Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO2 Electroreduction to C2H4.

Deeply electrolytic reduction of carbon dioxide (CO2) to high-value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C-C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper-based polyhedron (Cu2) that features uniformly distributed and atomically precise bi-Cu units, which can stabilize *OCCO dipole to facilitate the C-C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51% with a current density of 469.4 mA cm-2, much superior to the Cu single site catalyst (Cu SAC) (~0%). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h-1) compared to Cu nanoparticles (~9.42 h-1) and Cu SAC (~0.87 h-1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4.

A Metal-Sulfur-Carbon Catalyst Mimicking the Two-Component Architecture of Nitrogenase.

The production of ammonia (NH3) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N2. We draw inspiration from this structural enzymology, and design a two-component metal-sulfur-carbon (M-S-C) catalyst composed of sulfur-doped carbon-supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO3-) to NH3. The catalyst demonstrates a remarkable NH3 yield rate of ~37 mg L-1 h-1 and a Faradaic efficiency of ~97% for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP-surface nearby. This study proves a better understanding of how M-S-Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism-based catalyst design.

Steering the Site Distance of Atomic Cu-Cu Pairs by First-Shell Halogen Coordination Boosts CO2-to-C2 Selectivity.

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C-C coupling to unravel their structure-performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu-Cu dual sites with different site distance coordinated by halogen at the first-shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long-range Cu-Cu (Cu-I-Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long-range Cu-Cu dual site is accelerated to C2H4 generation and short-range Cu-Cu (Cu-Cl-Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long-range Cu-Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C-C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site-distance-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu-Cu dual sites.

Tuning the Local Environment of Pt Species at CNT@MO2-x (M = Sn and Ce) Heterointerfaces for Boosted Alkaline Hydrogen Evolution.

As the most promising hydrogen evolution reaction (HER) electrocatalysts, platinum (Pt)-based catalysts still struggle with sluggish kinetics and expensive costs in alkaline media. Herein, we accelerate the alkaline hydrogen evolution kinetics by optimizing the local environment of Pt species and metal oxide heterointerfaces. The well-dispersed PtRu bimetallic clusters with adjacent MO2-x (M = Sn and Ce) on carbon nanotubes (PtRu/CNT@MO2-x) are demonstrated to be a potential electrocatalyst for alkaline HER, exhibiting an overpotential of only 75 mV at 100 mA cm-2 in 1 M KOH. The excellent mass activity of 12.3 mA µg-1Pt+Ru and specific activity of 32.0 mA cm-2ECSA at an overpotential of 70 mV are 56 and 64 times higher than those of commercial Pt/C. Experimental and theoretical investigations reveal that the heterointerfaces between Pt clusters and MO2-x can simultaneously promote H2O adsorption and activation, while the modification with Ru further optimizes H adsorption and H2O dissociation energy barriers. Then, the matching kinetics between the accelerated elementary steps achieved superb hydrogen generation in alkaline media. This work provides new insight into catalytic local environment design to simultaneously optimize the elementary steps for obtaining ideal alkaline HER performance.

Shear-strained Pd Single-atom Electrocatalysts for Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction method (NitRR) is a low-carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper-based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO3. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by-product NO2-. In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd-CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol.gcat-1. h-1, and a Faraday efficiency of 90% for ammonia production at -0.5 V vs. RHE. Electrochemical in-situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision-making step for nitrate conversion to ammonia, further promote ammonia generation.

Synergy of Photogenerated Electrons and Holes toward Efficient Photocatalytic Urea Synthesis from CO2 and N2.

Directly coupling N2 and CO2 to synthesize urea by photocatalysis paves a sustainable route for urea synthesis, but its performance is limited by the competition of photogenerated electrons between N2 and CO2, as well as the underutilized photogenerated holes. Herein, we report an efficient urea synthesis process involving photogenerated electrons and holes in respectively converting CO2 and N2 over a redox heterojunction consisting of WO3 and Ni single-atom-decorated CdS (Ni1-CdS/WO3). For the photocatalytic urea synthesis from N2 and CO2 in pure water, Ni1-CdS/WO3 attained a urea yield rate of 78 µM h-1 and an apparent quantum yield of 0.15 % at 385 nm, which ranked among the best photocatalytic urea synthesis performance reported. Mechanistic studies reveal that the N2 was converted into NO species by ⋅OH radicals generated from photogenerated holes over the WO3 component, meanwhile, the CO2 was transformed into *CO species over the Ni site by photogenerated electrons. The generated NO and *CO species were further coupled to form *OCNO intermediate, then gradually transformed into urea. This work emphasizes the importance of reasonably utilizing photogenerated holes in photocatalytic reduction reactions.

Tailoring d-p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics.

The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d-p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co-substituted Ni3Se4 can hold the optimal d-p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH- adsorption-desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59 eV, matching well with the theoretical calculations). Coupling with the lower OH- diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200 times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery-type electrodes from a novel perspective of orbital-scale manipulation.

Efficient Hydrogen Generation from Ammonia Borane Hydrolysis on a Tandem Ruthenium-Platinum-Titanium Catalyst.

Hydrolysis of ammonia borane (NH3BH3, AB) involves multiple undefined steps and complex adsorption and activation, so single or dual sites are not enough to rapidly achieve the multi-step catalytic processes. Designing multi-site catalysts is necessary to enhance the catalytic performance of AB hydrolysis reactions but revealing the matching reaction mechanisms of AB hydrolysis is a great challenge. In this work, we propose to construct RuPt-Ti multi-site catalysts to clarify the multi-site tandem activation mechanism of AB hydrolysis. Experimental and theoretical studies reveal that the multi-site tandem mode can respectively promote the activation of NH3BH3 and H2O molecules on the Ru and Pt sites as well as facilitate the fast transfer of *H and the desorption of H2 on Ti sites at the same time. RuPt-Ti multi-site catalysts exhibit the highest turnover frequency (TOF) of 1293 min-1 for AB hydrolysis reaction, outperforming the single-site Ru, dual-site RuPt and Ru-Ti catalysts. This study proposes a multi-site tandem concept for accelerating the dehydrogenation of hydrogen storage material, aiming to contribute to the development of cleaner, low-carbon, and high-performance hydrogen production systems.

Ruthenium Single Atomic Sites Surrounding the Support Pit with Exceptional Photocatalytic Activity.

Single-metal atomic sites and vacancies can accelerate the transfer of photogenerated electrons and enhance photocatalytic performance in photocatalysis. In this study, a series of nickel hydroxide nanoboards (Ni(OH)x NBs) with different loadings of single-atomic Ru sites (w-SA-Ru/Ni(OH)x) were synthesized via a photoreduction strategy. In such catalysts, single-atomic Ru sites are anchored to the vacancies surrounding the pits. Notably, the SA-Ru/Ni(OH)x with 0.60 wt % Ru loading (0.60-SA-Ru/Ni(OH)x) exhibits the highest catalytic performance (27.6 mmol g-1 h-1) during the photocatalytic reduction of CO2 (CO2RR). Either superfluous (0.64 wt %, 18.9 mmol g-1 h-1; 3.35 wt %, 9.4 mmol-1 h-1) or scarce (0.06 wt %, 15.8 mmol g-1 h-1; 0.29 wt %, 21.95 mmol g-1 h-1; 0.58 wt %, 23.4 mmol g-1 h-1) of Ru sites have negative effect on its catalytic properties. Density functional theory (DFT) calculations combined with experimental results revealed that CO2 can be adsorbed in the pits; single-atomic Ru sites can help with the conversion of as-adsorbed CO2 and lower the energy of *COOH formation accelerating the reaction; the excessive single-atomic Ru sites occupy vacancies that retard the completion of CO2RR.

Breaking the Scaling Relationship in C-N Coupling via the Doping Effects for Efficient Urea Electrosynthesis.

Electrochemical C-N coupling reaction based on carbon dioxide and nitrate have been emerged as a new "green synthetic strategy" for the synthesis of urea, but the catalytic efficiency is seriously restricted by the inherent scaling relations of adsorption energies of the active sites, the improvement of catalytic activity is frequently accompanied by the decrease in selectivity. Herein, a doping engineering strategy was proposed to break the scaling relationship of intermediate binding and minimize the kinetic barrier of C-N coupling. A thus designed SrCo0.39Ru0.61O3-δ catalyst achieves a urea yield rate of 1522 µg h-1 mgcat. -1 and faradic efficiency of 34.1 % at -0.7 V versus reversible hydrogen electrode. A series of characterizations revealed that Co doping not only induces lattice distortion but also creates rich oxygen vacancies (OV) in the SrRuO3. The oxygen vacancies weaken the adsorption of *CO and *NH2 intermediates on the Co and Ru sites respectively, and the strain effects over the Co-Ru dual sites promoting the occurrence of C-N coupling of the two monomers instead of selective hydrogenating to form by-products. This work presents an insight into molecular coupling reactions towards urea synthesis via the doping engineering on SrRuO3.

Overcoming Electrostatic Interaction via Pulsed Electroreduction for Boosting the Electrocatalytic Urea Synthesis.

Electrocatalytic urea synthesis under ambient conditions offers a promising alternative strategy to the traditional energy-intensive urea industry protocol. Limited by the electrostatic interaction, the reduction reaction of anions at the cathode in the electrocatalytic system is not easily achievable. Here, we propose a novel strategy to overcome electrostatic interaction via pulsed electroreduction. We found that the reconstruction-resistant CuSiOx nanotube, with abundant atomic Cu-O-Si interfacial sites, exhibits ultrastability in the electrosynthesis of urea from nitrate and CO2. Under a pulsed potential approach with optimal operating conditions, the Cu-O-Si interfaces achieve a superior urea production rate (1606.1 µg h-1 mgcat. -1) with high selectivity (79.01 %) and stability (the Faradaic efficiency is retained at 80 % even after 80 h of testing), outperforming most reported electrocatalytic synthesis urea catalysts. We believe our strategy will incite further investigation into pulsed electroreduction increasing substrate transport, which may guide the design of ambient urea electrosynthesis and other energy conversion systems.

Tailoring Oxygen Reduction Reaction Kinetics of Fe-N-C Catalyst via Spin Manipulation for Efficient Zinc-Air Batteries.

The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the oxygen reduction reaction (ORR) kinetics. Herein, a new approach for boosting the inherent ORR activity of atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. The as-prepared catalyst delivers excellent ORR activity with half-wave potentials of 0.78 and 0.90 V in acidic and alkaline solutions, respectively. The decent ORR activity can also be validated from the high-performance rechargeable Zn-air battery. The experiments and density functional theory calculations reveal that the electron spin-state of monodispersed Fe active sites is transferred from the low spin (LS, t2g 6 eg 0) to the medium spin (MS, t2g 5 eg 1) due to the involvement of Fe atomic clusters, leading to the spin electron filling in σ∗ orbit, by which it favors OH- desorption and in turn boosts the reaction kinetics of the rate-determining step. This work paves a solid way for rational design of high-performance Fe-based single atom catalysts through spin manipulation.

Glycerol Electrooxidation over Precision-Synthesized Gold Nanocrystals with Different Surface Facets.

Electrochemical glycerol oxidation (EGO) emerges as a promising route to valorize glycerol, an underutilized byproduct from biodiesel production, into value-added chemicals. This study employed three types of gold (Au) nanocrystals with controlled shapes to elucidate the facet-dependent electrocatalytic behavior in EGO. Octahedral, rhombic dodecahedral, and cubic Au nanocrystals with {111}, {110}, and {100} facets, respectively, were precisely synthesized with uniform size and shape. Rhombic dodecahedra exhibited the lowest onset potential for EGO due to facile AuOH formation, while octahedra showed enhanced electrochemical activity for glycerol oxidation and resistance to poisoning. In-situ FTIR analysis revealed that Au {111} surfaces selectively favored C2 products, whereas Au {100} surfaces promoted C3 product formation, highlighting the significant effect of facet orientation on EGO performance and informing catalyst design.

Emerging electrospinning platform toward nanoparticle to single atom transformation for steering selectivity in ammonia synthesis.

The rising top-down synthetic methodologies for transition metal single-atom catalysts (SACs) require controlled movement of metal atoms through the substrates; however, their direct transportation towards the ideal carrier remains a huge challenge. Herein, we showed a "top down" strategy for Co nanoparticles (NPs) to Co SA transformation by employing electrospun carbon nanofibers (CNFs) as atom carriers. Under high-temperature conditions, the Co atoms migrate from the surfaces of Co NPs and are then anchored by the surrounding carbon to form a Co-C3O1 coordination structure. The synthesized Co SAs/CNF electrocatalyst exhibits excellent electrocatalytic nitrate reduction reaction (NO3RR) activity with an NH3 yield of 0.79 mmol h-1 cm-2 and Faraday efficiency (FE) of 91.3% at -0.7 V vs. RHE in 0.1 M KNO3 and 0.1 M K2SO4 electrolytes. The in situ electrochemical characterization suggests that the NOH pathway is preferred by Co SAs/CNFs, and *NO hydrogenation and deoxygenation easily occur on Co SAs due to the small adsorption energy between Co SAs and *NO, as calculated by theoretical calculations. It is revealed that a small energy barrier (0.45 eV) for the rate determining step (RDS) ranges from *NO to *NOH and a strong capability for inhibiting hydrogen evolution (HER) significantly promotes the NH3 selectivity and activity of Co SAs/CNFs.

Engineering a Dynamic Solvent-Phobic Liquid Electrolyte Interphase for Long-Life Lithium Metal Batteries.

The heterogeneity, species diversity, and poor mechanical stability of solid electrolyte interphases (SEIs) in conventional carbonate electrolytes result in the irreversible exhaustion of lithium (Li) and electrolytes during cycling, hindering the practical applications of Li metal batteries (LMBs). Herein, this work proposes a solvent-phobic dynamic liquid electrolyte interphase (DLEI) on a Li metal (Li-PFbTHF (perfluoro-butyltetrahydrofuran)) surface that selectively transports salt and induces salt-derived SEI formation. The solvent-phobic DLEI with C-F-rich groups dramatically reduces the side reactions between Li, carbonate solvents, and humid air, forming a LiF/Li3PO4-rich SEI. In situ electrochemical impedance spectroscopy and Ab-initio molecular dynamics demonstrate that DLEI effectively stabilizes the interface between Li metal and the carbonate electrolyte. Specifically, the LiFePO4||Li-PFbTHF cells deliver 80.4% capacity retention after 1000 cycles at 1.0 C, excellent rate capacity (108.2 mAh g-1 at 5.0 C), and 90.2% capacity retention after 550 cycles at 1.0 C in full-cells (negative/positive (N/P) ratio of 8) with high LiFePO4 loadings (15.6 mg cm-2) in carbonate electrolyte. In addition, the 0.55 Ah pouch cell of 252.0 Wh kg-1 delivers stable cycling. Hence, this study provides an effective strategy for controlling salt-derived SEI to improve the cycling performances of carbonate-based LMBs.

Symmetry-Broken Ru Nanoparticles with Parasitic Ru-Co Dual-Single Atoms Overcome the Volmer Step of Alkaline Hydrogen Oxidation.

Efficient dual-single-atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual-single-atom site generation remains formidable challenges. Here, we break the local symmetry of ultra-small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1 Ru1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen-affine Co atom disrupts the symmetry of ultra-small Ru nanoparticles, resulting in parasitic Ru and Co dual-single-atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2 O. As anticipated, Co1 Ru1,n /rGO exhibits ultrahigh mass activity (7.68 A mgRu -1 ) at 50 mV and exchange current density (0.68 mA cm-2 ), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi-single-atom and metal nanoparticle catalysis.

Why do Single-Atom Alloys Catalysts Outperform both Single-Atom Catalysts and Nanocatalysts on MXene?

Single-atom alloys (SAAs), combining the advantages of single-atom and nanoparticles (NPs), play an extremely significant role in the field of heterogeneous catalysis. Nevertheless, understanding the catalytic mechanism of SAAs in catalysis reactions remains a challenge compared with single atoms and NPs. Herein, ruthenium-nickel SAAs (RuNiSAAs ) synthesized by embedding atomically dispersed Ru in Ni NPs are anchored on two-dimensional Ti3 C2 Tx MXene. The RuNiSAA-3 -Ti3 C2 Tx catalysts exhibit unprecedented activity for hydrogen evolution from ammonia borane (AB, NH3 BH3 ) hydrolysis with a mass-specific activity (rmass ) value of 333 L min-1 gRu -1 . Theoretical calculations reveal that the anchoring of SAAs on Ti3 C2 Tx optimizes the dissociation of AB and H2 O as well as the binding ability of H* intermediates during AB hydrolysis due to the d-band structural modulation caused by the alloying effect and metal-supports interactions (MSI) compared with single atoms and NPs. This work provides useful design principles for developing and optimizing efficient hydrogen-related catalysts and demonstrates the advantages of SAAs over NPs and single atoms in energy catalysis.

Constructing Wide-Temperature Lithium-Sulfur Batteries by Using a Covalent Organic Nanosheet Wrapped Carbon Nanotube.

Lithium-sulfur (Li-S) batteries hold the superiority of eminent theoretical energy density (2600 Wh kg-1 ). However, the ponderous sulfur reduction reaction and the issue of polysulfide shuttling pose significant obstacles to achieving the practical wide-temperature operation of Li-S batteries. Herein, a covalent organic nanosheet-wrapped carbon nanotubes (denoted CON/CNT) composite is synthesized as an electrocatalyst for wide-temperature Li-S batteries. The design incorporates the CON skeleton, which contains imide and triazine functional units capable of chemically adsorbing polysulfides, and the underlaid CNTs facilitate the conversion of captured polysulfides enabled by enhanced conductivity. The electrocatalytic behavior and chemical interplay between polysulfides and the CON/CNT interlayer are elucidated by in situ X-ray diffraction detections and theoretical calculations. Resultantly, the CON/CNT-modified cells demonstrate upgraded performances, including wide-temperature operation ranging from 0 to 65 °C, high-rate performance (625 mAh g-1 at 5.0 C), exceptional high-rate cyclability (1000 cycles at 5.0 C), and stable operation under high sulfur loading (4.0 mg cm-2 ) and limited electrolyte (5 µL mgs -1 ). These findings might guide the development of advanced Li-S batteries.

Unraveling the Activity Trends and Design Principles of Single-Atom Catalysts for Nitrate Electrocatalytic Reduction.

Electrocatalytic nitrate (NO3-) reduction represents one of the most promising approaches to mitigate NO3- pollution and yield NH3, but it is still challenged by the atomic economy and selectivity issues of substantial active sites. Here, we describe a comprehensive investigation on a series of single-atom catalysts (SACs) using nitrogen-doped carbon as substrate (metal/NC). The essence of activity is related to the extent of the electron transfer capacity (SAs → NO3-). Among these examined SACs, the Cu/NC presents good performance toward NH3 synthesis, i.e., a maximum NH3 Faradaic efficiency of 100% with a high NH3 yield rate of up to 32,300 µg h-1 mgcat.-1. X-ray absorption fine structure spectra and density functional theory calculations provide evidence that the electronic structure of Cu-N4 coordination prohibits the formation of N2, N2O, and H2 and facilitates the orbital hybridization between the 2p orbitals of NO3- and 3d orbitals of Cu single-atom sites. Our study is believed to provide fundamental guidance for the future design of highly efficient electrocatalysts in NO3- reduction to NH3.

Ir-Sn pair-site triggers key oxygen radical intermediate for efficient acidic water oxidation.

The anode corrosion induced by the harsh acidic and oxidative environment greatly restricts the lifespan of catalysts. Here, we propose an antioxidation strategy to mitigate Ir dissolution by triggering strong electronic interaction via elaborately constructing a heterostructured Ir-Sn pair-site catalyst. The formation of Ir-Sn dual-site at the heterointerface and the resulting strong electronic interactions considerably reduce d-band holes of Ir species during both the synthesis and the oxygen evolution reaction processes and suppress their overoxidation, enabling the catalyst with substantially boosted corrosion resistance. Consequently, the optimized catalyst exhibits a high mass activity of 4.4 A mgIr-1 at an overpotential of 320 mV and outstanding long-term stability. A proton-exchange-membrane water electrolyzer using this catalyst delivers a current density of 2 A cm-2 at 1.711 V and low degradation in an accelerated aging test. Theoretical calculations unravel that the oxygen radicals induced by the π* interaction between Ir 5d-O 2p might be responsible for the boosted activity and durability.