CO Tolerance Research Articles

Synthesis and Electrochemical Performances of a Versatile Nitrogen-Doped Carbon Skeleton Material Derived from a Humate-CoFe-ZIF/Melamine Precursor

Humic acid (HA), melamine, and ZIFs are superior precursors for preparing carbon materials. Especially, metal ions in ZIFs are excellent nanocatalysts for synthesizing CNTs or graphene, while melamine and ZIFs are good dopants for fabricating nitrogen-doped carbon materials. Here, nitrogen-doped carbon skeletal materials (NCS) assembled by a large number of bamboo-like CNTs and a small number of graphene layers were elaborately synthesized by a two-step pyrolysis process using a humate-CoFe-ZIF (HA-CoFe-ZIF) composite material as the template and melamine as the carbon and nitrogen source. NCS-II exhibits desirable supercapacitive characteristics and superior support performance due to a harmoniously assembled graphitic structure, favorite nitrogen incorporation mainly including pyridinic N and pyrrolic N at a high dosage of 5.24 wt %, abundant mesoporous structure, and large specific surface. As a supercapacitor electrode material, NCS-II demonstrates a high electrochemical capacitance (324 F g–1 at 1 A g–1), wide operating current density range (1–50 A g–1), and rate capability (64% from 5 A g–1 to 50 A g–1). And the prepared NCS-II//AC asymmetric supercapacitor also displays a large specific capacitance (129 F g–1 at 1 A g–1), good cycling stability (96% at 5 A g–1 for 10 000 cycles), and high energy density (25.6 Wh kg–1 at 600 W kg–1). As a catalyst support, the NCS-II provides plentiful active sites and a large specific surface area for the highly dispersed loading of PtCo nanoparticles. The prepared 1:1-PtCo/NCS-II catalyst exhibits high catalytic activity, good cycling stability, and strong CO tolerance ability for methanol oxidation reaction (MOR). Its ECSA value, CV peak current density, and peak current retention after 500 CV turns are high, up to 265.7 m2 gpt–1, 850 mA mgPt–1, and 79%, respectively.

Electrooxidation of Methanol on PANI‐CeO2@Pt Catalysts

AbstractPolyaniline (PANI) and Pt were synthesized in sequence by in situ electrochemical deposition on CeO2 surface to prepare PANI/CeO2/Pt ternary composites (PANI‐CeO2@Pt composites). The electrocatalytic activity of PANI‐CeO2@Pt composite was measured to 226 mA⋅mg−1, which was 1.7‐, 2.3‐, 20‐flod as that of CeO2@Pt, Pt/C, and PANI@Pt catalyst, respectively. The PANI‐CeO2@Pt catalyst displayed noticeably the highest activity toward methanol oxidation after the 4000 s among the tested CeO2@Pt, Pt/C, and PANI@Pt catalyst. In a CO‐stripping experiment, PANI‐CeO2@Pt composites exhibited better CO tolerance. These results meant that highly dispersed Pt nanoparticles and the oxygen storage capacity of PANI‐CeO2@Pt contributed to admirable catalytic activities for methanol oxidation reaction (MOR).

Study on high-CO2 tolerant Dunaliella salina and its mechanism via transcriptomic analysis.

Microalgae has been regarded as a promising method for reducing CO2 emission. High CO2 concentration generally inhibits algal growth, and previous studies have mostly focused on breeding freshwater algae with high CO2 tolerance. In this study, one marine algal strain Dunaliella salina (D. salina) was grown under 0.03%-30 % CO2 and 3% NaCl conditions, and was evaluated to determine its potential for CO2 assimilation. The results showed that D. salina could tolerate 30% CO2 , and its maximum biomass concentration could reach 1.13g·L-1 after 8days incubation, which was 1.85 times higher than that of incubation in air (0.03%). The phenomenon of high-CO2 tolerance in D. salina culture was discussed basing on transcriptome analysis. The results showed that D. salina was subjected to oxidative stress under 30% CO2 conditions, and the majority genes involving in antioxidant system, such as SOD, CAT, and APX genes were up-regulated to scavenge ROS. In addition, most of the key enzyme genes related to photosynthesis, carbon fixation and metabolism were up-regulated, which are consistent with the higher physiological and biochemical values for D. salina incubation under 30% CO2 .

Electroshock synthesis of a bifunctional nonprecious multi-element alloy for alkaline hydrogen oxidation and evolution.

The design and production of active, durable, and nonprecious electrocatalysts toward alkaline hydrogen oxidation and evolution reactions (HOR/HER) are extremely appealing for the implementation of hydrogen economy, but remain challenging. Here, we report a facile electric shock synthesis of an efficient, stable, and inexpensive NiCoCuMoW multi-element alloy on Ni foam (NiCoCuMoW) as a bifunctional electrocatalyst for both HOR and HER. For the HOR, the current density of NiCoCuMoW could reach ∼11.2mA cm-2 when the overpotential is 100mV, higher than that for commercial Pt/C (∼7.2mA cm-2) and control alloy samples with less elements, along with superior CO tolerance. Moreover, for the HER, the overpotential at 10mA cm-2 for NiCoCuMoW is only 21mV, along with a Tafel slope of low to 63.7mV dec-1, rivaling the commercial Pt/C as well (35mV and 109.7mV dec-1). Density functional theory calculations indicate that alloying Ni, Co, Cu, Mo, and W can tune the electronic structure of individual metals and provide multiple active sites to optimize the hydrogen and hydroxyl intermediates adsorption, collaboratively resulting in enhanced electrocatalytic activity.

Surface Anion Promotes Pt Electrocatalysts with High CO Tolerance in Fuel-Cell Performance.

Platinum reaches considerable activity and stability as an electrocatalyst but is not always capable of maintaining such performance under CO poisoning, particularly in CO residual fuels for practical proton-exchange membrane fuel cells (PEMFCs). In this work, we report that surface anions including a series of nonmetal elements on Pt nanoparticles result in outstanding CO tolerance for electrocatalysts in fuel cells. In particular, phosphorus surface-anion-modified Pt (denoted as P-Pt) possesses more than 10-fold enhancement of CO tolerance (only 8.4% decay) than commercial Pt/C, which can serve as a robust electrocatalyst both in CO poisoning half cells and full cells. Moreover, the general mechanism and principle were proposed, stating that surface anions should be selected preferentially to offer electron feedback to downshift the d-band center for the Pt surface, successfully weakening CO adsorption and leading to high-tolerance capability. We anticipate that surface anions on a Pt surface can bring robust electrocatalysts for practical PEMFCs and offer novel insights for high-performance Pt-based electrocatalysts.

The RAM signaling pathway links morphology, thermotolerance, and CO2 tolerance in the global fungal pathogen Cryptococcus neoformans.

The environmental pathogen Cryptococcus neoformans claims over 180,000 lives each year. Survival of this basidiomycete at host CO2 concentrations has only recently been considered an important virulence trait. Through screening gene knockout libraries constructed in a CO2-tolerant clinical strain, we found mutations leading to CO2 sensitivity are enriched in pathways activated by heat stress, including calcineurin, Ras1-Cdc24, cell wall integrity, and Regulator of Ace2 and Morphogenesis (RAM). Overexpression of Cbk1, the conserved terminal kinase of the RAM pathway, partially restored defects of these mutants at host CO2 or temperature levels. In ascomycetes such as Saccharomyces cerevisiae and Candida albicans, transcription factor Ace2 is an important target of Cbk1, activating genes responsible for cell separation. However, no Ace2 homolog or any downstream component of the RAM pathway has been identified in basidiomycetes. Through in vitro evolution and comparative genomics, we characterized mutations in suppressors of cbk1Δ in C. neoformans that partially rescued defects in CO2 tolerance, thermotolerance, and morphology. One suppressor is the RNA translation repressor Ssd1, which is highly conserved in ascomycetes and basidiomycetes. The other is a novel ribonuclease domain-containing protein, here named PSC1, which is present in basidiomycetes and humans but surprisingly absent in most ascomycetes. Loss of Ssd1 in cbk1Δ partially restored cryptococcal ability to survive and amplify in the inhalation and intravenous murine models of cryptococcosis. Our discoveries highlight the overlapping regulation of CO2 tolerance and thermotolerance, the essential role of the RAM pathway in cryptococcal adaptation to the host condition, and the potential importance of post-transcriptional control of virulence traits in this global pathogen.

Synthesis of intermetallic FePtPd nanoparticles and their enhanced catalysis for electro-oxidation of methanol

Searching for efficient and CO-tolerant catalysts for electro-oxidation of methanol is desirable for the development of direct-methanol fuel cells. Here, we present a novel and facile procedure for the synthesis of intermetallic face-centered tetragonal (fct)-Fe50PtxPd50-x Nanoparticles (NPs) with Fe and Pt/Pd atoms forming alternative layers, which are highly active and stable in catalyzing methanol oxidation reaction (MOR) in 0.1 M HClO4 and 0.2 M methanol aqueous solution. The carbon-supported fct-Fe48Pt35Pd17 NPs show the highest peak current density of 626 A g−1Pt at 909 mV (vs RHE) over fcc-Fe48Pt35Pd17 (428 Ag−1Pt at 930 mV) and the commercial Pt (218 Ag−1Pt at 952 mV). The superior performance observed on the fct-Fe48Pt35Pd17 NPs is attributed to the stabilization of Pd by the intermetallic fct-structure, which improves the Pt CO-tolerance and catalytic activity. The activity of fct-FePtPd depends further on the Pt/Pd ratios. An increase in Pd content improves CO tolerance but reduces the number of active Pt sites on NPs surface, and the optimized Pt/Pd ratio should be around 1.0. Our work demonstrates a new approach to the rational design and synthesis of highly active NP catalysts for MOR.

Pt Single Atoms on CrN Nanoparticles Deliver Outstanding Activity and CO Tolerance in the Hydrogen Oxidation Reaction.

The large-scale application of proton exchange membrane fuel cells is currently hampered by high cost of commercial Pt catalysts and their susceptibility to poisoning by CO impurities in H2 feed. In this context, the development of CO-tolerant electrocatalysts with high Pt atom utilization efficiency for hydrogen oxidation reaction (HOR) is of critical importance. Herein, Pt single atoms are successfully immobilized on chromium nitride nanoparticles by atomic layer deposition method, denoted as Pt SACs/CrN. Electrochemical tests establish Pt SACs/CrN to be a very efficient HOR catalyst, with a mass activity that is 5.7 times higher than commercial PtRu/C. Strikingly, the excellent performance of Pt SACs/CrN is maintained after introducing 1000ppm of CO in H2 feed. The excellent CO-tolerance of Pt SACs/CrN is related to weaker CO adsorption on Pt single atoms. This work provides guidelines for the design and construction of active and CO-tolerant catalysts for HOR.

Direct utilization of crude and waste H2 via CO-tolerant hydrogenation

Direct utilization of crude and waste H2 via CO-tolerant hydrogenation

Probing the activity origin of the enhanced methanol electrooxidation on Ni-induced PdNix(OH)y-TaN/C catalyst with nitrogen vacancies

Engineering high-performance inexpensive TaN-modified Pd-based nanostructures for alkaline methanol oxidation reaction(MOR) has attracted extensive attention, yet the related enhancement mechanism of TaN for MOR remains lacked. The core-shell like Pd3Ni1-TaN/C catalyst decorated with Ni(OH)2/NiOOH that contains highly dispersed Ni sites and nitrogen defects has been fabricated for the first time. The unsaturated coordination environment and core-shell like morphology of Pd3Ni1-TaN/C bring fruitful active sites and a down-shifted d-band center, making it a highly-efficient electrocatalyst for alkaline MOR (17.3-fold that of commercial Pd/C). Besides the electronic effects and surface defect sites of Pd3Ni1-TaN/C, TaN also helps MOR proceed via HCOOad pathway (non-CO) accompanied by enhanced OH adsorption induced by the addition of Ni. DFT(Density Functional Theory) calculations also further confirm the energy barrier of the formation of HCOOad intermediate and desorption energy of CO on Pd3Ni1-TaN/C are reduced. The introduction of Ni species and nitrogen vacancies enhances the CO tolerance evidently.

Phosphoric-Acid Retention in High-Temperature Proton-Exchange Membranes.

Great efforts have been conducted to develop high temperature proton exchange membrane fuel cell (HT-PEMFC) due to its features of enhanced electrocatalyst reactivity, simplified hydrothermal management system and high CO tolerance of catalysts, and remarkable progress has been achieved. However, the easy leaching of phosphoric acid (PA) from the membranes during operation limits its commercial scale-up in complicated environments. This concept here mainly focuses on the recent developments for mitigation of PA loss in PEMs. The probable mechanisms of PA loss are proposed. The approaches to improve PA retention for example via introduction of phosphonic acid by covalent bond, using ion-pairs interaction and siphoning effect, and blending with inorganic nanoparticles are described in detail. Among these strategies, the siphoning effect from the intrinsic microporous PEMs is the most efficient and enables the cell to operate flexibly within a broad temperature range. Therefore, this concept may provide new ideas for the scientists to retain PA, to improve the cell performance and expand the potential applications of PA doped PEMs at elevated humidity and wide temperature range.

(Invited) Catalyst Challenges for Ion-Pair High Temperature Proton Exchange Membrane Fuel Cells

High temperature proton exchange membrane fuel cells (HT-PEMFCs) have several merits over low temperature PEMFCs, including simplified fuel cell systems and high CO tolerance. Recently developed ion-pair HT-PEMFCs1 has a significantly lower concentration of phosphoric acids in the membrane-electrode assembly (MEA) that allows ion-conducting binders (ionomers) in the electrodes. Here, we first explain the difference in MEA configurations and fuel cell performance between conventional polybenzimidazole-based and ion-pair HT-PEMFCs2. Next, we discuss catalyst challenges for ion-pair HT-PEMFCs by comparing half-cell and single-cell results.We focus on three critical areas in that electrocatalysts face challenges: i) phosphate anion poisoning on oxygen reduction reaction catalysts, ii) phenyl adsorption on hydrogen oxidation reaction catalysts and iii) phosphoric acid flooding. Research progress mitigating those adverse effects is demonstrated using various commercial Pt-based catalysts and homemade ionomers. Lastly, we provide general directions for designing high-performing catalysts of ion-pair HT-PEMFCs.References Lee, K. S.; Spendelow, J. S.; Choe, Y. K. Fujimoto, C.; Kim, Y. S. An Operationally Flexible Fuel Cell Based on Quaternary Ammonium-Biphosphate Ion Pairs, Nature Energy, 1, 16120 (2016).Lim, K. H.; Lee, A. S.; Atanasov, V.; Kerres, J.; Park, E. J.; Adhikari, S.; Maurya, S.; Manriquez, L. D.; Jung, J.; Fujimoto, C.; Matanovic, I.; Jankovic, J.; Hu, Z.; Jia, H.; Kim, Y. S. Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells, Nature Energy, 7, 248 (2022).

Pt Island Decorated Au Anode for Formic Acid Oxidation Reaction

For direct formic acid fuel cell (DFAFC), Pt-based catalyst is widely used as an anode. The Pt catalyst shows high activity and stability for formic acid oxidation reaction (FAOR) in acidic condition. For FAOR, it is generally accepted that Pt follows dual pathway including direct and indirect pathway. During the indirect pathway the Pt surface is vulnerable to CO poisoning, which cause the activity degradation. To enhance the CO tolerance, various Pt-based bi/ternary catalysts have been investigated. In recent, Pt–Au alloy catalysts have reported higher current density for direct FAOR pathway compared with pure Pt catalyst. The enhanced FAOR activity is originated from lower CO adsorption energy. However, the alloy structure has low catalyst utilization, which is not applicable to practical device.In this study, we report Pt islands decorated porous Au electrode for anode of the DFAFC. The porous Au transport layer was fabricated on carbon fiber by galvanic displacement and subsequent electrochemical etching process. Using Au transport layer as a substrate, Pt self-terminated electrodeposition (SED) was performed. By adjusting the SED condition, the Pt loading and coverage on Au surface cab be easily controlled. The FAOR activity test of Pt–Au electrodes was performed by cyclic voltammetry (CV). It was revealed that the current density for direct FAOR is linearly increased as the Pt coverage on Au surface is lower. By increasing the CV cycles, the current density for direct FAOR is gradually increased owing to enhanced ensemble effect. Furthermore, the cycled electrode was applicated into practical DFAFC single cell. The single cell demonstrates more than two-order higher Pt mass activity compared with previously reported single cell using Pt–Au anode.

(Invited) HT-PEMFC Based on Acid Doped Polybenzimidazoles of the Past Quarter Century

High-temperature proton exchange membrane (HT-PEM) fuel cells based on phosphoric acid-doped polybenzimidazole (PBI) membranes were invented in 1994 by professor Bob Savinell and his coworkers at Case Western Reserve University [1]. The membrane electrolyte is a unique material that is capable of practical proton conductivity at temperatures of up to 200oC under anhydrous conditions. This ground-breaking invention has led to the start of a frontier research area for fuel cells and related technologies, as indicated by an annual publication of ca. 200 items and citation of 10,000 times in the last decade.Based on this type of membrane materials, the HT-PEM technology has developed, with operating features including little humidification, high CO tolerance, easy thermal management and thermal integration with methanol reformer.[2] Significant efforts from international industries are currently made towards commercialization and products are now on the market. Research institutions and industries in Denmark have been active and leading in the research and development of the area. Further, the PBI membrane has also emerged as a promising membrane material for redox flow batteries (RFB).This presentation is devoted to a brief summary of the fundamental understanding and technological deployment of this technology [3], as a remark of the extraordinary contributions of Professor Savinell to the electrochemistry and electrochemical engineering research.

Cobalt-free fluorine doped Bi0.7Sr0.3FeO3-δ oxides for energetic cathodes of low-temperature solid oxide fuel cells

Cobalt-free fluorine doped Bi0.7Sr0.3FeO3-δ-xFx oxides are presented here as cathode catalysts of low-temperature solid oxide fuel cells (LT-SOFCs). Their crystal structure, thermal behaviors, catalytic activity, oxygen transport properties, oxygen reduction kinetics, long-term stability and CO2 tolerance are systematically exploited. At 600 °C, the optimized Bi0.7Sr0.3FeO2.9-δF0.10 (BSFF0.10) cathode possesses outstanding ORR activity with a low polarization resistance of 0.12 Ω cm2. When tested under realistic conditions, the anode-supported fuel cell with BSFF0.10 cathode delivers a high output of 837 mW cm−2 with stable operation for 110 h. Such outstanding performance can be ascribed to the improved oxygen transport kinetics, larger oxygen vacancy concentration, increased oxygen surface adsorption energy, and O 2p-band centers close to the Fermi level. In addition, the oxygen reduction process on BSFF0.10 electrode interface is mainly determined to be the dissociation of adsorbed molecule oxygen processes. The BSFF0.10 cathode exhibits superior CO2 tolerance because of the lower basicity resulting from the presence of Bi3+, Fe2+/Fe3+/Fe4+ and F−. Although the BSFF0.10 cathode is not reactive with CO2 to form carbonate species, post-characterizations reveal that the CO2 atmosphere can induce the migration of Bi ions to the surface, which in turn affects the performance of the cathode. These results show that fluorine doping is an effective approach to develop highly active and robust cathode for SOFCs.

Metal-organic-framework-derived electrocatalysts for alkaline polymer electrolyte fuel cells

Metal-organic frameworks were used as metal-nitrogen-carbon templates to synthesize Co–N–C catalysts through a facile synthesis approach that combined a cobalt-based zeolitic imidazolate framework (ZIF) structure and conductive carbon support. The spectroscopic, structural, and thermogravimetric analysis confirmed the synthesis of the Co-based ZIF, used to prepare catalysts with different ZIF/carbon support ratios by pyrolysis under inert atmosphere. Electrochemical characterization at alkaline pH demonstrated high activity towards oxygen reduction reaction (ORR). In addition to ORR activity, the Co–N–C electrocatalysts showed high methanol tolerance in the preliminary tests in a half-cell configuration. When assembled at the cathode side of both a hydrogen-fed anion exchange membrane fuel cell and an alkaline direct methanol fuel cell (ADMFC), the Co–N–C electrocatalysts showed competitive performance with the state-of-the-art Pt/C and other platinum-group-metal-free materials, using a FUMASEP® FAA-3-50 membrane. Exceptionally high performance (higher than 45 mW cm−2) was achieved in ADMFC fed with high methanol concentration (up to 10 M), due to the high methanol tolerance of Co–N–C electrocatalysts. Normalizing the performance to Pt loading, a value of 31.0 mW mgPt−1 was obtained, which is the highest power up to now recorded with this kind of membrane and one of the highest values in the literature for ADMFCs.

Co and Hf co-doped BaFeO3 cathode with obviously enhanced catalytic activity and CO2 tolerance for solid oxide fuel cell

It is essential to develop efficient and stable cathode materials operated at intermediate temperature for the application of solid oxide fuel cell. In this work, BaFeO3–δ based perovskite oxide was used to explore the influence of Co and Hf co-doping on the catalytic activity and CO2 tolerance of SOFC cathode materials. Among the series materials, BaCo0·2Fe0.7Hf0.1O3–δ (BC2FHO) shows excellent catalytic activity and CO2 stability. The EIS measurement shows that the polarization resistance (Rp) of BC2FHO is ∼0.04 Ω cm2 at 800 °C. In the CO2 tolerance test, the Rp decreases to ∼0.0435 Ω cm2 within 1 h after removing 10% CO2. The peak power density of the single cell with BC2FHO cathode are 1010.4, 649.4, and 256.6 mW cm−2 at 800, 700, and 600 °C, respectively. And the total degradation rate of the output voltage at 700 °C is only 0.009% h−1. The significantly enhanced activity and stability are attributed to Co and Hf co-doping. The incorporation of Hf allows BaFeO3 to obtain a highly symmetrical cubic structure with increased oxygen ion transport channels, which is conducive to promote the oxygen reduction reaction. In addition, Hf-doping can also increase the acidity to make the material resistant to CO2. The incorporation of Co improves the concentration of oxygen vacancies, which makes BC2FHO show excellent electrochemical performance.

Trace Doping of Pb(OH)2 Species on PdPb Alloys Boost Highly Active and Stable Ethanol Oxidation.

PdPb nanocrystals have drawn considerable attention due to their excellent catalytic properties, while their practical applications have been impeded by the severe degradation of activity, which is caused by the adsorption of intermediates (especially CO) during the operation. Herein, we first present porous PdPb alloys with the incorporation of amorphous Pb(OH)2 species as highly active and stable electrocatalysts. Alloying Pd with Pb species is initially proposed to optimize the Pd–Pd interatomic distance and adjust the d-band center of Pd. Importantly, the amorphous Pb(OH)2 species are beneficial to promoting the formation of OHad and the removal of COad. Therefore, PdPb-Pb(OH)2 catalysts show a mass activity of 3.18 A mgPd–1 and keep excellent stability for the ethanol oxidation reaction (EOR). In addition, further CO stripping and a series of CO poisoning experiments indicate that PdPb-Pb(OH)2 composites possess much better CO tolerance benefiting from the tuned electronic structure of Pd and surface incorporation of Pb(OH)2 species.

Systematic DFT studies of CO-Tolerance and CO oxidation on Cu-doped Ni surfaces

Nickel-based surfaces have received significant attention as an efficient substrate for electrooxidation. This work studied doped nickel surfaces with Cu atoms to enhance the CO-Tolerance. A comparative study was performed for CO adsorption upon different cleavage facets of pristine and Cu-doped nickel surfaces, whereas the adsorption energy, charge transfer, and density of state for CO were estimated using GGA-RPBE calculation method. Several adsorption probabilities were considered, and the change in adsorption energy and bond lengths were used to explain the CO adsorption mechanism. Otherwise, the density of state was employed to study the 3σ and 1π orbital to demonstrate the adsorption of CO onto the different facets. According to our analysis, the Cu-doped nickel surface showed higher CO tolerance than the pristine nickel surface. Whereas the calculated CO adsorption energies of Cu-doped surfaces have more positive values than the non-doped counterparts. The catalytic ability of pristine and Cu-doped Ni(111) was studied to evaluate the ability of surface poisoning resistance. Thus, oxidation of CO to CO2 was studied using the Eley-Rideal mechanism upon the pristine and Cu-doped surfaces of Ni(100) where the rate-determining step for CO oxidation upon the reported surfaces was estimated as CO + O2* → CO2* + O* by an energy barrier of 1.05 and 0.9 eV for pristine, and Cu-doped Ni (100).

Regulating the Surface Electronic Structure of RuNi Alloys for Boosting Alkaline Hydrogen Oxidation Electrocatalysis

Nickel (Ni) is a promising electrocatalyst for alkaline hydrogen oxidation reaction (HOR). However, the strong hydrogen binding at Ni site (Ni–H) limits its electrocatalytic HOR activity. Herein, ruthenium (Ru) is introduced to regulate the surface electronic structure of Ni and optimize the Ni–H. Simultaneously, constructing the interfacial-oxygen (O) configuration endows Ni with suitable oxophilic components to optimize the adsorption energy for surface hydroxyl species (OH*). The density functional theory (DFT) simulation and characterization results confirm that electron transfer from Ni to Ru causes the d-band center of Ni to shift down, weakening the hydrogen binding energy (HBE) and hydroxyl binding energy (OHBE), which synergistically contributes the enhanced HOR performance for the optimal O-RuNi@C-400 with a diffusion-limiting current density of 2.87 mA cm–2 and mass activity of 601 mA mg–1PGM at an overpotential of 50 mV, which is ∼1.20 and 7.90 times higher than that of Pt/C, respectively. Besides, because of the protective shell of oxophilic Ni–O–C interface to reduce the affinity with CO, O-RuNi@C-400 exhibits better CO tolerance (1000 ppm) than that of commercial Pt/C in alkaline media, making it a promising HOR electrocatalyst for hydrogen fuel cells.