Adsorption Of Intermediates Research Articles

Synergistic effect of Fe-Ru alloy and Fe-N-C sites on oxygen reduction reaction

In the pursuit of optimizing Fe-N-C catalysts for the oxygen reduction reaction (ORR), the incorporation of alloy nanoparticles has emerged as a prominent strategy. In this work, we effectively synthesized the FeRu-NC catalyst by anchoring Fe-Ru alloy nanoparticles and FeN4 single atom sites onto carbon nanotubes. The FeRu-NC catalyst exhibits significantly enhanced ORR activity and long-term stability, with a high half-wave potential of 0.89 V (vs. RHE) in alkaline conditions, and the half-wave potential remains nearly unchanged after 5000 cycles. The zinc-air battery (ZAB) assembled with FeRu-NC demonstrates a power density of 169.1 mW cm−2, surpassing that of commercial Pt/C. Density functional theory (DFT) calculations reveal that the synergistic interaction between the Fe–Ru alloy and FeN4 single atoms alters the electronic structure and facilitates charge transfer at the FeN4 sites, thereby modulating the adsorption and desorption of ORR intermediates. This enhancement in catalytic activity for the ORR process underscores the potential of this approach for refining M-N-C catalysts, providing novel insights into their optimization strategies.

Nitrogen-rich carbon nanosheets supported copper catalysts for oxidative carbonylation of ethanol

Two-dimensional (2D) nitrogen-rich carbon nanosheets NC-x with a nitrogen content of 5.2 %-6.8 wt% were characterized by a one-step co-pyrolysis method and employed as Cu catalyst supports for oxidative carbonylation of ethanol. Carbon nanosheets with abundant nitrogen defects were achieved by tuning the dosage of ammonium oxalate, in which the Cu/NC-12 catalyst performed excellent activity. Furthermore, Cu/NC-x catalysts presented significantly superior catalytic activity than that of copper/carbon nanosheets (Cu/C) catalyst, it can be ascribed to the most suitable nitrogen doping to promote the exposure and dispersion of Cu species and pyridine nitrogen served as the main anchor sites to increase the ratio of Cu+/(Cu++Cu0). Density functional theory calculations further proved that introducing nitrogen atoms into carbon nanosheets effectively reinforced binding to Cu4 and adsorption of intermediates with NC, and a remarkable activity on Cu/NC-12 was achieved by a more favorable insertion of CO in the rate-determining step.

Construction of high‐loading WO3‐x sub‐nanometer clusters via orderly‐anchored top–down strategy boost acidic hydrogen evolution

AbstractExploring a simple, rapid, and scalable synthesis method for the synthesis of high loading nonprecious metal sub‐nanometer clusters (SNCs) electrocatalysts is one of the most promising endeavors today. Herein, an orderly‐anchored top–down strategy is proposed for fabricating a new type of high loading WO3‐x SNCs on O‐functional group‐modified Ketjen black (WO3‐x‐C(O)) to balance the high loading (49.29 wt.%) and sub‐nanometer size. By optimizing the vacancy number, WO2.71‐C(O) has extremely large electrochemically active surface area (402 m2 g−1) and high turnover frequency value of 1.722 s−1 at −50 mV (vs. reversible hydrogen electrode). The overpotential of WO2.71‐C(O) reaches 22 mV at a current density of 10 mA cm−2, which is significantly better than the commercial Pt/C level (32 mV), achieving a breakthrough in the hydrogen evolution reaction (HER) catalytic activity of nonprecious metals in acidic environment. Theoretical calculations and in situ characterization show that this material allows for the enrichment of reactants (H*) and the optimization of intermediate adsorption, which leads to the enhancement of acidic HER catalytic activity.

Rhenium-promoter-free ruthenium–zirconia catalyst for high-yield direct conversion of succinic acid to 1,4-butanediol in water

The direct conversion of succinic acid to 1,4-butanediol (1,4-BDO) in water was investigated using Ru deposited on oxygen-vacant zirconia (Ru–OvZrOx) as the catalyst. 1,4-BDO was produced in high yield (89.5 %) and space–time yield (0.19 h−1) at 200 °C. The proximity of Ru to OvZrOx stabilized the nanosized Ru0 particles, enabled hydrogen spillover, increased the acidity of the catalyst, and achieved intermediate adsorption. The Zrδ+ center (2 ≤ δ < 4)—which featured abundant Lewis acid sites and was adjacent to the Ov sites—activated the γ-butyrolactone ring-opening reaction via a route involving 2-hydroxytetrahydrofuran formation. The electron-rich Ru0 center facilitated heterolytic hydrogen dissociation, and the dissociated H– and H+ ions traveled to the Zrδ+ sites and water molecules via hydrogen-shuttling mechanism. Moreover, the weakly bonded hydrogen actively participated in the hydrodeoxygenation and hydrogenation of intermediates to 1,4-BDO.

Atomically dispersed ruthenium in transition metal double layered hydroxide as a bifunctional catalyst for overall water splitting

Efficient and sustainable energy conversion depends on the rational design of single-atom catalysts. The control of the active sites at the atomic level is vital for electrocatalytic materials in alkaline and acidic electrolytes. Moreover, fabrication of effective catalysts with a well-defined surface structure results in an in-depth understanding of the catalytic mechanism. Herein, a single atom ruthenium dispersed in nickel-cobalt layered hydroxide (Ru-NiCo LDH) is reported. Through the precise controlling of the atomic dispersion and local coordination environment, Ru-NiCo LDH//Ru-NiCo LDH provides an ultra-low overpotential of 1.45 mV at 10 mA cm−2 for the overall water splitting, which surpasses that of the state-of-the-art Pt/C/RuO2 redox couple. Density functional theory calculations show that Ru-NiCo LDH optimizes hydrogen evolution intermediate adsorption energies and promotes O-O coupling at a Ru-O active site for oxygen evolution, while Ni serves as the water dissociation site for effective water splitting. As a potential model, Ru-NiCo LDH shows enhanced water splitting performance with potential for the development of promising water-alkaline catalysts.

Rationalizing the catalytic surface area of oxygen vacancy‐enriched layered perovskite LaSrCrO4 nanowires on oxygen electrocatalyst for enhanced performance of Li–O2 batteries

AbstractEfficient electrocatalysis at the cathode is crucial to addressing the limited stability and low rate capability of Li−O2 batteries. This study examines the kinetic behavior of Li−O2 batteries utilizing layered perovskite LaSrCrO4 nanowires (NWs) composed of lower oxidation states. Layered perovskite LaSrCrO4 NWs exhibited improved rate capability over a wide range of current densities and longer cycle life in Li−O2 batteries than V‐based layered perovskite (LaSrVO4) and simple perovskite (La0.8Sr0.2CrO3) NWs. X‐ray photoelectron spectroscopy and electrochemical surface area analyses showed that the observed performance variations primarily stemmed from active sites such as oxygen vacancies. In situ Raman analysis showed that these active sites significantly modulate the kinetics of oxygen reduction and evolution, which are related to LiO2 intermediate adsorption. Electrochemical impedance spectroscopy showed that the active sites in layered perovskite LaSrCrO4 NWs contributed to their high charge transfer capability and reduced polarization. This study presents an appealing method for the precise fabrication and analysis of Cr‐based layered perovskites, aimed at achieving highly efficient and stable bifunctional oxygen electrocatalysis.

Gapped and Rotated Grain Boundary Revealed in Ultra-Small Au Nanoparticles for Enhancing Electrochemical CO2 Reduction.

Although gapped grain boundaries have often been observed in bulk and nanosized materials, and their crucial roles in some physical and chemical processes have been confirmed, their acquisition at ultrasmall nanoscale presents a significant challenge. To date, they had not been reported in metal nanoparticles smaller than 2 nm owing to the difficulty in characterization and the high instability of grain boundary (GB) atoms. Herein, we have successfully developed a synthesis method for producing a novel chiral nanocluster Au78(TBBT)40 (TBBT=4-tert-butylphenylthiolate) with a 26-atom gapped and rotated GB. This nanocluster was precisely characterized using single-crystal X-ray crystallography and mass spectrometry. Additionally, an offset atomic defect linked to the peripheral Au(TBBT)2 staple was found in the structure. Comparing it to similarly face-centered cubic-structured Au36(TBBT)24, Au44(TBBT)28, Au52(TBBT)32, Au92(TBBT)44, and ~5 nm nanocrystals, the bridging Au78(TBBT)40 nanocluster exhibited higher catalytic activity in the electroreduction of CO2 to CO. This enhanced activity was explained through density functional theory calculations and X-ray photoelectron spectroscopy analysis, which highlight the impact of GBs and point defects on the surface properties of metal nanoclusters in balancing intermediate adsorption and product desorption.

Inclusion Strategy for Constructing S/N Orbital Hybridization-Regulated sp3/sp2 Carbon toward Boost Electrocatalysis.

Metal-free carbon-based electrocatalysts have gained significant attention in the field of zinc-air batteries (ZABs) due to their affordability, good conductivity and chemical stability. However, unmodified carbon materials typically fall short in adsorbing and activating the substrates and intermediates involved in oxygen reduction reactions (ORR). Here, a metal-free carbon-based electrocatalyst with S atom p orbital hybrid modified N-sp3/sp2 carbon structure (C/NS) were prepared by cyclodextrins inclusion. The catalyst demonstrates impressive ORR activity (E1/2=0.885 V vs. RHE) and robust ZABs performance with a power density of 171.3 mW cm-2 and a specific capacity of 781.2 mAh g-1. Density functional theory (DFT) calculation reveals that S atom effectively regulates the charge distribution and p-band center of active site carbon atom in the N-sp3/sp2 carbon structure. This modification prompts the adsorption and dissociation of O2 and intermediates, resulting in higher reactive activity. This work provides a valuable and practical strategy for preparing cost-effective metal-free carbon-based electrocatalysts for ORR with high performance.

Microwave‐Assisted PtRu Alloying on Defective Tungsten Oxide: A Pathway to Improved Hydroxyl Dynamics for Highly‐Efficient Hydrogen Evolution Reaction

AbstractPlatinum (Pt)‐based compounds are the benchmarked catalysts for hydrogen evolution reaction (HER) but exhibit slow kinetics in alkaline environments. The *OH accumulation on Pt surface can block active sites, affecting proton reduction and water re‐adsorption. Alloying Ruthenium (Ru) with Pt sites can significantly modulate the adsorption and desorption of water dissociation intermediates. Choosing suitable supports and utilizing metal‐support interaction (MSI) is crucial for active site optimization. PtRu alloy anchored on tungsten oxide (WO3) with rich oxygen vacancies (OV) is prepared through an ultrafast microwave‐assisted approach. Benefiting from the coupling effects between alloying and MSI, PtRu/WO3‐OV exhibits exceptionally high HER activity. In 1 m KOH, 1 m KOH + seawater, and 0.5 m H2SO4, it requires ultralow overpotentials of 9, 26, and 6 mV to achieve 10 mA cm−2, respectively. The designed catalyst surpasses commercial Pt/C in mass activity and demonstrates considerable potential for intermittent energy integration. Density functional theory reveals that alloying Ru with Pt sites significantly reduces the energy barrier of dissociating *OH, modulating blockage on the surface and then promoting the overall alkaline HER process. This study offers insights into the rapid synthesis of non‐carbon supported catalysts with Pt site modulation for alkaline hydrogen generation.

Modulating Spin of Atomic Manganese Center for High-Performance Oxygen Reduction Reaction.

Single atom catalysts (SACs) are promising non-precious catalysts for oxygen reduction reaction (ORR). Unfortunately, the ORR SACs usually suffer from unsatisfactory activity and in particular poor stability. Herein, we report atomically dispersed manganese (Mn) embedded on nitrogen and sulfur co-doped graphene as an efficient and robust electrocatalyst for ORR in alkaline electrolyte, realizing a half-wave potential (E1/2) of 0.883 V vs. reversible hydrogen electrode (RHE) with negligible activity degradation after 40,000 cyclic voltammetry (CV) cycles in 0.1 M KOH. Introducing sulfur (S) to form Mn-S coordination changes the spin state of single Mn atom from high-spin to low-spin, which effectively optimizes the oxygen intermediates adsorption over the single Mn atomic sites and thus greatly improves the ORR activity.

Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production

Copper (Cu)-based catalysts show promise for electrocatalytic CO2 reduction (CO2RR) to multi-carbon alcohols, but thermodynamic constraints lead to competitive hydrocarbon (e.g., ethylene) production. Achieving selective ethanol production with high Faradaic efficiency (FE) and current density is still challenging. Here we show a multivalent Cu-based catalyst, Cu-2,3,7,8-tetraaminophenazine-1,4,6,9-tetraone (Cu-TAPT) with Cu2+ and Cu+ atomic ratio of about 1:2 for CO2RR. Cu-TAPT exhibits an ethanol FE of 54.3 ± 3% at an industrial-scale current density of 429 mA cm−2, with the ethanol-to-ethylene ratio reaching 3.14:1. Experimental and theoretical calculations collectively unveil that the catalyst is stable during CO2RR, resulting from suitable coordination of the Cu2+ and Cu+ with the functional groups in TAPT. Additionally, mechanism studies show that the increased ethanol selectivity originates from synergy of multivalent Cu sites, which can promote asymmetric C–C coupling and adjust the adsorption strength of different carbonaceous intermediates, favoring hydroxy-containing C2 intermediate (*HCCHOH) formation and formation of ethanol.

Modulating Spin of Atomic Manganese Center for High‐Performance Oxygen Reduction Reaction

Single atom catalysts (SACs) are promising non‐precious catalysts for oxygen reduction reaction (ORR). Unfortunately, the ORR SACs usually suffer from unsatisfactory activity and in particular poor stability. Herein, we report atomically dispersed manganese (Mn) embedded on nitrogen and sulfur co‐doped graphene as an efficient and robust electrocatalyst for ORR in alkaline electrolyte, realizing a half‐wave potential (E1/2) of 0.883 V vs. reversible hydrogen electrode (RHE) with negligible activity degradation after 40,000 cyclic voltammetry (CV) cycles in 0.1 M KOH. Introducing sulfur (S) to form Mn‐S coordination changes the spin state of single Mn atom from high‐spin to low‐spin, which effectively optimizes the oxygen intermediates adsorption over the single Mn atomic sites and thus greatly improves the ORR activity.

Interstitial Boron Atoms in Pd Aerogel Selectively Switch the Pathway for Glycolic Acid Synthesis from Waste Plastics.

Electro-reforming of poly(ethylene terephthalate) (PET) into valuable chemicals is garnering significant attention as it opens a mild avenue for waste resource utilization. However, achieving high activity and selectivity for valuable C2 products during ethylene glycol (EG) oxidation in PET hydrolysate on Pd electrocatalysts remains challenging. The strong interaction between Pd and carbonyl (*CO) intermediates leads to undesirable over-oxidation and poisoning of Pd sites, which hinders the highly efficient C2 products production. Herein, a nonmetallic alloying strategy is employed to fabricate a Pd-boron alloy aerogel (PdB), wherein B atoms are induced to regulate the electron structure and surface oxophilicity. This approach allows a remarkable mass activity of 6.71 A mgPd -1, glycolic acid (GA) Faradaic efficiency (FE) of 93.8%, and stable 100 h cyclic electrolysis. In situ experiments and density functional theory calculations reveal the contributions of B inserted in Pd lattice on highly effective EG-to-GA conversion. Interestingly, the heightened surface oxophilicity and regulated electronic structure by B incorporation weakened *CO intermediates adsorption and enhanced hydroxyl species affinity to accelerate oxidative *OH adspecies formation, thereby synergistically avoiding over-oxidation and boosting GA synthesis. This work provides valuable insights for the rational design of high-performance electrocatalysts for GA synthesis via an oxophilic B motifs incorporation strategy.

Cerium-doped construction of oxygen vacancies in IrO2 to promote acidic OER reaction

Proton exchange membrane electrolysis of water is currently recognized in the world as an up-and-coming method for the preparation of green hydrogen energy. Due to its sustainability and low pollution, it has attracted much attention from practitioners recently. The most advanced iridium oxide (IrO2) is the most promising catalyst.However, developing a highly efficient and stable IrO2 catalyst that can adapt to industrial conditions remains a terrific challenge. One of the main problems to be solved is that the slow oxygen evolution reaction(OER) at the anode limits the production of hydrogen. We propose a straightforward method for synthesizing Ce metal-doped IrO2 with a high oxygen vacancy concentration while simultaneously improving the IrO2 catalytic activity and stability.The Ce-doped IrO2 (Ce-IrO2) exhibits a microscopic nanoparticle morphology and a high density of oxygen vacancies, enabling a rapid oxygen evolution reaction (OER) process with a low overpotential of 240 mV at 10 mA·cm-2 and a remarkable stability of over 50 h under acidic conditions.A growing body of research shows a synergistic effect of oxygen vacancies and mental dopants on the adsorption and evolution of active intermediates in the active center so that the oxygen evolution reaction activity of the Ir-based catalyst can be improved. We hope that ourwork will provide a sample method for acquiring catalysts capable of adapting to a wide range of conditions via metal doping.

Complementary Multisite Turnover Catalysis toward Superefficient Bifunctional Seawater Splitting at Ampere-Level Current Density.

The utilization of seawater for hydrogen production via water splitting is increasingly recognized as a promising avenue for the future. The key dilemma for seawater electrolysis is the incompatibility of superior hydrogen- and oxygen-evolving activities at ampere-scale current densities for both cathodic and anodic catalysts, thus leading to large electric power consumption of overall seawater splitting. Here, in situ construction of Fe4N/Co3N/MoO2 heterostructure arrays anchoring on metallic nickel nitride surface with multilevel collaborative catalytic interfaces and abundant multifunctional metal sites is reported, which serves as a robust bifunctional catalyst for alkaline freshwater/seawater splitting at ampere-level current density. Operando Raman and X-ray photoelectron spectroscopic studies combined with density functional theory calculations corroborate that Mo and Co/Fe sites situated on the Fe4N/Co3N/MoO2 multilevel interfaces optimize the reaction pathway and coordination environment to enhance water adsorption/dissociation, hydrogen adsorption, and oxygen-containing intermediate adsorption, thus cooperatively expediting hydrogen/oxygen evolution reactions in base. Inspiringly, this electrocatalyst can substantially ameliorate overall freshwater/seawater splitting at 1000mA cm-2 with low cell voltages of 1.65/1.69V, along with superb long-term stability at 500-1500mA cm-2 for over 200 h, outperforming nearly all the ever-reported non-noble electrocatalysts for freshwater/seawater electrolysis. This work offers a viable approach to design high-performance bifunctional catalysts for seawater splitting.

One-step corrosion inducing the amorphous/crystalline-Co0.8Ru0.2/RuCoOx heterostructures for urea-assisted water decomposition at ampere-level current density

It is challenging to directionally construct the amorphous/crystalline (a/c)-alloy/oxide heterostructures with exceptional bifunctional electrocatalytic performances via a facile method. With these in mind, the a/c-RuCo NWs/NF electrode with the unique hollow structure and a/c-Co0.8Ru0.2/RuCoOx heterostructure was constructed by cleverly controlling the corrosion time. As expected, the well-designed a/c-RuCo NWs/NF||a/c-RuCo NWs/NF only needs 1.46 V to reach an industrial-grade current density of 1 A cm−2, outperforming other advanced electrodes. Strikingly, density functional theory (DFT) and in-situ Raman reveal that the Ruδ+-Ru0 dual-sites and Coδ+ at the a/c-Co0.8Ru0.2/RuCoOx heterointerface act as active species for alkaline HER and UOR, synergistically promoting urea-assisted water splitting. Surprisingly, the unique Co0.8Ru0.2 alloy exhibits the potential to surpass the pure Ru metal in optimizing d-band centers and the adsorption of reaction intermediates. Overall, the a/c-alloy/oxide bifunctional electrode with Ruδ+-Ru0-Coδ+ multi-active sites was constructed by one-step corrosion, providing a new idea for designing efficient a/c-alloy/oxide electrodes and realizing industrial urea-assisted water splitting.

Synergistic effects of Co/Fe bimetallic polymer catalysts for enhanced ORR/OER: Insights from thermodynamic and in-situ kinetic study

Bifunctional catalysts for oxygen reduction reaction and oxygen evolution reaction in Zinc-air batteries have been long pursued for the development of clean energy transformation devices. Yet, the underlying mechanism of the promoted electrocatalytic performance is still vague. Herein, a pyrolysis-free Co/Fe bimetallic phthalocyanine coordination polymer Co/Fe-TPDA-CP is firstly synthesized using heterometal tetra-aminophthalocyanines (MTAPcs, M=Co/Fe) as structural model and N,N,N’,N’-tetra(4-folmylphenyl)-p-phenylenediamine (TPDA) as linker. The Co/Fe-TPDA-CP exhibits the high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities with low ΔE of 692 mV, superior to monometallic Fe-TPDA-CP and Co-TPDA-CP polymers. Density functional theory (DFT) calculation and thermodynamic analysis find that ORR and OER happened separately on Fe and Co sites, in which the presence of second metal modulates the d-band center and optimizes the intermediates adsorption, thereby improving the ORR/OER synergistically. Moreover, dynamic analysis explains that the enhanced ORR stability originated from the fast H2O2 decomposition catalyzed by Co-N4 sites. Furthermore, the Zn-air battery with Co/Fe-TPDA-CP electrode also exhibits a high peak power density (97 mW cm−2) and specific capacity (780 mA h g−1). Through the proof-of-concept bifunctional electrocatalyst with clear structure and synergistic mechanism, this work paves the way for future molecular oxygen electrocatalyst design.

Modulating the electronic structure of PdCoP nanonetworks alloy for efficient electro-catalysis of methanol oxidation

Modulating the d-orbital electronic structure of active metals by doping heteroatoms is efficient for the electro-catalysis of methanol oxidation reaction (MOR). However, precise doping hybrid atoms into the lattices of alloy catalysts remains challenging. Herein, the selected doping of electron-rich P atoms at the active site of Pd was achieved by hydrothermal reduction. We found that P atoms prefer to bond Pd atoms, thus tuning the electronic structure of active sites in PdCoP alloy. Consequently, the tailored PdCoP catalyst exhibited remarkable mass activity of 2.13 A mgPd−1 towards MOR, which surpasses most reported Pd-based alloy nanocatalysts. Theoretical calculations revealed that the tailored d-band center of Pd in PdCoP catalyst exhibited moderate adsorption of CO and OH intermediates, thus maximizing the MOR performance. The current work highlights the fabrication of P-doped Pd-based catalysts for realizing high MOR, which can be further extended to other energy-related applications.

Boosting the bifunctional electrocatalytic performance of Co2C via engineering the d-band center and hydrophilicity

Replacing the sluggish oxygen evolution reaction with the oxidation of benzyl alcohol to construct the hybrid water electrolysis system has been attractive for its merits of environmentally friendly and economically efficient. However, the activity of the catalyst to oxidize alcohols needs to be further improved. Tailoring the d-band center (Ed) has been proven as an effective method to promote the hydrogen evolution reaction (HER). How feasible is this strategy in the oxidation of benzyl alcohol? Here, using Co2C as a research platform, the doping nonmetal heteroatom (P, S, N) engineering is adopted to promote its electrocatalytic BA oxidation and HER performance. The results of electrochemical tests show that the P-doped Co2C (P–Co2C) only requires a low potential of 1.33 and 1.38 V vs. RHE to achieve current densities of 20 and 100 mA cm−2 for BA oxidation, which is superior to that of S–Co2C, N–Co2C, and pristine Co2C. The conversation and faradaic efficiency for BA is up to 98.1% and 93.8% during ten consecutive cycle tests. The P–Co2C also exhibited outstanding activity and stability toward HER. The density functional theory (DFT) calculation revealed that specified P doping could modify the d-band center of Co2C approaching the peak of the volcano map (electrochemical overpotentials ∼ Ed). The Gibbs free energy of the BA oxidation was also reduced, thus optimizing the adsorption and desorption process of intermediates. On the other hand, the catalyst surface physical properties of Co2C such as hydrophilicity was promoted by the doped heteroatoms which was favorable for the gas-liquid-solid triphase electrocatalytic reaction. This work offers a facial perception of regulating the d-band to design advanced bifunctional electrocatalysts for organic matter oxidation and HER.

Factors influencing the stability of Pt-based ORR electrocatalysts in HT-PEMFCs: A theoretical investigation

Electrocatalyst stability is a key parameter for commercializing high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Here, we used density functional theory (DFT) to investigate the stability of Pt-based electrocatalysts by calculating the binding energy (ΔEb) of surface Pt atoms under working conditions. Our results show that Pt(111) is more stable than Pt(100) and Pt(110) under vacuum conditions. Stress hurts the stability of Pt(111), regardless of compressive or tensile stress. Most of the transition metals alloyed with Pt improve the stability of Pt(111), especially PtV, PtY, and PtTa, which increase the ΔEb by 0.60–0.70 eV (ΔΔEb). However, the stability of Pt is significantly destroyed under the working conditions of oxygen reduction reaction (ORR). The specific adsorption of ORR intermediates and electrolyte ions decreases the ΔEb of Pt(111) by 0.35–0.95 eV, and the effect of PO43-* is more significant. Furthermore, when the electric field of the electrochemical double layer is coupled with PO43-* specific adsorption, ΔΔEb further increases to 1.12 eV. Our results highlight the importance of the intrinsic ΔEb and the working conditions for the stability of Pt-based electrocatalysts. This work provides important guidelines for the design of stable ORR electrocatalysts for HT-PEMFCs.