High Activity For Methanol Oxidation Reaction Research Articles

Design and catalytic performance of Cu/γ-Al2O3 for electrocatalytic methanol oxidation reaction by using density functional theory and molecular dynamics

The electrocatalytic activity of methanol oxidation reaction (MOR) on Cu/γ-Al2O3 and the growth behavior of Cu on γ-Al2O3 are investigated by using density functional theory and molecular dynamics. It is found that the interaction between the Cu3 cluster and γ-Al2O3(110) is stronger than that between the Cu4 cluster and γ-Al2O3(110). Consequently, the d-band center of the Cu3 cluster locates close to the Fermi level compared to the d-band center of the Cu4 cluster, resulting in high electrocatalytic MOR activity on Cu3/γ-Al2O3(110). The electrocatalytic MOR pathway is non-CO pathway on Cu3/γ-Al2O3(110). The highest Gibbs free energy pathway is CH3O* → CH2O*, which the Gibbs free energy is 0.53 eV. To achieve a high proportion of 2D Cu cluster on γ-Al2O3, it is recommended to prepare the catalyst at temperatures below 500 K with Cu loading below 21.78 wt%. These findings provide valuable insights into the design of MOR catalysts.

Hybrid Acid/Base Electrolytic Cell for Hydrogen Generation and Methanol Conversion Implemented by Bifunctional Ni/MoN Nanorod Electrocatalyst.

Combining the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) within an integrated electrolytic system may offer the advantages of enhanced kinetics of the anode, reduced energy consumption, and the production of high-purity hydrogen. Herein, it is reported the construction of Ni─MoN nanorod arrays supported on a nickel foam substrate (Ni─MoN/NF) as a bifunctional electrocatalyst for electrocatalytic hydrogen production and selective methanol oxidation to formate. Remarkably, The optimal Ni─MoN/NF catalyst displays exceptional HER performance with an overpotential of only 49mV to attain 10mAcm-2 in acid, and exhibits a high activity for MOR to achieve 100mAcm-2 at 1.48V in alkali. A hybrid acid/base electrolytic cell with Ni─MoN/NF electrode as anode and cathode is further developed for an integrated HER-MOR cell, which only requires a voltage of 0.56V at 10mAcm-2 , significantly lower than that of the HER-OER system (0.70V). The density functional theory studies reveal that the incorporation of Ni effectively modulates the electronic structure of MoN, thereby resulting in enhanced catalytic activity. The unique combination of high electrocatalytic activity and excellent stability make the Ni─MoN/NF catalyst a promising candidate for practical applications in electrocatalytic hydrogen production and methanol oxidation.

Electronic and Coordination Effect of PtPd Nanoflower Alloys for the Methanol Electrooxidation Reaction

Platinum-based electrocatalysts usually exhibit limited and quickly vanished activity for the methanol oxidation reaction (MOR) due to active site occupation and surface intermediate poisoning, especially CO. The attendant synergistic effect of the alloy strategy is often executed to improve these flaws. Here, PtPd nanoflower alloys uniformly anchored on the carbon paper were successfully synthesized by electrodeposition to construct well-defined active sites, over which high MOR activity and tolerance were realized. The homogeneous alloy structure of PtPd nanoflowers was confirmed by TEM and XAFS. Impressively, the Pt1Pd1-N NFs/CP exhibited an excellent mass activity of 9.25 A mgPt+Pd–1 and specific activity of 13.2 mA cmECSA–2 of MOR in the alkaline electrolyte, and 87.8% of the initial activity was still retained after 500 cycles. In situ infrared spectroscopy revealed that Pt1Pd1-N NFs/CP ensured the complete oxidation of methanol following a CO-free path. The investigation of the electronic and coordination structure demonstrated that the Pt–Pd adjacent sites with a zero valence are the highly active center for MOR, and the synergistic effect between Pt and Pd greatly improved the MOR electrocatalytic performance. This work offers an effective strategy to precisely control the number and structure of decorating species for constructing alloy nanocatalysts to enhance the electroactivity toward MOR.

Ultrafine PtRh-Co3O4 ternary alloy nanoparticles with enhanced electrocatalytic activity and long-term stability for alcohol electro-oxidation

To date, the development of structure-sensitive electrocatalysts is crucial, consisting of oxophilic metals and a conductive support with Pt-rich surfaces. In this study, PtRh-Co3O4 ternary alloy nanoparticles (∼2–3 nm) were uniformly distributed on carbon (PtRh-Co3O4/C) via a co-chemical reduction method. The chemical inertness and oxophilicity of Rh, along with the abundant oxygen defects of Co3O4, contributed to improving the kinetics of the methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) in PtRh-Co3O4/C by promoting the scission of C-C and C-H bonds. PtRh-Co3O4/C displayed high intrinsic activity for both MOR (6.8 mA/cm2Pt) and EOR (3.17 mA/cm2Pt) due to the strong electronic, ligand, and bifunctional effects. Even after 7000 potential cycles, it retained 81% (MOR) and 84% (EOR) of its initial value, indicating extended stability. Compared to other Pt-based benchmark catalysts, PtRh-Co3O4/C exhibited higher CO tolerance, extended activity, and stability, making it a promising electrocatalyst with competitive performance for alcohol electro-oxidation.

ZIF-67-derived CoP/NC effectively supported Pt nanoparticles for methanol oxidation reaction.

Metal-support interaction plays an important role in the catalysis reaction, and an effective support is highly desired in the hybrid catalyst construction. Herein, we demonstrated an effective catalyst system by coupling Pt nanoparticles over the ZIF-67-derived CoP/NC support for methanol oxidation reaction (MOR) in acidic and alkaline solutions. The results indicated that the Pt-CoP/NC catalyst showed high catalytic activity and stability for MOR owing to the oxophilic properties of CoP and the strong metal-support interaction, as well supported by the electrochemical measurements and the spectroscopic analysis, which far exceeded that of the Pt-Co/NC and commercial Pt/C catalysts. Specifically, the forward peak current density of the Pt-CoP/NC catalyst was 74.2 mA cm-2 for MOR in an acidic electrolyte, which was 2.2 times higher than that of a commercial Pt/C catalyst. Further, in an alkaline electrolyte, the Pt-CoP/NC catalyst showed the highest forward peak current density of 118.6 mA cm-2, which was 4.5 times higher than that of a commercial Pt/C catalyst. High catalytic kinetics and stability for MOR were also carefully discussed. Moreover, the Pt-CoP/NC catalyst exhibited excellent anti-poisoning ability in comparison to the Pt-Co/NC and commercial Pt/C catalysts with the help of the CO-stripping technique. The current work would be instructive for high-performance catalyst system construction based on the ZIF-67-derived CoP/NC support.

Three-dimensional porous PtCu as highly efficient electrocatalysts for methanol oxidation reaction

Exploring affordable, durable, and effective electrocatalysts for methanol oxidation reaction (MOR) is of great importance to the industrial application of direct methanol fuel cells. Herein, a three-dimensional (3D) porous PtCu catalyst is synthesized by a facile and effective galvanic replacement method, which exhibits high activity and durability for MOR. The modulated electronic and strain effects of the Pt atoms are verified by extensive characterizations, and the mass and specific activities of the prepared catalyst are roughly 3.8 and 9.9 times higher than those of the commercial Pt/C catalysts, respectively. The robust activity of the prepared catalyst is probably owing to the optimized affination between Pt and the adsorbed poisoning species (mainly CO) induced by the electronic and strain effects of the Pt, as well as the unique 3D porous nanostructure.

Porphyrinic MOF derived Single-atom electrocatalyst enables methanol oxidation

Electrochemical methanol oxidation reaction (MOR) serves as a key route for renewable energy technologies. However, unmet challenges remain in the preparation of low-cost, efficient and robust electrocatalysts for MOR. Herein, a porphyrinic metal–organic framework (MOF) with spatially isolated Ni centres is prepared. Upon pyrolysis, this affords a single-atom Ni implanted nitrogen-doped porous carbon (20% Ni-N-C). Integrating abundant and accessible single-atom Ni sites, hierarchical porosity, excellent conductivity with stable Ni-N4 moieties all in one, the derived ultra-stable 20% Ni-N-C exhibits high MOR activity, impressive durability and CO tolerance, thereby outperforming state-of-the-art nonprecious metal based electrocatalysts. Computational insights reveal a low energy barrier of 1.19 eV for the rate-determining step, in agreement with the experimental observations of superior MOR activity. As the first foray into improving MOR efficiency with nonprecious metal based single-atom electrocatalysts, the yet-unrealized potential for MOFs and related modular hybrids is demonstrated.

Pt-SDC alloy anode for methanol fueled low temperature solid oxide fuel cell

Direct methanol-fueled low-temperature solid oxide fuel cells (DM LT-SOFCs) operating temperature ≤ 500 ℃ are promising candidates as portable power sources owing to the high energy density and portability of methanol. Herein, we have systematically studied the Pt-samaria-doped ceria (SDC) cermet alloy anodes with varying Pt: SDC ratios to achieve high methanol oxidation reaction activity (MOR) and resistance to CO poisoning. It is observed that the optimal composition of the Pt-SDC alloy anode is Pt0.83SDC0.17, which exhibited lower activation resistance by 63 %, better tolerance to CO poisoning by 44 %, and higher thermal stability than that of pure Pt upon direct methanol operation at 450 ℃. Such improvements were ascribed to high Pt-SDC interfacial density of reaction sites with less CO poisoning due to oxygen spill over from SDC, while thermally stable SDC also helped preserve the morphology of the Pt anode at elevated temperatures.

Electrocatalytic Oxidation of Methanol Over Silver-Based Ag-M/C (M = Cu, Zn, Fe, Cr, Mn) Electrocatalysts Synthesized by Solution Combustion Technique

Herein, we report the electrocatalytic properties of Ag-M/C (M = Cu, Zn, Fe, Cr, Mn) catalysts synthesized using solution combustion synthesis (SCS) method for methanol oxidation reaction (MOR). The morphological properties of the synthesized catalysts were studied using SEM, EDX, TEM, XRD and XPS techniques. The results indicated AgCu/C to be the most porous catalyst with small and well distributed nanoparticles making it a suitable choice for electrocatalytic applications. The XPS results showed a shift in peak in the AgCu/C sample due to the charge transfer between Ag and Cu indicating a strong interaction in the compound. The electrochemical measurements in 1 M methanol with 1 M KOH electrolyte by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) revealed that AgCu/C showed high electrocatalytic activity for MOR. Further studies on AgCu/C for methanol concentrations of 0.5 M, 1 M, 1.5 M, 2.5 M to evaluate the rate dependency of the catalyst indicated a power-law dependency with an order of 0.55 on methanol concentration. According to chronoamperometry analysis, the catalyst was stable for at least 20 h.

Silk‐Derived N‐Doped Fe@NPC as Efficient Bifunctional Electrocatalyst for Direct Methanol Fuel Cell (DMFC)

AbstractThe development of economic and efficient bifunctional electrocatalysts, which can boost both the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is quite necessary for the evolution of direct methanol fuel cell (DMFC). Herein, a novelty of precious metal‐free, iron, nitrogen and phosphorus‐doped porous carbon (Fe@NPC) was prepared by using cheap and renewable biomass silk as basic nitrogen sources, as an efficient ORR and MOR electrocatalyst with its high nitrogen content (8.16 wt%). The Fe@NPC catalyst exhibits extremely high onset potential (1.125 V vs RHE), current density (−6.089 mA cm−2) and methanol tolerance for ORR, even exceeds the corresponding values of Pt/C (1.007 V vs RHE, 5.068 mA cm−2). Furthermore, it also served as a good carrier for Pt nanoparticles (NPs). Pt/Fe@NPC shows high catalytic activity and stability for MOR in acidic condition.

Rational design ternary platinum based electrocatalysts for effective methanol oxidation reaction

Exploring effective, durable, and affordable electrocatalysts of methanol oxidation reaction (MOR) is of vital significance for the industrial application of direct methanol fuel cells. Herein, an efficient, general, and expandable method is developed to synthesis two-dimensional (2D) ternary PtBiM nanoplates (NPLs), in which various M (Co, Ni, Cu, Zn, Sn) is severed as the third component to the binary PtBi system. The MOR performance of PtBiM NPLs is entirely investigated, demonstrating that both the MOR activity and durability is enhanced with the introduction of the additional composition. Pt3Bi3Zn NPLs shows much higher MOR activity and stability than that of the PtBi counterparts, not to mention the current advanced PtRu/C and Pt/C catalysts. The prominent performances are attributed to the modulated electronic structure of the surface Pt in PtBi NPLs by the addition of Zn, resulting in a weakened affination between Pt and the adsorbed poisoning species (mainly CO) compared with PtBi NPLs, verified by density functional theory (DFT) calculations. In addition, the absorbed OH can be generated on the surface of Zn atom due to its favorable water activation properties, thus the CO removal on the adjacent Pt atoms is accelerated, further leading to a high activity and anti-poisoning performance of the resulting Pt3Bi3Zn catalyst. This work provides new insights and robust strategy for highly efficient MOR electrocatalyst with extraordinary anti-poisoning performance and stability.

Highly Conductive and CO‐Resistant Cobalt‐Based Monolithic Electrodes for the Catalytic Oxidation of Methanol

AbstractTo develop active and stable electrocatalysts for the methanol oxidation reaction (MOR), many non‐noble metal‐based nanomaterials have been explored, which are physically loaded on conductive substrates to form electrodes. During a long‐term MOR under high current density, these electrodes usually lose activity due to the aggregation or falling off of active nanomaterials. To overcome these problems, we report a simple strategy to synthesize an active, stable, and carbon monoxide (CO)‐resistant monolithic electrode for the MOR: cobalt nanocrystal/nitrogen, oxygen‐doped carbon (Co@N,O−C, CP) monolith. CP monolith shows a high electrical conductivity (1.54×104 S/cm), which can be directly used as an electrode without any substrate. Co nanocrystals are dispersed uniformly in the N,O−C matrix as the active site for MOR, whereas the N,O−C matrix protects Co nanocrystals and also facilitates the mass and charge transfer between electrolyte and the electrode. The optimized CP−FT‐500 electrode presents a high MOR activity of 352 mA/cm2 at 0.6 V vs SCE (unsaturated calomel electrode) in alkaline electrolyte, which exceeds most previously reported Co‐based MOR catalysts. The optimal CP−FT‐500 catalyst also presents excellent durability and anti‐CO poisoning capability (93.3 % retention of activity), which exceeds that of Pt/C (67.5 % retention). Based on its excellent catalytic activity, stability, and high resistance to CO poisoning, CP−FT‐500 catalyst is a promising low‐cost catalyst for MOR.

Probing the enhanced methanol electrooxidation mechanism by promoted CO tolerance on the Pd catalyst modified with TaN: A combined experimental and theoretical study

The low-palladium Pd/TaN–C catalyst is synthesized by a surfactant-free solvothermal approach and exhibits high activity (2613.18 mA mgPd−1), durability and CO tolerance for MOR (methanol oxidation reaction) in alkaline media, 12.4 folds that of the commercial Pd/C. XPS and electrochemical results indicate that the interfacial Pd–TaNO bond is generated. This also brings the enhancement of OHad adsorption responsible for anti-CO poisoning ability. Density Functional Theory (DFT) calculations indicate that the reaction pathway and the rate-determining step are changed for methanol decomposition to CO on the Pd4/TaN(001) surface compared with Pd (111). The preferred pathway can be described as: CH3OH→CH3O→CH2O→CHO→CO. Furthermore, the results indicate that the adsorption of OH is enhanced and the energy barrier of COOH formation from CO + OH is reduced with the high concentration of hydroxyl on the Pd4/TaN(001) surface, further confirming the bi-functional effect of hydroxyl on the CO tolerance.

Enhanced oxygen reduction and methanol oxidation reaction over self-assembled Pt-M (M = Co, Ni) nanoflowers

Herein, we introduce a facile approach to synthesize a unique class of Pt-M (M = Ni, Co) catalysts with a nanoflower structure for boosting both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). By controlling the surface-active agents, we modified the functional groups surrounding the Pt atoms, tuned the alloying of Pt and the transition metals Ni and Co, and prepared two different kinds of nanodendrites. Their successful synthesis depends on the selection and amount of surfactants (hexadecyltrimethylammonium bromide (CTAB), Polyvinylpyrrolidone (PVP)). Besides, by controlling reaction time, we also explored the forming procedures for Pt-Co globularia nanodendrite (Pt-Co GND) and Pt-Ni petalody nanodendrite (Pt-Ni PND). Our investigation highlights the importance of complex nanoarchitecture, which enables surface and interface modification to achieve excellent catalytic performance in fuel cell electrocatalysis. The characterization of the as-prepared catalysts reveals a high electrochemical surface area and mass activity (2041 mAmgPt-1and 950 mAmgPt-1 for Pt-Co GND and Pt-Ni PND, respectively, for ORR). Furthermore, Pt-Co GND showed a high MOR activity, with a mass activity value recorded at 1615 mAmgPt-1 which is far superior to that for Pt/C. Moreover, both catalysts retain high activity after accelerated durability tests (ADTs). The electron transfer number was calculated by performing the rotating ring-disk electrode (RRDE) measurements. Due to abundant active sites of Pt, both Pt-Co GND and Pt-Ni PND exhibit a 4e− pathway for ORR with electron transfer number of >3.95.

Highly efficient methanol oxidation reaction on durable Co9S8 @N, S-doped CNT catalyst for methanol fuel cell applications

The implementation of direct methanol fuel cells is seen as a reliable factor in the future energy mix. Efficient energy conversion from methanol requires an active and durable catalyst to drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells. As an alternative to high cost noble metals, cobalt-based electrocatalysts are considered potential replacements that meet the high activity and long-term stability for MOR. Herein, we report the preparation of hierarchical Co9S8 nanowires trapped in N-doped carbon nanotubes (N,S–Co@CNT) derived from melamine showing high activity for MOR in alkaline medium. In order to identify the main active sites, we synthesized cobalt particles embedded in carbon structures in absence of a sulphur source (Co@CNT) and evaluated its performance for MOR. The material characterization shows that adding sulphur during pyrolysis enhances the surface area, pore size and lattice defect. In addition, the morphology changes from hemi-spherical particles to nanowires, that significantly improves the electrochemical properties. The current density of N,S–Co@CNT is exceptionally higher (5.5 times) and the onset potential of MOR is shifted to lower potential when compared to Co@CNT. The enhanced activity, durability and stability of N,S–Co@CNT is ascribed to the unique hierarchical structure and surface properties.

An Enhanced‐Activity and High‐Stability PtCo/N‐Doped Carbon Skeleton Electrocatalyst Derived from UA‐ZIF‐67 Template for Methanol Oxidation

AbstractTo improve electrocatalytic performances of Pt‐based catalysts toward methanol oxidation reaction (MOR) and reduce the consumption of Pt, we report a novel strategy for preparing a PtCo/NCS catalyst with bimetallic PtCo nanoparticles supported on the nitrogen‐doped carbon skeleton (NCS) derived from ulmic‐acid ‐based ZIF‐67 (UA‐ZIF‐67) template. The synthesized optimal NCS has rich mesoporous structure with a BET specific surface area of 451 m2 g−1and average pore diameterof 4.5 nm, possesses graphitic structure containing some CNTs and many graphene layers, and is doped by 8.16 at% nitrogen in the form of pyridine N and pyrrole N. In the optimum PtCo/NCS, metallic Pt and Co nanoparticles with an average size of 3.0±0.5 nm are uniformly supported on the NCS. This PtCo/NCS catalyst shows a high electrocatalytic activity and stability for MOR due to its high electrochemically active specific surface area (ECSA) value, current density, steady‐state current and current retention. The results are attributed to small highly‐dispersed PtCo nanoparticles with good synergistic effects of bimetallic active components supported on the NCS possessing CNTs and graphene layers, suitable nitrogen doping and well‐matched hierarchical pore structure.These findings will provide a new insight in designing and synthesizing high‐performance electrocatalysts.

Robust copper nanocrystal/nitrogen-doped carbon monoliths as carbon monoxide-resistant electrodes for methanol oxidation reaction

Noble metal-based electrocatalysts present high activities for methanol oxidation reaction (MOR), but are limited by their high cost, low stability and poor resistance to carbon monoxide (CO) poisoning. The development of active and stable non-noble metal electrocatalysts for MOR is desired, but remains a challenge. Herein, we report a simple strategy to make copper nanocrystal/nitrogen-doped carbon (Cu/N-C) monoliths, which can serve as active and robust electrodes for MOR. Copper nanocrystals were electrochemically deposited onto a conductive polyaniline hydrogel and calcined to form Cu/N-C monolith, where the active copper nanocrystals are protected by nitrogen-doped carbon. Owing to their extremely high electrical conductivity (1.25 × 105 S cm−1) and mechanical robustness, these Cu/N-C monoliths can be directly used as electrodes for MOR, without using substrates or additives. The optimal Cu/N-C (FT) @500 monolith shows a high MOR activity of 189 mA cm−2 at 0.6 V vs. SCE in alkaline methanol solution, superior to most of reported Cu-based MOR catalysts. Cu/N-C (FT)@500 also presents a better stability than Pt/C catalyst in the long-term MOR test at high current densities. Upon carbon monoxide (CO) poisoning, Cu/N-C (FT)@500 retains 96% of its MOR activity, far exceeding the performance of Pt/C catalyst (61% retention). Owing to its facile synthesis, outstanding activity, high stability and mechanical robustness, Cu/N-C (FT)@500 monolith is promising as a low-cost, efficient and CO-resistant electrocatalyst for MOR.

Facile synthesis of alloyed PtNi/CNTs electrocatalyst with enhanced catalytic activity and stability for methanol oxidation

Pt-based alloy electrocatalysts, PtNi/CNTs and PtNi, were synthesized through facile chemical reduction reaction for methanol oxidation reaction (MOR). Morphology, structure and composition of the PtNi/CNTs and PtNi electrocatalysts were physical characterized by the means of SEM, EDS, XRD and XPS. The catalytic activity, stability and durability of the obtained electrocatalysts were studied by cyclic voltammetry (CV) and amperrometric i-t cueves (i-t). The PtNi catalysts nanoparticles (NPs) obtained around 20 nm were homogenous distribution of two metal elements, and PtNi were well doped on the carbon nanotubes (CNTs) for PtNi/CNTs catalysts. The incorporation of Ni and high surface area of CNTs make the PtNi/CNTs and PtNi catalysts showing high eletrocatalytic activity for MOR. Furthermore, both PtNi/CNTs and PtNi electrocatalysts exhibit outstanding stability and durability at room temperature in acidic medium. This research provides positive guidance to prepare high performance and excellent stability electrocatalysts for MOR.

Thermal Radiation Synthesis of Ultrafine Platinum Nanoclusters toward Methanol Oxidation

AbstractDirect methanol fuel cells (DMFCs) are considered as a promising candidate for portable electronic devices and small electric vehicles due to their high gravimetric and volumetric energy densities. The operation of DMFCs requires efficient catalysts, especially on the anode to promote methanol oxidation reaction (MOR). To date, platinum has emerged as a chief contender for MOR. Unfortunately, most catalysts suffer from severe CO poisoning, which can passivate the catalytic surface and decrease the activity over time. Herein, a transient, thermal radiation method to synthesize ultrafine platinum nanoclusters (0.68 ± 0.13 nm) supported on carbon black (Pt NC/CB) is demonstrated. The sample demonstrates a great CO poisoning resistance and excellent activity toward MOR. The ultrafine platinum nanoclusters with increased active sites can promote the oxidation of CO at potential as low as 0.4 V. The Pt NC/CB displays an onset potential of 0.4 V and a peak current density of 1.30 mA cm−2ECSA (electrochemical active surface area), which is superior than that of reported catalysts (0.57–1.06 mA cm−2ECSA), while many of the catalysts are alloys involving noble metals. This work showcases an efficient method to prepare Pt nanoclusters with high MOR activity and great CO poisoning resistance.

Quatermetallic Pt-based ultrathin nanowires intensified by Rh enable highly active and robust electrocatalysts for methanol oxidation

Inferior stability and anti-poisoning capacity of Pt-based ultrathin nanowires (NWs) are critical weaknesses under detrimental acidic running conditions for proton-exchange membrane fuel cell applications due to their energetic surface. Here 1.5-nm-thin quatermetallic PtCoNiRh NWs with high atomic-exposure are fabricated to serve as robust electrocatalysts for acidic methanol oxidation reaction (MOR). Surpassing Rh-free PtCoNi NWs and most of state-of-the-art catalysts, the PtCoNiRh NWs achieve extremely high MOR activity (1.36 A·mg−1Pt and 2.08 mA cm−2) with substantially lowered onset-potential and improved CO-tolerance. The anticorrosion effect of incorporated-Rh can effectively stabilize the PtCoNiRh NWs in the corrosive MOR. Electrochemical in situ Fourier transform infrared spectroscopy and density functional theory simulation cooperatively reveal that the methanol dehydrogenation is inclined to occur at the interatomic Pt–Rh sites, where the intermediate COads prefers bridge binding mode rather than linear mode with facilitated removal. Integratedly, the complete 6e−-transferred MOR process is reliably accelerated and stays efficient on the quaternary PtCoNiRh NWs.