Yixin Hao

Designing acid‐stable anodic electrocatalysts with low noble‐metal loading is essential for the industrial‐scale application of proton exchange membrane water electrolysis (PEMWE). However, existing catalyst systems struggle to fully utilize the intrinsic properties of active sites. Here, a precisely engineered nanocatalyst is unveiled through a hierarchical atomic assembly strategy for synthesis, featuring an ultralow‐content Ir─Ru single‐atom alloy integrated into robust titanium dioxide nanowires (Ir ₁ Ru/TiO ₂ ). This lattice‐embedded structure induces the support to reduce the dissolution and excessive oxidation of Ru/Ir sites through strong interfacial coupling, significantly enhancing the corrosion resistance of catalysts. Moreover, atomically dispersed Ir induces the formation of uniquely shortened Ru─O ligand bonds, serving as stable self‐limiting motifs, in contrast to the conventional formation of amorphous oxide layers. The Ir ₁ Ru/TiO ₂ catalyst showcases an initial mass activity of 1971.5 A , enabling stable operation at 10 mA cm ⁻² for over 3200 h and at the rated current density of 2 A cm ⁻² for 2000 h in PEMWE.

Efficient proton supply and enhanced *CO intermediate adsorption are crucial strategies for boosting CO ₂ methanation. Herein, we construct a hydrogen‐bonded (H‐bonded) photocatalytic membrane by integrating a MAPbBr ₃ /cyano‐g‐C ₃ N ₄ (MPB/CN‐g‐CN) heterojunction with ethyl cellulose (ECE) binder through a simple sol–gel process, achieving significantly enhanced CO ₂ methanation efficiency. ECE functions as a novel proton source, with hydroxyl (‐OH) groups that are readily oxidized by photogenerated holes, resulting in efficient proton supply compared to H ₂ O. Moreover, ECE facilitates membrane assembly via interfacial H‐bonding between the ‐OH moieties of ECE and the modified nitrogen sites of MPB/CN‐g‐CN, generating proton‐rich interfaces and local H‐bond microenvironments that synergistically enhance proton supply and CO adsorption, thus steering the reaction toward CH ₄ production. As a result, the MPB/CN‐g‐CN membrane achieves a remarkable increase in CH ₄ yield from 0.01 to 35.85 µmol g ⁻¹ h ⁻¹ and selectivity from 0.4% to 82% compared to the pristine heterojunction. Furthermore, the MPB/CN‐g‐CN/ECE membrane demonstrates exceptional recyclability through a re‐crosslinking membrane formation process, effectively reactivating proton‐supply sites while maintaining superior CH ₄ selectivity across multiple operational cycles.

Enhancing the mechanistic regulation of the oxygen evolution reaction (OER) is crucial for developing efficient and stable electrocatalysts. However, the dynamic variation of surface structure during the electrocatalytic process limits the accurate identification of the active source and underlying reaction mechanism. Herein, we report an iodine-doping strategy to direct the reconstruction of active species in CuS catalysts toward an unconventional oxygen vacancy oxidation mechanism, thereby overcoming the activity and stability limitations. Mechanistic analysis indicates that the electronic manipulation, weak coordination of Cu-S bonds, and lattice distortion induced by iodine-doping facilitate the thermodynamically favorable Cu²⁺ to Cu³⁺ oxidation during OER. The decisively formed oxygen vacancies are emphasized as a genuine active source to promote hydroxyl adsorption, with hypervalent Cu species acting as auxiliary sites to accelerate deprotonation by strengthening Cu-O covalent. Consequently, the optimal iodine-doped CuS exhibits a reduced overpotential of 189 mV at 10 mA cm^-2 and superb stability prolonging to 1250 h. When used as a bifunctional electrode in a membrane electrode assembly electrolyzer, it also exhibits a low voltage of 1.65 V at 1 A cm^-2, with electrolysis durability of 480 h and a low hydrogen cost of US$1.70/kg H₂, outperforming the 2026 targets set by the U.S. Department of Energy.

Molecular catalysts play a critical role in regulating the selectivity of electrocatalytic CO ₂ reduction reaction (CO ₂ RR), yet the understanding of ligand function is largely restricted to modulating the electronic structure of the metal and reaction kinetics. Herein, a hydroxyl (─OH) ligand is introduced into a sterically hindered amino‐porphyrin (o‐TAPP) to synthesize the atropisomers porphyrin‐salicylimine‐Cu (o‐Cu‐Por‐Sa) with hydrogen‐bonding interactions (O─H⋯O), enabling efficient selection of CO and CH ₄ under dual effects. Detailed analysis shows that the ─OH of o‐Cu‐Por‐Sa (αβαβ) forms a noncovalent hydrogen bond with carbonate, characterized by a bond length of 2.01 Å and an angle of 27.6°, and this interaction reduces the reaction energy barrier, achieving a faradaic efficiency (FE) of 84% for CH ₄ . Moreover, the steric hindrance effect of the symmetric distribution of ─OH facilitates protonation reactions by preventing C–C coupling. In contrast, ─OH aggregated on o‐Cu‐Por‐Sa (αααα) forms a pocket‐like hydrogen bond grid, which restricts free CO ₂ adsorption, and the rapid dissociation of *CO also interrupts the reaction. This work highlights the pivotal role of dual effects induced by ligand atropisomerization in regulating selectivity, offering new insights for the design of efficient molecular catalysts.

The space charge effect induced by high‐quality heterojunctions is essential for efficient electrocatalytic processes. Herein, we delicately manipulate intermolecular charge transfer by modifying substituents (−g=‐CH₃, ‐H, ‐NO₂) with various electron donating/withdrawing capabilities in CoPc‐g/CoS organic–inorganic heterostructures. CoPc‐CH₃, as a typical electron donor, transfers more electrons to CoS due to the presence of ‐CH₃, forming the strongest space electric field and thus regulating the dual active sites at the interface. Furthermore, oxygen‐containing intermediates preferentially adsorb on the positively charged CoPc‐CH₃ side, and the rapid accumulation of electrons on the CoS side decelerates catalyst dissolution at the oxygen evolution reaction (OER) potential, ensuring the stable OER process under the optimized adsorbate evolution mechanism. As a result, CoPc‐CH₃/CoS catalyst exhibits the lowest overpotential and remains stable for 150 h at 0.5 A cm⁻² in the membrane electrode assembly electrolyzer. The method provides a novel strategy for accurately regulating the space electric field of heterojunctions.

The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H‐down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN ₃ exhibit record‐breaking activity (E _ORR@1/2 /E _OER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere‐scale zinc‐air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large‐scale energy storage.

Realizing an efficient turnover frequency in the acidic oxygen evolution reaction by modifying the reaction configuration is crucial in designing high-performance single-atom catalysts. Here, we report a “single atom–double site” concept, which involves an activatable inert manganese atom redox chemistry in a single-atom Ru-Mn dual-site platform with tunnel Ni ions as the trigger. In contrast to conventional single-atom catalysts, the proposed configuration allows direct intramolecular oxygen coupling driven by the Ni ions intercalation effect, bypassing the secondary deprotonation step instead of the kinetically sluggish adsorbate evolution mechanism. The strong bonding of Ni ions activates the inert manganese terminal groups and inhibits the cross-site disproportionation process inherent in the Mn scaffolding, which is crucial to ensure the dual-site platform. As a result, the single-atom Ru-Ni-Mn octahedral molecular sieves catalyst delivers a low overpotential, adequate mass activity and good stability.

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of Fe─N─C catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the Fe─N bond, inhibiting the demetalation effect of Fe─N─C. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the Fe─N bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of Fe─Mn dual sites can overcome the high energy barriers to direct O─O bond dissociation and modulate the electronic states of Fe─N₄ sites. The resulting FeMn─N─C exhibits excellent ORR activity with a high half‐wave potential of 0.92 V in alkaline electrolytes. FeMn─N─C as a cathode catalyst for Zn‐air batteries has a cycle stability of 700 h at 25 °C and a long cycle stability of more than 210 h under extremely cold conditions at −40 °C. These findings contribute to the development of efficient and stable metal‐nitrogen‐carbon catalysts for various energy devices.

Developing ruthenium‐based heterogeneous catalysts with an efficient and stable interface is essential for enhanced acidic oxygen evolution reaction (OER). Herein, we report a defect‐rich ultrathin boron nitride nanosheet support with relatively independent electron donor and acceptor sites, which serves as an electron reservoir and receiving station for RuO₂, realizing the rapid supply and reception of electrons. Through precisely controlling the reaction interface, a low OER overpotential of only 180 mV (at 10 mA cm⁻²) and long‐term operational stability (350 h) are achieved, suggesting potential practical applications. In situ characterization and theoretical calculations have validated the existence of a localized electronic recycling between RuO₂ and ultrathin BN nanosheets (BNNS). The electron‐rich Ru sites accelerate the adsorption of water molecules and the dissociation of intermediates, while the interconnection between the O‐terminal and B‐terminal edge establishes electronic back‐donation, effectively suppressing the over‐oxidation of lattice oxygen. This study provides a new perspective for constructing a stable and highly active catalytic interface.

Doping engineering is an effective strategy to improve the electrocatalytic activity of manganese oxides by enhancing their poor electrical conductivity and oxygen adsorption capacity. Herein, p‐block aluminum group metal ions (Al³⁺, Ga³⁺, and In³⁺) are introduced into cryptomelane‐type manganese oxide octahedral molecular sieves (OMS‐2), leading to p−d orbital hybridization between the p‐orbitals of the aluminum group metals and d‐orbitals of Mn, facilitating the oxygen reduction reaction. The aluminum group metal‐doped OMS‐2 exhibits excellent catalytic activity, rapid reaction kinetics, and favorable stability compared to commercial Pt/C. Among the three prepared catalysts, Ga‐doped OMS‐2 (Ga‐OMS‐2) has stronger oxygen reduction activity. Experimental and theoretical calculations show that the superiority of Ga‐OMS‐2 is attributed to p−d hybridization, which enriches the reaction sites and enhances the binding strength of the catalyst to the O₂ reaction intermediates. As a proof of concept, Zinc−air batteries assembled with Ga‐OMS‐2 as a catalyst exhibit superior power density and cycle life to commercial Pt/C. This p−d hybridization strategy gives insight into the p‐block metal doping of catalysts prepared with other transition metals with excellent electrocatalytic activity and durability for energy storage and conversion.