Propane dehydrogenation to propylene represents a key route for replacing traditional petroleum-based processes. However, conventional Pt-based catalysts are limited by an intrinsic scaling relationship between C–H activation capability and propylene adsorption strength, such that enhancing catalytic activity would lead to the reduction of propylene selectivity and even coking. Herein, we demonstrate that the cooperative frustrated Ga···N and Ga···Ga pairs on GaN can effectively break the linear scaling relationship. The frustrated Lewis pairs (Ga···N) facilitate the rate-limiting step of the first C–H bond dissociation in propane, with a Gibbs free energy of activation of 1.63 eV, slightly lower than that on the conventional Pt–Sn catalyst (1.82 eV). The frustrated metal pairs (Ga···Ga) are responsible for 1-propyl dehydrogenation, exhibiting weak propylene adsorption and further suppressing the deep dehydrogenation of propylene. Kinetic Monte Carlo simulations based on the overall reaction network indicate that GaN exhibits excellent catalytic activity, with a turnover frequency of 18.33 s⁻¹ for propylene production, significantly higher than that of Pt-based catalysts. This study not only elucidates how the cooperation of frustrated Ga···N and Ga···Ga pairs breaks the linear scaling relationship, but also provides insights for the design of novel catalysts for propane dehydrogenation.

Li–CO₂ batteries (LCOBs) have garnered significant research interest in recent years owing to their exceptional theoretical energy density and potential carbon neutrality responses. However, challenges such as the stable thermodynamic properties of CO₂ and the nonconductivity of product Li₂CO₃ still hinder the practical application of LCOBs, resulting in high overpotential, poor energy conversion efficiency, and restricted capacity. It is believed that changing the electronic structure of the CO₂ cathodic catalyst to improve the inert interface of product nucleation and decomposition by manipulating the d-band center of transition metal-based materials could effectively solve the problem of sluggish kinetics of both CO₂ reduction reaction (CO₂RR) and CO₂ evolution reaction (CO₂ER). In this review, we summarize the ongoing progresses of representative cathodic catalysts for LCOBs from 2015 to 2024. We also evaluate the correlation between catalyst morphology and structure characteristics on the electrochemical activity of LCOBs. More importantly, we systematically discuss the d-band center regulation strategies that alter the electronic properties of catalysts, including heteroatom doping, defect/vacancy engineering, surface/interface engineering, crystalline engineering, heterojunction, atomic-sized catalysis, and strain modulation. We believe that this review would offer a profound understanding on the optimization of electronic configuration for CO₂ cathodic materials in LCOBs.

The catalytic conversion of CO₂ into functionalized chemical products has evolved into a pivotal scientific frontier, garnering substantial research investment from multidisciplinary domains. Among diverse transformation pathways, the atomically economical cycloaddition between CO₂ and epoxides to synthesize cyclic carbonates stands out as a paradigm of sustainable synthesis, fully complying with green chemistry metrics and circular economy principles. These value-added cyclic carbonates serve as critical components in advanced energy storage systems (e.g., lithium-ion battery electrolytes), bioactive molecule synthesis, and specialty chemical production. This critical review systematically explores recent progress, technical barriers, and strategic directions within CO₂ cycloaddition research. The analysis commences with a mechanistic dissection of three predominant activation modes (CO₂ activation, epoxides activation, and dual activation), subsequently conducting comparative assessments of catalytic systems spanning molecular complexes to heterogeneous frameworks. A techno-economic evaluation is then presented regarding reactor configurations, including batch processing, continuous flow systems, and microchannel technologies. Notably, the work emphasizes an urgent need for innovative catalytic materials capable of dual-functionality: selective adsorption of dilute CO₂ streams from industrial flue gases or ambient air under mild conditions (25 ℃, 1 atm), coupled with in situ catalytic transformation into target carbonates without intermediate separation. The proposed research matrix establishes theoretical foundations and practical guidelines for developing next-generation carbon capture-utilization integrated technologies.

Activation of molecular O₂ is the most critical step in gold-catalyzed oxidation reactions; however, the underlying mechanisms of this process remain under debate. In this study, we propose an alternative O₂ activation pathway with the assistance of hydrogen-containing substrates using density functional theory. It is demonstrated that the co-adsorbed H-containing substrates (R–H) not only enhance the adsorption of O₂, but also transfer a hydrogen atom to the adjacent O₂, leading to O₂ activation by its transformation to a hydroperoxyl (OOH) radical species. The activation barriers of the H-transfer from 16 selected R–H compounds (H₂O, CH₃OH, NH₂CHCOOH, CH₃CH=CH₂, (CH₃)₂SiH₂, etc.) to the co-adsorbed O₂ are lower than 0.50 eV in most cases, indicating the feasibility of the activation of O₂ via OOH under mild conditions. The formed OOH oxidant, with an increased O–O bond length of ~1.45 Å, either participates directly in oxidation reactions through the end-on oxygen atom, or dissociates into atomic oxygen and hydroxyl (OH) by crossing a fairly low energy barrier of 0.24 eV. Using CO oxidation as a probe, we have found that OOH has superior activity than activated O₂ and atomic oxygen. This study reveals a new pathway for the activation of O₂, and may provide insight into the oxidation catalysis of nanosized gold.