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Due to the superior catalytic activity and efficient utilization of noble metals, nanocatalysts are extensively used in the modern industrial production of chemicals. The surface structures of these materials are significantly influenced by reactive adsorbates, leading to dynamic behavior under experimental conditions. The dynamic nature poses significant challenges in studying the structure–activity relations of catalysts. Herein, we unveil an anomalous entropic effect on catalysis via surface pre‐melting of nanoclusters through machine learning accelerated molecular dynamics and free energy calculation. We find that due to the pre‐melting of shell atoms, there exists a non‐linear variation in the catalytic activity of the nanoclusters with temperature. Consequently, two notable changes in catalyst activity occur at the respective temperatures of melting for the shell and core atoms. We further study the nanoclusters with surface point defects, i.e. vacancy and ad‐atom, and observe significant decrease in the surface melting temperatures of the nanoclusters, enabling the reaction to take place under more favorable and milder conditions. These findings not only provide novel insights into dynamic catalysis of nanoclusters but also offer new understanding of the role of point defects in catalytic processes. [ABSTRACT FROM AUTHOR]

Synthesis of formate from hydrogenation of carbon dioxide (CO2) is an atom‐economic reaction but is confronted with challenges in developing high‐performance non‐precious metal catalysts for application of the process. Herein, we report a highly durable edge‐rich molybdenum disulfide (MoS2) catalyst for CO2 hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h−1 surpassing those of previously reported non‐precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS2 edges are the active sites and the selective production of formate is enabled via a completely new water‐mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO2 with residual O* reduced by hydrogen. This study provides a new route for developing low‐cost high‐performance catalysts for CO2 hydrogenation to formate. [ABSTRACT FROM AUTHOR]

Heterogeneous Catalysis. In their Communication (e202405379), Jun Cheng et al. use machine learning molecular dynamics to demonstrate anomalous entropic effect on catalysis via surface pre‐melting of nanoclusters...By Fu‐Qiang Gong; Yun‐Pei Liu; Ye Wang; Weinan E; Zhong‐Qun Tian and Jun ChengReported by Author; Author; Author; Author; Author; Author [Extracted from the article]

Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal‐2D material interfaces remain unclear. Herein, hot‐electron transfer at Au‐graphene interfaces has been in situ studied using surface‐enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot‐electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene. [ABSTRACT FROM AUTHOR]

The adsorption and electrooxidation of CO molecules at well‐defined Pt(hkl) single‐crystal electrode surfaces is a key step towards addressing catalyst poisoning mechanisms in fuel cells. Herein, we employed in situ electrochemical shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) coupled with theoretical calculation to investigate CO electrooxidation on Pt(hkl) surfaces in acidic solution. We obtained the Raman signal of top‐ and bridge‐site adsorbed CO* molecules on Pt(111) and Pt(100). In contrast, on Pt(110) surfaces only top‐site adsorbed CO* was detected during the entire electrooxidation process. Direct spectroscopic evidence for OH* and COOH* species forming on Pt(100) and Pt(111) surfaces was afforded and confirmed subsequently via isotope substitution experiments and DFT calculations. In summary, the formation and adsorption of OH* and COOH* species plays a vital role in expediting the electrooxidation process, which relates with the pre‐oxidation peak of CO electrooxidation. This work deepens knowledge of the CO electrooxidation process and provides new perspectives for the design of anti‐poisoning and highly effective catalysts. [ABSTRACT FROM AUTHOR]

The spillover of hydrogen species and its role in tuning the activity and selectivity in catalytic hydrogenation have been investigated in situ using surface‐enhanced Raman spectroscopy (SERS) with 10 nm spatial resolution through the precise fabrication of Au/TiO2/Pt sandwich nanostructures. In situ SERS study reveals that hydrogen species can efficiently spillover at Pt‐TiO2‐Au interfaces, and the ultimate spillover distance on TiO2 is about 50 nm. Combining kinetic isotope experiments and density functional theory calculations, it is found that the hydrogen spillover proceeds via the water‐assisted cleavage and formation of surface hydrogen–oxygen bond. More importantly, the selectivity in the hydrogenation of the nitro or isocyanide group is manipulated by controlling the hydrogen spillover. This work provides molecular insights to deepen the understanding of hydrogen activation and boosts the design of active and selective catalysts for hydrogenation. [ABSTRACT FROM AUTHOR]

Conversion of carbon monoxide to high value‐added ethylene with high selectivity by traditional syngas conversion process is challenging because of the limitation of Anderson‐Schulz–Flory distribution. Herein we report a direct electrocatalytic process for highly selective ethylene production from CO reduction with water over Cu catalysts at room temperature and ambient pressure. An unprecedented 52.7 % Faradaic efficiency of ethylene formation is achieved through optimization of cathode structure to facilitate CO diffusion at the surface of the electrode and Cu catalysts to enhance the C−C bond coupling. The highly selective ethylene production is almost without other carbon‐based byproducts (e.g. C1–C4 hydrocarbons and CO2) and avoids the drawbacks of the traditional Fischer–Tropsch process that always delivers undesired products. This study provides a new and promising strategy for highly selective production of ethylene from the abundant industrial CO. [ABSTRACT FROM AUTHOR]

It is vital to understand the oxygen reduction reaction (ORR) mechanism at the molecular level for the rational design and synthesis of high activity fuel‐cell catalysts. Surface enhanced Raman spectroscopy (SERS) is a powerful technique capable of detecting the bond vibrations of surface species in the low wavenumber range, however, using it to probe practical nanocatalysts remains extremely challenging. Herein, shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) was used to investigate ORR processes on the surface of bimetallic Pt3Co nanocatalyst structures. Direct spectroscopic evidence of *OOH suggests that ORR undergoes an associative mechanism on Pt3Co in both acidic and basic environments. Density functional theory (DFT) calculations show that the weak *O adsorption arise from electronic effect on the Pt3Co surface accounts for enhanced ORR activity. This work shows SHINERS is a promising technique for the real‐time observation of catalytic processes. [ABSTRACT FROM AUTHOR]

Electrocatalytic CO2 reduction to CO emerges as a potential route of utilizing emitted CO2. Metal‐N‐C hybrid structures have shown unique activities, however, the active centers and reaction mechanisms remain unclear because of the ambiguity in true atomic structures for the prepared catalysts. Herein, combining density‐functional theory calculations and experimental studies, the reaction mechanisms for well‐defined metal–N4 sites were explored using metal phthalocyanines as model catalysts. The theoretical calculations reveal that cobalt phthalocyanine exhibits the optimum activity for CO2 reduction to CO because of the moderate *CO binding energy at the Co site, which accommodates the *COOH formation and the *CO desorption. It is further confirmed by experimental studies, where cobalt phthalocyanine delivers the best performance, with a maximal CO Faradaic efficiency reaching 99 %, and maintains stable performance for over 60 hours. To the "CO2RR": Metal phthalocyanines (MePcs) with well‐defined metal–N4 structures were used as model catalysts to study the active centers and reaction mechanisms for the electrocatalytic CO2 reduction reaction (CO2RR). Theoretical and experimental studies identify CoPc as the optimum catalyst for the selective electrocatalytic CO2RR to deliver CO. The Co site serves as the active center for achieving a Faradaic efficiency (FE) of up to 99 % with long‐term stability. [ABSTRACT FROM AUTHOR]