Peiyu Ma

Platinum-group metals have an irreplaceable role in electrocatalyzing oxygen reduction reaction (ORR) process due to their affinity for oxygen and oxygenated intermediates. However, large overpotential and poor long-term durability prohibit their utilization in scalable industrial applications. Owing to their inherent scarcity, substantial improvements in the electrocatalytic performance (both selectivity and stability) of the catalysts are urgently necessary. Herein, a synergistic hybrid PtPd-Al2O3 catalyst is developed for highly selective and long-term stable hydrogen peroxide (H2O2) electroproduction. Synchrotron radiation characterizations are carried out to clarify the synergistic effect in the catalyst. The incorporation of Pd with Pt induces a valence band restructuring and reconstructs the coordination environment of the nanoparticles. For H2O2 electrosynthesis through the 2e− ORR, these electronic and structural modifications resulted in optimal adsorption energies of reaction intermediates. Therefore, the synergy hybrid of Pt and Pd not only enhances electrocatalytic activity and selectivity (96%) but also creates a new coordination structure in the catalyst, increasing its long-term durability. This study introduces a new paradigm for the development of high-performance H2O2 electrocatalyst by demonstrating the synergistic dual function of Pd as electron promoter and structure stabilizer.

Renewable‐powered water electrolysis is pivotal to sustainable hydrogen production, yet the alkaline hydrogen evolution reaction (HER) remains kinetically sluggish at high current densities. This limitation stems not only from the extra water‐dissociation step, but also from an unfavorable interfacial water microenvironment that hampers charge transport—challenges that become even more pronounced at ultralow noble‐metal loadings. Herein, an ultralow‐loading PtRu alloy nanocluster catalyst on heterophase MoO _x (PtRu/MoO _x ) synthesized by ultrafast flash Joule heating (FJH) is reported. This nonequilibrium thermal shock drives PtRu alloying, preserves a defect‐rich interface, and establishes a pronounced electronic metal‐support interaction (EMSI) that renders the alloy surface electron‐deficient. Operando spectroscopy and density functional theory (DFT) calculations reveal that this electron‐deficient surface strengthens water adsorption, balances water dissociation with intermediate conversion, and promotes the evolution of interfacial water from isolated, cation‐dominated motifs into a surface‐coupled, hydrogen‐bond‐connected network. Consequently, PtRu/MoO _x requires only 56.15 mV to reach 100 mA cm ⁻² in 1 M KOH; as the cathode in an anion exchange membrane water electrolyzer, it achieves 1.836 V at 1.0 A cm ⁻² and operates stably for over 2000 h at 0.5 A cm ⁻² . This work provides a viable strategy for ultralow‐loading cathodes by synergistically coupling alloying‐governed reaction energetics with interfacial‐water microenvironment engineering.

Dimethyl carbonate (DMC) is a versatile green chemical. However, traditional synthesis routes are often hindered by toxicity, equilibrium constraints, and equipment corrosion. The decarbonylation of dimethyl oxalate (DMO) offers an atom‐economical alternative, though its industrial viability hinges on developing catalysts that balance activity, stability, and cost. In this study, we report a series of carbon‐supported K/Cs‐based catalysts for DMO decarbonylation. Through systematic characterization, the 7%Cs–2%K/C catalyst calcined at 250°C was identified as the optimal formulation. Notably, while static slurry‐bed reactor tests showed performance degradation over successive cycles, the transition to a custom‐designed continuous slurry‐bed reactor system substantially improved operational stability. In this continuous configuration, the catalyst maintained an average DMO conversion of 96.05% and a DMC mass yield of 93.67% during a 204‐h stability test. Furthermore, after scaling up the 250°C–7%Cs–2%K/C catalyst and continuous slurry‐bed reaction process to the pilot‐plant scale, the system still maintained excellent catalytic efficiency and stability. This work integrates catalyst design with process engineering, providing a viable and scalable strategy for the industrial‐scale production of DMC.

Single‐atom catalysts (SACs) have been extensively explored for the oxygen evolution reaction (OER) owing to their maximal atom utilization and high mass activity. However, isolated single‐metal centers often suffer from intrinsic linear scaling relationships among oxygenated intermediates, thereby limiting their catalytic efficiency in the complex four‐electron OER process. To overcome these limitations, we construct atomically dispersed Ir‐Ir duet atoms anchored on CoOOH surface (Ir ₂ /CoOOH) to break the intrinsic scaling relationships governing the OER. Benefiting from the synergistic interaction between adjacent Ir atoms, Ir ₂ /CoOOH exhibits an ultralow overpotential of ∼235 mV at 10 mA cm ⁻² and outstanding durability over 1200 h at 500 mA cm ⁻² in 1 M KOH. Remarkably, Ir ₂ /CoOOH achieves a turnover frequency approximately three times higher than that of isolated Ir single atoms on the CoOOH surface (Ir ₁ /CoOOH), highlighting the critical role of synergistic duet cooperation in enhancing intrinsic OER activity. Operando spectroscopic measurements combined with theoretical calculations reveal that cooperative Ir‐Ir interactions and strong metal‐support interactions optimize the local charge density of Ir active centers, regulate the rate‐determining step, and significantly lower the activation free energy of the OER. These findings demonstrate the effectiveness of atomically dispersed duet‐metal sites in overcoming activity limitations in water oxidation catalysis.

The intermediate adsorption on single‐atom sites critically governs the catalytic performance of single‐atom catalysts. Site‐specific single atoms exhibit distinct intrinsic properties that modulate their intermediate adsorption behaviors. Herein, we elucidate the site‐dependent hydrogen adsorption of Pt single atoms by anchoring them at oxygen vacancies (Pt _V /CoOOH), three‐fold hollow sites (Pt _T /CoOOH), and lattice sites (Pt _L /CoOOH), respectively. Electrochemical measurements demonstrate Pt _T /CoOOH achieves an overpotential of 8 mV at a current density of 10 mA cm ⁻² and long‐term stability for 1000 h. Anion exchange membrane water electrolyzer (AEMWE) integrated Pt _T /CoOOH just required 1.90 V to reach the industrial current density of 1.0 A cm ⁻² with 1000 h stability time. In situ/operando x‐ray absorption fine structure (XAFS), ambient pressure x‐ray photoelectron spectroscopy (AP‐XPS), attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), and theoretical calculations collectively demonstrate that Pt _T /CoOOH exhibits moderate H ₂ O dissociation kinetics and near‐thermoneutral hydrogen binding energy. The optimal hydrogen adsorption facilitated a balanced H adsorption‐H ₂ desorption kinetics, thereby contributing to a superior alkaline hydrogen evolution reaction (HER) activity compared to Pt _V /CoOOH with weaker hydrogen adsorption and Pt _L /CoOOH with stronger hydrogen adsorption. This work proposes a precise synthesis strategy to anchor single atoms at diverse sites and elucidates the influence of site‐dependent intermediate adsorption on catalytic performance.

The intermediate adsorption on single‐atom sites critically governs the catalytic performance of single‐atom catalysts. Site‐specific single atoms exhibit distinct intrinsic properties that modulate their intermediate adsorption behaviors. Herein, we elucidate the site‐dependent hydrogen adsorption of Pt single atoms by anchoring them at oxygen vacancies (Pt _V /CoOOH), three‐fold hollow sites (Pt _T /CoOOH), and lattice sites (Pt _L /CoOOH), respectively. Electrochemical measurements demonstrate Pt _T /CoOOH achieves an overpotential of 8 mV at a current density of 10 mA cm ⁻² and long‐term stability for 1000 h. Anion exchange membrane water electrolyzer (AEMWE) integrated Pt _T /CoOOH just required 1.90 V to reach the industrial current density of 1.0 A cm ⁻² with 1000 h stability time. In situ/operando x‐ray absorption fine structure (XAFS), ambient pressure x‐ray photoelectron spectroscopy (AP‐XPS), attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), and theoretical calculations collectively demonstrate that Pt _T /CoOOH exhibits moderate H ₂ O dissociation kinetics and near‐thermoneutral hydrogen binding energy. The optimal hydrogen adsorption facilitated a balanced H adsorption‐H ₂ desorption kinetics, thereby contributing to a superior alkaline hydrogen evolution reaction (HER) activity compared to Pt _V /CoOOH with weaker hydrogen adsorption and Pt _L /CoOOH with stronger hydrogen adsorption. This work proposes a precise synthesis strategy to anchor single atoms at diverse sites and elucidates the influence of site‐dependent intermediate adsorption on catalytic performance.

Grain boundary induced tensile strain tunes catalyst oxophilicity, thereby reorganizing interfacial water and accelerating proton and water transfer to break the kinetic pH effect in HER.

Advanced in situ / operando characterization techniques for investigating catalyst structure evolution and reaction intermediates of the oxygen evolution reaction.

Electrocatalytic water splitting is an efficient method for hydrogen energy production. In alkaline water electrolysis, the hydrogen evolution reaction (HER) involves a kinetically sluggish two‐electron transfer process which limits the reaction rate. There are two reaction mechanisms for the alkaline water electrolysis, which are Volmer–Heyrovsky mechanism and Volmer–Tafel mechanism. Both mechanisms require the dissociation of hydrogen into H ^* . Pt has a weak ability to dissociate H ₂ O but a strong ability to couple H ^* . Meanwhile, transition metal has a strong ability to dissociate H ₂ O but a weak ability to couple H ^* . Therefore, coupling Pt and transition metal species into one catalytic system is an effective strategy to achieve efficient hydrogen evolution. Herein, a Co–Pt cluster–cluster heterogeneous electrocatalyst (Co _n Pt _n /C ₃ N ₄ ) for efficient alkaline hydrogen evolution is constructed. Specifically, Co _n Pt _n /C ₃ N ₄ exhibits excellent electrochemical performance such that it only requires an overpotential of 15 mV to achieve a current density of 10 mA cm ⁻² and 75 mV to achieve a current density of 100 mA cm ⁻² . It is proved that the Co–Pt cluster–cluster synergistic interaction in catalyst improves the electrochemical performance for HER.