced Jahn-Teller distortion can improve the intrinsic OER activity of RuO₂.

Surface characterization of metal nanoparticles is a critical need in nanocatalysis for in-depth understanding of the structure–function relationships. The surface structure of nanoparticles is often different from the subsurface, and it is challenging to separately characterize the surface and the subsurface. In this work, theoretical calculations and extended X-ray absorption fine structure (EXAFS) analysis illustrate that the surface atoms of noble metals (Pt and Pd) are oxidized in the air, while the subsurface atoms are not easily oxidized. Taking advantage of the oxidation properties, we suggest a stepwise reduction–oxidation approach to determine the surface atomic arrangement of noble metal nanoparticles, and confirm the rationality of this approach by identifying the surface structure of typical 2–3 nm Pt and Pd nanoparticles. The reduction–oxidation approach is applied to characterize the surface structure of model Pd-Sb bimetallic catalyst, which illustrates that the surface Pd is well isolated by Sb atoms with short bond distance at 2.70 Å, while there are still Pd–Pd bonds in the subsurface. Density functional theory (DFT) calculations and Pd L edge X-ray absorption near edge structure (XANES) indicate that the isolation of surface Pd significantly decreases the adsorption energies of Pd-hydrocarbon, which leads to the high propylene selectivity and turnover frequency Pd-Sb bimetallic catalyst for propane dehydrogenation.

Metal-nitrogen-carbon (M-N-C) single-atom catalysts exhibit desirable electrochemical catalytic properties. However, the replacement of N atoms by heteroatoms (B, P, S, etc.) has been regarded as a useful method for regulating the coordination environment. The structure engineered M-N-C sites via doping heteroatoms play an important role to the adsorption and activation of the oxygen intermediate. Herein, we develop an efficient strategy to construct dual atomic site catalysts via the formation of a Co₁-PN and Ni₁-PN planar configuration. The developed Co₁-PNC/Ni₁-PNC catalyst exhibits excellent bifunctional electrocatalytic performance in alkaline solution. Both experimental and theoretical results demonstrated that the N/P coordinated Co/Ni sites moderately reduced the binding interaction of oxygen intermediates. The Co₁-PNC/Ni₁-PNC endows a rechargeable Zn-air battery with excellent power density and cycling stability as an air-cathode, which is superior to that of the benchmark Pt/C+IrO₂. This work paves an avenue for design of dual single-atomic sites and regulation of the atomic configuration on carbon-based materials to achieve high-performance electrocatalysts.

With high energy density and low material cost, lithium-sulfur batteries (LSBs) emerge quite expeditiously as a fascinating energy storage system over the past decade. Broad applications of LSBs ranging from electric vehicles to stationary grid storage seem rather bright in recent literatures. However, there still exist many pressing challenges to be addressed because we do not yet fully understand and control the electrode-electrolyte interface chemistries during battery operation, such as polysulfide shuttling and poor utilization of active sulfur. Single-atom catalysts (SACs) pave new possibilities of tackling the tough issues due to their decent applicability in the atomic-level identification of structure-activity relationships and reaction mechanism, as well as their structural tunability with atomic precision. This review comprehensively summarizes the very recent advances in utilization of highly active SACs for LSBs by stating and discussing the related publications, which involves catalyst synthesis routes, battery performance, catalytic mechanisms, optimization strategies, and promises to achieve long-life, high-energy LSBs. We see that endeavors to employ SACs to modify sulfur cathode have allowed efficient polysulfide conversion and confinement, leading to the minimization of shuttle effect. Parallel efforts are being devoted to extending the scope of SACs to cell separator and lithium metal anode in order to unlock the full potential of LSBs. We also obtain mechanistic insights into battery chemistries and nature of SACs in their strong interactions with polysulfides through advanced in situ characterizations documented. Overall, acceleration in the development of LSBs by introducing SACs is noticeable, and this cutting edge needs more attentions to further promoting the design of better LSBs.

Metal isolated single atomic sites catalysts have attracted intensive attention in recent years owing to their maximized atom utilization and unique structure. Despite the success of single atom catalyst synthesis, directly anchoring metal single atoms on three-dimensional (3D) macro support, which is promising to achieve the heterogenization of homogeneous catalysis, remains a challenge and a blank in this field. Herein, we successfully fabricate metal single atoms (Pd, Pt, Ru, Au) on porous carbon nitride/ reduced graphene oxide (C₃N₄/rGO) foam as highly efficient catalysts with convenient recyclability. C₃N₄/rGO foam features two-dimensional microstructures with abundant N chelating sites for the stabilization of metal single atoms and vertically-aligned hierarchical mesostructure that benefits the mass diffusion. The obtained Pd₁/C₃N₄/rGO monolith catalyst exhibits much enhanced activity over its nanoparticle counterpart for Suzuki-Miyaura reaction. Moreover, the Pd₁/C₃N₄/rGO monolith catalyst can be readily assembled in a flow reactor to achieve the highly efficient continuous production of 4-nitro-1,1'-biphenyl through Suzuki-Miyaura coupling.

Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu_1.94S-Zn_0.23Cd_0.77S semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.