Oxygen Binding Energy Research Articles

Optimization of Oxygen Reduction Activity Via Transition Metal-Oxide Based Composite Electrodes in Acidic Medium

Global warming has occurred due to the usage of fossil fuels and greenhouse gas emissions. Therefore, a change in the energy paradigm can overcome the problems of global warming and air pollution and provide new energy to humanity continuously. Fuel cells are an eco-friendly system that utilizes the electricity generated during the process of producing water from hydrogen fuel. In general, 20 wt% Pt/C is used as the commercial catalyst for polymer electrolyte fuel cells (PEFCs), but challenges remain to solve such as cost and durability. In PEFCs, oxygen reduction reaction (ORR) is an important key as a rate-determining step (RDS) to react the overall reaction. Therefore, it is necessary to develop efficient materials (electrode, membrane, cell, etc.) for improving RDS. Recently, transition metal oxide (TMO) composite electrodes have gained interest in the electrochemical fields. Especially, nickel, cobalt, iron-based oxides are promising materials as non-noble metal electrocatalysts due to their high electric conductivity and various oxidation state.The purpose in this research is to improve ORR performance by controlling active sites and electric conductivity using low amount of noble metals on transition metal doped oxides for the use at the electrode. We have developed composite oxide electrodes with noble-transition metal alloy using solid-state methods. Small amount of noble metal can be alloyed with transition metal to form appropriate oxygen binding energy for oxygen adsorption and desorption, which can improve ORR activity. To check the catalytic activity, cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were analyzed using a rotating disk electrode, and it was found that the noble metal-transition metal alloy oxide composite electrode was effective in enhancing the ORR kinetics. Additionally, the strong interaction between the alloy nanoparticles and oxide support surface enhances chemical stability when used in harsh environments such as acidic media. Furthermore, based on the previous ORR data, we fabricated membrane electrode assembly (MEA) using developed catalysts and confirmed their potential for PEFCs applications.

Concave Grain Boundaries Stabilized by Boron Segregation for Efficient and Durable Oxygen Reduction.

The oxygen reduction reaction (ORR) is a critical process that limits the efficiency of fuel cells and metal-air batteries due to its slow kinetics, even when catalyzed by platinum (Pt). To reduce Pt usage, enhancing both the specific activity and electrochemically active surface area (ECSA) of Pt catalysts is essential. Here, ultrafine, grain boundary (GB)-rich Pt nanoparticle assemblies are proposed as efficient ORR catalysts. These nanowires offer a large ECSA and a high density of concave GB sites, which improve specific activity. Atoms at these GB sites exhibit increased coordination and lattice distortion, leading to a favorable reduction in oxygen binding energy and enhanced ORR performance. Furthermore, boron segregation stabilizes these GBs, preserving active sites during catalysis. The resulting boron-stabilized Pt nanoassemblies demonstrate ORR specific and mass activities of 9.18 mA cm-2 and 6.40 A mg-1 Pt (at 0.9 V vs. RHE), surpassing commercial Pt/C catalysts by over 35-fold, with minimal degradation after 60000 potential cycles. This approach offers a versatile platform for optimizing the catalytic performance of a wide range of nanoparticle systems.

Removal of levofloxacin by H2O2 and PMS co-activation by sulfide-supported oxalate zero-valent iron enhanced with simultaneous catalysis of SO4-• and 1O2: Major free radicals, synergistic effects and mechanism exploration

It is reported in the literature that sulfide and oxalate are promising ways to modify zero-valent iron (ZVI) for the degradation of antibiotics, but the synergistic activation mechanism of H2O2 and PMS is still unclear. In order to explore this effect, a new type of oxalated and sulfided ZVI (OA-S-ZVI) was synthesized in this study, and levofloxacin (LEV) was degraded in H2O2, PMS and H2O2/PMS systems. The batch experiments confirmed that the removal ability of OA-S-ZVI/H2O2/PMS was 1.65–10 times that of other systems. This result was achieved by modifying ZVI surface catalytic sites and cooperating with H2O2/PMS. At the same time, the synergistic factor S (1.74) confirmed that the composite system H2O2/PMS can capture electrons from the catalyst Fe0 to Fe2+ and adsorb active sites of the catalyst, such as ≡Fe-C2O4-, ≡Fe-OH/OOH and ≡Fe-S. Further calculation and analysis revealed that the binding energy of singlet oxygen (1O2) and sulfate radical (SO4-•) in the composite system decreased and multiple molecular orbitals participated in the removal process. The characterization experiments and EPR experiments explained the transfer free radicals to non-free radicals from a single system to a composite system. This study provides a new perspective on modifying ZVI and utilizing multi-system synergy to effectively remove organic micropollutants from water.

Enhanced catalytic performance and antichlorine poisoning over Cu-doped cobalt oxide nanosheets for chlorobenzene oxidation

The degradation of Chlorinated volatile organic compounds (CVOCs) by catalytic oxidation forms toxic products, and catalysts may be poisoned by chlorine at low temperatures. To address this, a Cu-assisted strategy is proposed for enhancing the catalytic degradation of chlorobenzene (CB) over cobalt oxide nanosheets. The Cu-doped Co3O4 catalysts exhibited lower T90 values (temperatures with 90 % conversion) and improved stability compared to the unmodified catalyst. These results were attributed to strong metal-metal interactions between Cu species and cobalt oxide nanosheets, which showed a high specific surface area, reduced binding energy of lattice oxygen, higher surface oxygen concentration, and more surface Co3+ species. These properties promoted low-temperature catalytic activity. In addition, the disappearance of Cu2+ satellite peak after the catalyst is used, indicating that the Cu2+ also contributes to the catalytic activity. Furthermore, the in situ FTIR spectra provided details about the reaction mechanism of CB degradation over Cu-doped cobalt oxide nanosheets. The oxygen vacancy generation and the surface absorption of chlorine-containing intermediates were calculated using density functional theory calculations. This study provides new insight into novel pathways for catalyst design aimed at CB degradation.

NC Loaded PtM Alloy from M-NC with Ultralow Pt Loading for Oxygen Reduction Reaction

Developing low Pt or non-precious metal catalysts for oxygen reduction reaction (ORR) has becoming necessary in recent years. Herein, PtM alloy anchored on nitrogen-doped carbon (PtM/NC, M=Fe, Co) catalyst with ultralow Pt loading (∼1 wt%) is prepared from the simple two-process pyrolysis, namely from C to M-NC then to PtM/NC. The as-prepared PtM/NC (M=Fe, Co) shows an excellent ORR catalytic performance with the peak potential and half-wave potential of 0.901 and 0.870 V for PtFe/NC, 0.868 and 0.845 V for Pt3Co/NC. The ORR on PtM/NC (M=Fe, Co) is a mainly direct 4-electron reaction pathway (3.75–3.90) in alkaline solution. Moreover, they possess good methanol tolerance and stability. Synergistic effect of Pt and M together with N species result in the excellent ORR catalytic activity of PtM/NC (M=Fe, Co). The negative shift of Pt binding energy caused by both lattice contraction and electron orbital coupling from M is beneficial for reducing the d-band center of Pt, weakening the oxygen binding energy and enhancing the ORR intrinsic activity of Pt. The strong interactions between NC and PtM alloy are beneficial for anchoring PtM nanoparticles, promoting the stability of catalyst. This work provides a new strategy for preparing ultralow Pt loading catalysts.

Effect of Chlorine on Copper Electrodissolution

A computational study on the role of adsorbed Cl ions on copper dissolution is presented. Extensive grand canonical Monte Carlo (GCMC) calculations using reactive force-field (ReaxFF) are used to check the formation chlorine (Cl) adlayer structures on Cu (100) surface as a function of the chemical potential (µ). From experimental studies conducted by other researchers it has been observed that Cl adlattice on Cu in c(2X2) at maximum coverage. We observe that at low µ, Cl adlayer is disordered and moves to ordered c(2X2) structure at high µ. The binding energy of Cl, oxygen (O), hydroxide (OH-) and H2O on Cu at different sites is calculated and compared with Density-functional theory (DFT) values. Metal surface is often highly uneven and rough during electrodissolution process. Therefore, we also discuss the adsorption isotherm, disorder-order transformation, and preferential adsorption sites for rough surfaces. Specific anion adsorption (SAA) of Cl involves partial charge transfer to Cu substrate and these effect the type of bond and bond strength which is also briefly discussed. The electrodissolution of Cu in the presence of Cl is modelled using kinetic Monte Carlo simulation to obtain the polarization curve.Keywords: Adsorbed chlorine, electrodissolution, grand canonical monte carlo, molecular dynamics, ReaxFF, kinetic monte carlo.

Tailoring hierarchical porous core–shell SnO2@Cu upon Cu–Sn alloys through oxygen binding energy difference for high energy density lithium-ion storage

Rational design and construction of self-supporting anodes with high energy density is an essential part of research in the field of lithium-ion batteries. Tin oxide (SnO2) is restricted in application as a prospective high energy density anode due to inherent low conductivity and huge volume expansion of the charge/discharge process. A new strategy that combines high energy ball milling and nonsolvent induced phase separation (NIPS) method was employed to synthesize self-supporting electrodes in which porous SnO2 was encapsulated in a three-dimensional hierarchical porous copper (Cu) shell structure (3DHPSnO2@Cu). This unique structure was constructed due to the different binding energy of the alloy with oxygen, which are −0.91 eV for Cu41Sn11 and −1.17 eV for Cu5.6Sn according to the density functional theory calculation. 3DHPSnO2@Cu electrodes exhibited excellent discharge capacity with an initial reversible capacity of 4.35 mAh cm−2 and a reversible capacity of 3.13 mAh cm−2 after 300 cycles at a current density of 1.4 mA cm−2. It is attributed that the porous Cu shell encapsulated with porous SnO2 provides buffer volume. Among them, the SnO2-Cu-SnO2 interface increases the electrical conductivity and the porous structure provides ion transport channels. This strategy opens a new pathway in the development of self-supporting electrode materials with high energy density.

DFT study on ORR catalyzed by bimetallic Pt-skin metals over substrates of Ir, Pd and Au

Bimetallic Pt-skin catalyst is a class of near-surface alloy (NSA) that owns a high degree of control over composition. Herein, density functional theory (DFT) is used to calculate the energetics of oxygen reduction reaction (ORR) on Pt-skin over Ir, Pd and Au substrates. A Brønsted-Evans-Polanyi (BEP) relationship can be determined for the oxygen molecule dissociation. The binding energy of both atomic oxygen and hydroxyl radical is found to correlate well with the d band center of Pt-skin atoms. Their catalytic activities show the volcano relationship as the positions of each substrate in the periodic table. The effect of surface strain, band structure and charge transfer on the d band center is well studied, and it can be found that the surface strain effect plays a dominant role for all Pt-skin catalysts. Ir substrate makes the d band center of Pt-skin go far away from the Fermi level, while Au substrate makes it move towards the Fermi level. Being different from both Ir and Au, Pd substrate makes the d band center of Pt-skin comparable with the monometallic Pt.

The Relationship between the Structural Characteristics of α-Fe2O3 Catalysts and Their Lattice Oxygen Reactivity Regarding Hydrogen.

In this paper, the relationship between the structural features of hematite samples calcined in the interval of 800-1100 °C and their reactivity regarding hydrogen studied in the temperature-programmed reaction (TPR-H2) was studied. The oxygen reactivity of the samples decreases with the increasing calcination temperature. The study of calcined hematite samples used X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), and Raman spectroscopy, and their textural characteristics were studied also. According to XRD results, hematite samples calcined in the temperature range under study are monophase, represented by the α-Fe2O3 phase, in which crystal density increases with increasing calcination temperature. The Raman spectroscopy results also register only the α-Fe2O3 phase; the samples consist of large, well-crystallized particles with smaller particles on their surface, having a significantly lower degree of crystallinity, and their proportion decreases with increasing calcination temperature. XPS results show the α-Fe2O3 surface enriched with Fe2+ ions, whose proportion increases with increasing calcination temperature, which leads to an increase in the lattice oxygen binding energy and a decrease in the α-Fe2O3 reactivity regarding hydrogen.

Remarkably Enhanced Lattice Oxygen Participation in Perovskites to Boost Oxygen Evolution Reaction.

Enhancing the participation of the lattice oxygen mechanism (LOM) in several perovskites to significantly boost the oxygen evolution reaction (OER) is daunting. With the rapid decline in fossil fuels, energy research is turning toward water splitting to produce usable hydrogen by significantly reducing overpotential for other half-cells' OER. Recent studies have shown that in addition to the conventional adsorbate evolution mechanism (AEM), participation of LOM can overcome their prevalent scaling relationship limitations. Here, we report the acid treatment strategy and bypass the cation/anion doping strategy to significantly enhance LOM participation. Our perovskite demonstrated a current density of 10 mA cm-2 at an overpotential of 380 mV and a low Tafel slope (65 mV dec-1) much lower than IrO2 (73 mV dec-1). We propose that the presence of nitric acid-induced defects regulates the electronic structure and thereby lowers oxygen binding energy, allowing enhanced LOM participation to boost OER significantly.

Dual lattice oxygens in amorphous Zr-doped manganese oxide for highly efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

One hurdle in developing transition metal oxide (TMO) catalysts for aerobic oxidation reactions is their need for a low binding energy of the lattice oxygen (OL) to create active OL and a high OL binding energy to maintain structural stability during catalysis. In this work, we prepared amorphous Zr-doped manganese oxide (amor-Zr:MnOx) catalysts carrying dual lattice oxygens that can address such conflicting objectives in catalyst development. In the aerobic oxidation of 5-(hydroxymethyl)furfural (HMF), the amor-Zr0.2MnOx catalyst gave 99% selectivity for 2,5-furandicarboxylic acid (FDCA) and a high FDCA formation rate of 3600 µmolFDCA gcat−1 h−1 in 1 h. To the best of our knowledge, the aerobic oxidation performance of the amor-Zr0.2MnOx catalyst is superior to those of most Mn-based and related TMO-based catalysts under comparable conditions. Experimental and theoretical studies show that the OL in amor-Zr: MnOx can be divided into two groups. One group includes the more stable OL that strengthens the catalyst structure and prevents phase transition, while the other group includes the more reactive OL that improves catalyst activity through the strong adsorption/activation of O2 and helps regenerate OL during catalysis.

Synergistic effects of Zr doping and Li2ZrO3/WO3 co-coating on the physicochemical and electrochemical properties of cobalt-free LiNi0.8Mn0.2O2

Particle fragmentation and thermal stability during repeated delithiation and lithiation are key issues that affect nickel-rich cobalt-free LiNixMn1-xO2. In this study, the physicochemical and electrochemical characteristics of LiNi0.8Mn0.2O2 (NM) cathode materials were improved by Zr doping and Li2ZrO3/WO3 co-coatings. During solid-phase sintering, ZrO2 reacts with residual lithium on the surface of NM materials to form the lithium-ion conductor Li2ZrO3, while Zr4+ occupies transition metal sites in the material lattice. The reversible capacity of NM modified by 1 mol% ZrO2 and 1 mol% WO3 was 179.5 mAh/g (10.16 % loss) after 200 cycles at 1C (200 mAh/g), while the discharge capacity of pristine NM was 138.0 mAh/g (21.15 % loss). Moreover, the Li+ diffusion coefficient of the co-modified material increased from 4.429 × 10−13 cm2/s to 1.772 × 10−12 cm2/s. According to density functional theory calculations, Zr ion doping enhances the electrical conductivity of NM materials and the binding energy of molecular oxygen. By comparing the structure and morphology of the two samples after cycling, it was demonstrated that elemental co-modification effectively stabilises the crystal structure, reduces electrolyte erosion and improves the electrochemical performance of the material. Thus, this study details a method for improving the structure and thermal stability of cobalt-free nickel-rich cathode materials.

Ab initio study of changing the oxygen reduction activity of Co-Fe-based perovskites by tuning the B-site composition.

Perovskite oxides are promising low-cost and stable alternative electrocatalysts for the oxygen reduction reaction (ORR), relative to the precious metal-based electrocatalysts. Despite the experimental research on substituting various transition metals into the B-site of perovskite catalysts to improve the ORR performance, the detailed ORR mechanism due to the substitution process is rarely studied. In this paper, the ORR activity of La0.5Sr0.5CoxFe1-xO3 perovskites (x = 0, 0.25, 0.5, 0.75, and 1) is studied by density functional theory (DFT). The ORR mechanism in alkaline solution is theoretically examined as a function of the Co/Fe composition at different potentials. The substitution of Co for Fe at the B-site of the perovskites dramatically changes the theoretical overpotential and enhances the activity. The HOO* formation is the potential-determining step for all the Co/Fe compositions. In comparison with the other compositions, the Co0.5/Fe0.5 composition exhibits the lowest overpotential and bonding with the reaction intermediates moderately. Furthermore, the oxygen binding energy is correlated with the bulk oxygen p-band center relative to the Fermi level. Among all the Co/Fe compositions, the Co0.5/Fe0.5 composition shows neither too low nor too high oxygen p-band center value. These results provide deep insights into the ORR mechanism on B-site substituted perovskites and guidelines for the design of cost-effective and Pt-free electrocatalysts for oxygen reduction.

PtCo-based nanocatalyst for oxygen reduction reaction: Recent highlights on synthesis strategy and catalytic mechanism

PtCo-based catalyst with high activity, efficiency, and stability towards ORR Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells. However, low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilization efficiency and durability by doping non-noble metals to form Pt-based alloy catalysts. Alloying Pt with Co has been recognized as one of the most effective approaches to achieve this goal. PtCo bimetal combination is one of the most promising candidates to synthesized highly efficient catalysts for ORR applications, owing to its relatively more suitable oxygen binding energy for four-electron transfer reactions. Recently, impressive strategies have been developed to fabricate more active and stable PtCo-based multimetallic alloys with tailorable size and morphology. This paper aims to summarize the most recent highlights on the study of the relationship between preparation strategies, morphologies, electroactivities of the PtCo-based catalyst at atomic level and further the relevant reaction mechanism. The challenges and opportunities on the further development of electrocatalysts for fuel cells are included to provide reference for the practical application.

Reduced Potential Barrier of Sodium-Substituted Disordered Rocksalt Cathode for Oxygen Evolution Electrocatalysts.

Cation-disordered rocksalt (DRX) cathodes have been viewed as next-generation high-energy density materials surpassing conventional layered cathodes for lithium-ion battery (LIB) technology. Utilizing the opportunity of a better cation mixing facility in DRX, we synthesize Na-doped DRX as an efficient electrocatalyst toward oxygen evolution reaction (OER). This novel OER electrocatalyst generates a current density of 10 mA cm-2 at an overpotential (η) of 270 mV, Tafel slope of 67.5 mV dec-1, and long-term stability >5.5 days' superior to benchmark IrO2 (η = 330 mV with Tafel slope = 74.8 mV dec-1). This superior electrochemical behavior is well supported by experiment and sparse Gaussian process potential (SGPP) machine learning-based search for minimum energy structure. Moreover, as oxygen binding energy (OBE) on the surface closely relates to OER activity, our density functional theory (DFT) calculations reveal that Na-doping assists in facile O2 evolution (OBE = 5.45 eV) compared with pristine-DRX (6.51 eV).

Structural and electronic properties with respect to Si doping in oxygen rich ZnSnO amorphous oxide semiconductor

The effect of Si doping in the presence of excess oxygen on the zinc-tin-oxide (ZTO) thin-film transistor is investigated. The threshold voltage increases from 3.86 to 10.8 V, and the ON current reduces from 4 × 10 -4 to 1.1 × 10 -4 A for the undoped and 1 wt% Si-doped ZTO transistor, respectively. The changes in the threshold voltage and the ON current are attributed to the suppression of free charge carriers due to excess oxygen in the film. The annihilation of oxygen vacancy-related defects states is substantiated by the density of states extracted from the photonic capacitance-voltage characteristic of the undoped and Si-doped ZTO thin-film transistors. Moreover, due to the high binding energy of Si and oxygen, excess oxygen is introduced into the film. The excessive oxygen forms the O-O ex dimer that acts as the electron trap and degrades the device's stability. From the bias stress measurement and the density of states extraction, it is concluded that 0.5 wt% doping of Si in ZTO is optimal for moderate device performance, less defects density, and high stability.

Manipulating Selectivity of Hydroxyl Radical Generation by Single-Atom Catalysts in Catalytic Ozonation: Surface or Solution.

Hydroxyl radical-dominated oxidation in catalytic ozonation is, in particular, important in water treatment scenarios for removing organic contaminants, but the mechanism about ozone-based radical oxidation processes is still unclear. Here, we prepared a series of transitional metal (Co, Mn, Ni) single-atom catalysts (SACs) anchored on graphitic carbon nitride to accelerate ozone decomposition and produce highly reactive ·OH for oxidative destruction of a water pollutant, oxalic acid (OA). We experimentally observed that, depending on the metal type, OA oxidation occurred dominantly either in the bulk phase, which was the case for the Mn catalyst, or via a combination of the bulk phase and surface reaction, which was the case for the Co catalyst. We further performed density functional theory simulations and in situ X-ray absorption spectroscopy to propose that the ozone activation pathway differs depending on the oxygen binding energy of metal, primarily due to differential adsorption of O3 onto metal sites and differential coordination configuration of a key intermediate species, *OO, which is collectively responsible for the observed differences in oxidation mechanisms and kinetics.

The influence of steric and ligand effects on metal- and alloy-supported oxygenated and hydrogenated Pt(111)

<h2>Abstract</h2> Understanding the mechanisms of the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER) is key to the development of modern energy storage and transport materials. The technology inherent in these materials contributes significantly to sustainable chemical production, whose energy footprint is an imperative concern when designing catalysts and networks of catalysts. In this presentation a comparative study of the unreacted and reacted uniaxially strained Pt(111) and the layered (111)-Pt/Ni/Pt3Ni and (111)-Pt/Ni/PtNi3 surfaces has been performed using density functional theory (DFT). Through an analysis of the binding energies of oxygen and hydrogen over the high-symmetry binding positions of all surfaces, the study has shown that O and H tend to bind more strongly to the (111)-Pt/Ni/Pt3Ni surface and less strongly to the (111)-Pt/Ni/PtNi3 surface compared to binding on the equivalently strained Pt(111) surfaces. An estimate the error in the computational binding energies as well as a critical comparative analysis of the binding mechanisms which contribute to these energetic differences has been performed by comparing the predictions of different density functionals. Changes in the surface magnetisation of the surfaces overlaying the ferromagnetic alloys during adsorption are highlighted and discussed, as well as the behaviour of the d-band centre across all surfaces to provide causal explanations of the mechanism changes.

Transformation of the Active Moiety in Fe-N-C Electrocatalyst through Invasive P-Doping for Highly Efficient Oxygen Reduction Reaction

Iron- and nitrogen-doped carbon (Fe-N-C) materials have been suggested as the most promising replacement for Pt-based catalysts in oxygen reduction reaction (ORR) owing to the FeN4 active moiety. Based on the relationship between the oxygen binding energy and the catalytic activity, Fe-N-C has very strong oxygen binding energy so that hard to desorb the final reaction intermediate of *OH. Herein, we provide for the first time an effective method of tuning the active moiety using a phosphine gas-phase treatment for Fe-N-C. Combined analyses of experimental and computational results reveal that the conventional FeN4 moiety is transformed into FeN3PO through the P-doping post-treatment. Furthermore, we propose an ORR mechanism on the unique FeN3PO moiety based on a microkinetic model, in which *OH intermediates are considered. The invasive P-doping effects on the ORR performance are also validated in both anion exchange membrane fuel cell (AEMFC) and proton exchange membrane fuel cell (PEMFC). Figure 1

Revealing the Role of Mo Doping in Promoting Oxygen Reduction Reaction Performance of Pt3Co Nanowires

Highly active and durable electrocatalysts towards oxygen reduction reaction (ORR) are imperative for the commercialization application of proton exchange membrane fuel cells. By manipulating ligand effect, structural control, and strain effect, we report here the precise preparation of Mo-doped Pt3Co alloy nanowires (Pt3Co-Mo NWs) as the efficient catalyst towards ORR. The as-prepared Pt3Co-Mo NWs deliver high specific activity (0.596 mA cm-2) and mass activity (MA, 0.84 A mg -1Pt), much higher than those of undoped counterparts. Besides activity, Pt3Co-Mo NWs also demonstrate excellent structural stability and cyclic durability even after 50,000 cycles (76% MA retain), again surpassing control samples without Mo dopants. The superior catalytic performance can be attributed to several structural advantages. First, both ultrafine nanowire morphology and controlled growth ensure the exposure of abundant highly active high-index facets, resulting in increased electrochemical active surface area (ECSA, 141 m2 g−1 Pt). Second, one dimensional (1D) Pt nanostructure, particularly ultrafine Pt nanowires, are less subject to dissolution, aggregation, and even Ostwald ripening than nanoparticles, leading to much-improved durability. Third and most importantly, the Mo doping directly changes the local electronic structure of both element Pt and Co, not only effectively endowing the Pt3Co electrocatalysts with an enhanced activity but also efficiently preventing element Co from leaching leading to improved durability.The geometric phase analysis (GPA) strain maps and the density function theory (DFT)calculations were conducted to further analyze the role of Mo dopants. GPA strain maps reveal that Mo dopants are inclined to be the tensile strain cores, generating local lattice expansion to adjust the excessively compressive strain effect introduced by Co alloying. Benefiting from the optimized d-band center, the oxygen binding energy (Eo) on Pt3Co-Mo slabs is closest to the optimal value compared with those of undoped counterparts. Moreover, the energy required to remove Co atoms from Pt3Co slab with Mo doping is increased by 0.195 eV compared to the slab without Mo doping, indicating the electronic effect of Mo dopants to stabilize Co. This work provides not only a facile methodology but also an in-depth investigation of the relationship between structure and properties to provide general guidance for future design and optimization.