Insights into the roles of nitrogen and phosphorus co-doping for efficient methanol electrooxidation.

Anchoring Pt onto multi-heteroatom doped carbon materials has been recognized as an effective approach to improve the performance of electrocatalytic methanol oxidation. However, distinct contributions and specific behavior mechanisms of different heteroatoms, notably N and P, the specific behavior mechanisms in synergistically promoting Pt NPs remain elusive. In this work, we construct 1D N and P co-doped carbon nanotube (N, P-CNTs) supports with abundant defect anchors for Pt. The as-prepared Pt/N, P-CNTs exhibit outstanding activity and exceptional stability in methanol oxidation reaction (MOR), achieving high mass activity up to 6481.3 mA mg-1Pt. Moreover, they can retain 90.5 % of their initial current density even after 800 cycles tests. Detailed characterizations and theoretical calculations indicate that the robust strong metal-support interactions (SMSI) effect caused by N doping within the unique N and P co-doped coordination structure controllably regulate the coordination environment of Pt, reduce the d-band center of Pt, thus promoting the adsorption and decomposition of CH3OH. However, P doping weakens the adsorption strength of CO on the Pt active site by sacrificing partial electron transfer, accelerating the oxidative conversion of the CO-like poisoning species (COads). Significantly, the synergistic mechanism of N and P species on the modification of Pt's electronic structure and its subsequent impact on the electrocatalytic methanol oxidation behaviors on the Pt surface was thoroughly elucidated, providing a constructive route for designing robust MOR electrocatalysts with high MOR activity and durability.

Polythiophene-coated carbon nano boxes for efficient platinum-based catalysts for methanol electrooxidation.

To improve the efficiency of the methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), it is essential to develop catalysts with high catalytic activity. However, constructing polyatomic doped carbon nanomaterials and understanding the interaction mechanisms between dopant elements remain significant challenges. In this study, we propose nitrogen-doped carbon nanobox (CNB) derived from Zeolitic Imidazolate Framework-67 (ZIF-67) crystals as precursors to serve as carriers for highly efficient platinum nanoparticles (Pt NPs). We synthesized platinum/poly(3,4-propylenedioxythiophene)/carbon nanobox (Pt/PProDOT/CNB) composites by wrapping CNB around PProDOT films via in situ oxidative polymerization. This unique structural design provides several advantages to the catalyst, including a large active surface area, numerous accessible electrocatalytic active centers, an optimized electronic structure, and good electronic conductivity. The Pt/PProDOT/CNB composites demonstrated excellent methanol oxidation performance, with a remarkable mass activity (MA) of 1639.9 mA mg-1Pt and a high electrochemical active surface area (ECSA) of 160.8 m2/g. Furthermore, the catalyst exhibited good CO resistance and outstanding durability.

Rationally Designed L12-Pt2RhFe Intermetallic Catalyst with High CO-Tolerance for Alkaline Methanol Electrooxidation.

It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L12-Pt2RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt2RhFe/C achieves a superior mass activity of 6.43 A mgPt -1, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt2RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt2RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.

Adsorbed Carbon Monoxide-Enabled Self-Terminated Au-Grafting on Pt6 Nanoclusters for Enhanced Methanol Electrooxidation.

The study presents the first example of an adsorbed carbon monoxide (CO) enabled self-terminated Au-grafting on triphenylphosphine (PPh3) stabilized Pt6 nanoclusters (NCs) (Pt6 (PPh3)4Cl5 NCs or Pt6 NCs). Adsorbed PPh3 ligands weaken the Pt-CO bond enabling the self-terminated Au-grafting on Pt6 NCs. The Au-grafted Pt6 NCs exhibit enhanced methanol electrooxidation (MOR) in acidic solutions. The surface is composed of a PtAu ensemble exhibiting enhanced MOR and CO tolerance due to the synergistic interaction of Pt with Au and PPh3. The hydrogen underpotential deposition (H-UPD) signal from a CO-covered surface reveals the existence of free-Pt sites on the PtAu ensemble causing higher MOR reactivity. The Au and PPh3 ensure electrocatalytic activity of the NCs, depriving of them at anodic potentials results in "a death-valley" trend.

Pt1.8Pd0.2CuGa Intermetallic Nanocatalysts with Enhanced Methanol Oxidation Performance for Efficient Hybrid Seawater Electrolysis.

Seawater electrolysis is a potentially cost-effective approach to green hydrogen production, but it currently faces substantial challenges for its high energy consumption and the interference of chlorine evolution reaction (ClER). Replacing the energy-demanding oxygen evolution reaction with methanol oxidation reaction (MOR) represents a promising alternative, as MOR occurs at a significantly low anodic potential, which cannot only reduce the voltage needed for electrolysis but also completely circumvents ClER. To this end, developing high-performance MOR catalysts is a key. Herein, a novel quaternary Pt1.8Pd0.2CuGa/C intermetallic nanoparticle (i-NP) catalyst is reported, which shows a high mass activity (11.13 A mgPGM -1), a large specific activity (18.13 mA cmPGM -2), and outstanding stability toward alkaline MOR. Advanced characterization and density functional theory calculations reveal that the introduction of atomically distributed Pd in Pt2CuGa intermetallic markedly promotes the oxidation of key reaction intermediates by enriching electron concentration around Pt sites, resulting in weak adsorption of carbon-containing intermediates and favorable adsorption of synergistic OH- groups near Pd sites. MOR-assisted seawater electrolysis is demonstrated, which continuously operates under 1.23 V for 240 h in simulated seawater and 120 h in natural seawater without notable degradation.

Facile Synthesis of PtP2 Nanocrystals as Highly Active Electrocatalysts for Methanol Oxidation.

Although significant efforts have been made in the past few decades, the development of affordable, durable, and effective electrocatalysts for direct methanol fuel cells (DMFCs) remains a formidable challenge. Herein, we present a facile and efficient phosphorization approach for synthesizing PtP2 intermetallic nanocrystals and utilize them as electrocatalysts in the methanol oxidation reaction (MOR). Impressively, the synthesized PtP2 nanocatalysts exhibit a mass activity of 2.14 mA µg-1 and a specific activity of 6.28 mA cm-2, which are 5.1 and 9.5 times higher than those achieved by the current state-of-the-art commercial Pt/C catalyst, respectively. Moreover, the PtP2 nanocatalysts demonstrate improved stability toward acidic MOR by retaining 92.1% of its initial mass activity after undergoing 5000 potential cycles, far surpassing that of the commercial Pt/C (38%). Further DMFC tests present a 2.7 times higher power density than that of the commercial Pt/C, underscoring their potential for application in methanol fuel cells. Density functional theory calculations suggest that the accelerated MOR kinetics and improved CO tolerance on PtP2 can be attributed to the attenuated binding strength of CO intermediates and the enhanced stability due to strong Pt-P interaction. To our knowledge, this is the first report identifying the MOR performance on PtP2 intermetallic nanocrystals, highlighting their potential as highly active and stable nanocatalysts for DMFCs.

Evolution of High-Index Facets Pt Nanocrystals Induced by N-Defective Sites in the Integrated Electrode for Enhanced Methanol Oxidation.

Highly efficient and durable Pt electrocatalysts are the key to boost the performance of fuel cells. The high-index facets (HIF) Pt nanocrystals are regarded as excellent catalytic activity and stability catalysts. However, nucleation, growth and evolution of high-index facets Pt nanocrystals induced by defective sites is still a challenge. In this work, tetrahexahedron (THH) and hexactahedron (HOH) Pt nanocrystals are synthesized, which are loaded on the nitrogen-doped reduced graphene oxide (N-rGO) support of the integrated electrodes by the square wave pulse method. Experimental investigations and density functional theory (DFT) calculations are conducted to analyze the growth and evolution mechanism of HIF Pt nanocrystals on the graphene-derived carbon supports. It shows that the H adsorption on the N-rGO/CFP support can induce evolution of Pt nanocrystals. Moreover, the N-defective sites on the surface of N-rGO can lead to a slower growth of Pt nanocrystals than that on the surface of reduced graphene oxide (rGO). Pt/N-rGO/CFP (20 min) shows the highest specific activity in methanol oxidation, which is 1.5 times higher than that of commercial Pt/C. This research paves the way on the design and synthesis of HIF Pt nanocrystal using graphene-derived carbon materials as substrates in the future.

Tailoring the Activity of Electrocatalytic Methanol Oxidation on Cobalt Hydroxide by the Incorporation of Catalytically Inactive Zinc Ions.

Catalytically inactive Zn2+ is incorporated into cobalt hydroxide to synthesize hierarchical ZnCo-layered double hydroxide nanosheet networks supported on carbon fiber (ZnCo-LDH/CF). The incorporation of Zn2+ is revealed to endow ZnCo-LDH/CF with significantly superior performance in the aspects of the activity and selectivity for methanol electrooxidation to formic acid and the boosting effect for cathodic hydrogen production compared with the counterpart without Zn2+. Density functional theory (DFT) calculation reveals that the incorporation of nonactive Zn2+ can increase the density of states near the Fermi level of LDH (i.e., elevate electrical conductivity to form favorable charge transportation during electrocatalysis) and promote the adsorption and subsequent cleavage of methanol, thus leading to the enhanced methanol electrooxidation performance.

Resolving Atomic-Scale Structure and Chemical Coordination in High-Entropy Alloy Electrocatalysts for Structure-Function Relationship Elucidation.

The recent breakthrough in confining five or more atomic species in nanocatalysts, referred to as high-entropy alloy nanocatalysts (HEAs), has revealed the possibilities of multielemental interactions that can surpass the limitations of binary and ternary electrocatalysts. The wide range of potential surface configurations in HEAs, however, presents a significant challenge in resolving active structural motifs, preventing the establishment of structure-function relationships for rational catalyst design and optimization. We present a methodology for creating sub-5 nm HEAs using an aqueous-based peptide-directed route. Using a combination of pair distribution function and X-ray absorption spectroscopy, HEA structure models are constructed from reverse Monte Carlo modeling of experimental data sets and showcase a clear peptide-induced influence on atomic-structure and chemical miscibility. Coordination analysis of our structure models facilitated the construction of structure-function correlations applied to electrochemical methanol oxidation reactions, revealing the complex interplay between multiple metals that leads to improved catalytic properties. Our results showcase a viable strategy for elucidating structure-function relationships in HEAs, prospectively providing a pathway for future materials design.

Design of Pt-Sn-Zn Nanomaterials for Successful Methanol Electrooxidation Reaction.

This work highlights the potential for the synthesis of new PtSnZn catalysts with enhanced efficiency and durability for methanol oxidation reaction (MOR) in low-temperature fuel cells. In this research, PtZn and PtSnZn nanoparticles deposited on high surface area Vulcan XC-72R Carbon support were created by a microwave-assisted polyol method. The electrochemical performances of synthesized catalysts were analyzed by cyclic voltammetry and by the electrooxidation of adsorbed CO and the chronoamperometric method. The physicochemical properties of obtained catalysts were characterized by transmission electron microscopy (TEM), thermogravimetric (TGA) analysis, energy dispersive spectroscopy (EDS) and by X-ray diffraction (XRD). The obtained findings showed the successful synthesis of platinum-based catalysts. It was established that PtSnZn/C and PtZn/C catalysts have high electrocatalytic performance in methanol oxidation reactions. Catalysts stability tests were obtained by chronoamperometry. Stability tests also confirmed decreased poisoning and indicated improved stability and better tolerance to CO-like intermediate species. According to activity and stability measurements, the PtSnZn/C catalyst possesses the best electrochemical properties for the methanol oxidation reaction. The observed great electrocatalytic activity in the methanol oxidation reaction of synthesized catalysts can be attributed to the beneficial effects of microwave synthesis and the well-balanced addition of alloying metals in PtSnZn/C catalysts.

Molybdenum Carbide/Ni Nanoparticles Embedded into Carbon Nanofibers as an Effective Non-Precious Catalyst for Green Hydrogen Production from Methanol Electrooxidation.

Molybdenum carbide co-catalyst and carbon nanofiber matrix are suggested to improve the nickel activity toward methanol electrooxidation process. The proposed electrocatalyst has been synthesized by calcination electrospun nanofiber mats composed of molybdenum chloride, nickel acetate, and poly (vinyl alcohol) under vacuum at elevated temperatures. The fabricated catalyst has been characterized using XRD, SEM, and TEM analysis. The electrochemical measurements demonstrated that the fabricated composite acquired specific activity for methanol electrooxidation when molybdenum content and calcination temperature were tuned. In terms of the current density, the highest performance is attributed to the nanofibers obtained from electrospun solution having 5% molybdenum precursor compared to nickel acetate as a current density of 107 mA/cm2 was generated. The process operating parameters have been optimized and expressed mathematically using the Taguchi robust design method. Experimental design has been employed in investigating the key operating parameters of methanol electrooxidation reaction to obtain the highest oxidation current density peak. The main effective operating parameters of the methanol oxidation reaction are Mo content in the electrocatalyst, methanol concentration, and reaction temperature. Employing Taguchi's robust design helped to capture the optimum conditions yielding the maximum current density. The calculations revealed that the optimum parameters are as follows: Mo content, 5 wt.%; methanol concentration, 2.65 M; and reaction temperature, 50 °C. A mathematical model has been statistically derived to describe the experimental data adequately with an R2 value of 0. 979. The optimization process indicated that the maximum current density can be identified statistically at 5% Mo, 2.0 M methanol concentration, and 45 °C operating temperature.

Enhancing electrocatalytic methanol oxidation of Pd-Ir nanoalloy through electron-rich catalytic interface induced by incorporating phosphorus.

Incorporating less expensive nonmetal phosphorus (P) into noble metal-based catalysts has become a developing strategy to enhance the catalytic performance of electrocatalysts for methanol electrooxidation reaction (MOR), attributing to the electronic and synergistic structure alteration mechanism. In the work, three-dimensional nitrogen-doped graphene anchoring ternary Pd-Ir-P nanoalloy catalyst (Pd7IrPx/NG) was prepared by co-reduction strategy. As a multi-electron system, elemental P adjusts the outer electron structure of Pd and diminishes the particle size of nanocomposites, which heightens the electrocatalytic activity effectively and accelerate MOR kinetics in alkaline medium. The study reveals that the electron effect and ligand effect induced by P atoms on the hydrophilic and electron-rich surface of Pd7Ir/NG and Pd7IrPx/NG samples can reduce the initial oxidation potential and peak potential of COads, showing significantly enhanced the anti-poisoning ability compared with commercial Pd/C as the benchmark. Meanwhile, the stability of Pd7IrPx/NG is significantly higher than that of commercial Pd/C. The facile synthetic approach provides an economic option and a new vision for the development of electrocatalysts in MOR.

Fe-Ni Diatomic Sites Coupled with Pt Clusters to Boost Methanol Electrooxidation via Free Radical Relaying.

Pt-based catalysts for direct methanol fuel cells (DMFCs) are still confronted with the challenge of over-oxidation of Pt and poisoning effect of intermediates; therefore, a spatial relay strategy was adopted to overcome these issues. Herein, Pt clusters were creatively fixed on the N-doped carbon matrix with rich Fe-Ni diatoms, which can provide independent reaction sites for methanol oxidation reaction (MOR) and enhance the catalytic activity due to the electronic regulation effect between Pt cluster and atomic-level metal sites. The optimized Pt/FeNi-NC catalyst shows MOR electrocatalytic activity of 2.816 A mgPt -1 , 2.6 times that of Pt/C (1.115 A mgPt -1 ). Experiments combined with DFT study reveal that Fe-Ni diatoms and Pt clusters take charge of hydroxyl radical (⋅OH) generation and methanol activation, respectively. The free radical relaying of ⋅OH could prevent the over-oxidation of Pt. Meanwhile, ⋅OH from Fe-Ni sites accelerates the elimination of intermediates, thus improving the durability of catalysts.

Dinitrogen Reduction Coupled with Methanol Oxidation for Low Overpotential Electrochemical NH3 Synthesis Over Cobalt Pyrophosphate as Bifunctional Catalyst.

Electrochemical dinitrogen (N2 ) reduction to ammonia (NH3 ) coupled with methanol electro-oxidation is presented in the current work. Here, methanol oxidation reaction (MOR) is proposed as an alternative anode reaction to oxygen evolution reaction (OER) to accomplish electrons-induced reduction of N2 to NH3 at cathode and oxidation of methanol at anode in alkaline media thereby reducing the overall cell voltage for ammonia production. Cobalt pyrophosphate micro-flowers assembled by nanosheets are synthesized via a surfactant-assisted sonochemical approach. By virtue of structural and morphological advantages, the maximum Faradaic efficiency of 43.37% and NH3 yield rate of 159.6 µg h-1 mgca -1 is achieved at a potential of -0.2 V versus RHE. The proposed catalyst is shown to also exhibit a very high activity (100 mA mg-1 at 1.48 V), durability (2 h) and production of value-added formic acid at anode (2.78 µmol h-1 mgcat -1 and F.E. of 59.2%). The overall NH3 synthesis is achieved at a reduced cell voltage of 1.6 V (200 mV less than NRR-OER coupled NH3 synthesis) when OER at anode is replaced with MOR and a high NH3 yield rate of 95.2 µg h-1 mgcat -1 and HCOOH formation rate of 2.53 µmol h-1 mg-1 are witnessed under full-cell conditions.

MnCo2O4/NiCo2O4/rGO as a Catalyst Based on Binary Transition Metal Oxide for the Methanol Oxidation Reaction.

The demands for alternative energy have led researchers to find effective electrocatalysts in fuel cells and increase the efficiency of existing materials. This study presents new nanocatalysts based on two binary transition metal oxides (BTMOs) and their hybrid with reduced graphene oxide for methanol oxidation. Characterization of the introduced three-component composite, including cobalt manganese oxide (MnCo2O4), nickel cobalt oxide (NiCo2O4), and reduced graphene oxide (rGO) in the form of MnCo2O4/NiCo2O4/rGO (MNR), was investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive X-ray (EDX) analyses. The alcohol oxidation capability of MnCo2O4/NiCo2O4 (MN) and MNR was evaluated in the methanol oxidation reaction (MOR) process. The crucial role of rGO in improving the electrocatalytic properties of catalysts stems from its large active surface area and high electrical conductivity. The alcohol oxidation tests of MN and MNR showed an adequate ability to oxidize methanol. The better performance of MNR was due to the synergistic effect of MnCo2O4/NiCo2O4 and rGO. MN and MNR nanocatalysts, with a maximum current density of 14.58 and 24.76 mA/cm2 and overvoltage of 0.6 and 0.58 V, as well as cyclic stability of 98.3% and 99.7% (at optimal methanol concentration/scan rate of 20 mV/S), respectively, can be promising and inexpensive options in the field of efficient nanocatalysts for use in methanol fuel cell anodes.

Electrocatalysis of Methanol Oxidation in Alkaline Electrolytes over Novel Amorphous Fe/Ni Biphosphate Material Prepared by Different Techniques.

In this work, novel phosphate materials based on bimetallic character (Fe and Ni) were introduced by different chemical fabrication methods, the reflux method (FeNiP-R) and the sol-gel technique (FeNiP-S), and evaluated as non-precious electrodes for methanol electrooxidation in KOH electrolytes. The designed FeNiP-R and FeNiP-S samples were investigated using different characterization techniques, namely TEM, SEM, XPS, BET, DLS, and FT-IR, to describe the impact of the fabrication technique on the chemistry, morphology, and surface area. The characterization techniques indicate the successful fabrication of nanoscale-sized particles with higher agglomeration by the sol-gel technique compared with the reflux strategy. After that, the electrochemical efficiency of the fabricated FeNiP-R and FeNiP-S as electrodes for electrocatalytic methanol oxidation was studied through cyclic voltammetry (CV) at different methanol concentrations and scan rates in addition to impedance analysis and chronoamperometric techniques. From electrochemical analyses, a sharp improvement in the obtained current values was observed in both electrodes, FeNiP-R and FeNiP-S. During the MeOH electrooxidation over FeNiP-S, the current value was improved from 0.14 mA/cm2 at 0.402 V to 2.67 mA/cm2 at 0.619 V, which is around 109 times the current density value (0.0243 mA/cm2 at 0.62 V) found in the absence of MeOH. The designed FeNiP-R electrode showed an improved electrocatalytic character compared with FeNiP-S at different methanol concentrations up to 80 mmol/L. The enhancement of the anodic current density and charge transfer resistance indicates the methanol electrooxidation over the designed bimetallic Fe/Ni-phosphates.

Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance.

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt1 Fe3 @NC/MWCNTs catalyst with moderate Fe3+ feeding content (0.86 mA/mgPt ) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mgPt ). Furthermore, the CO oxidation initial potential of Pt1 Fe3 @NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt1 Fe3 @NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.

Tunable Assembly of Protein Enables Fabrication of Platinum Nanostructures with Different Catalytic Activity.

Proteins are promising biofunctional units for the construction of nanomaterials (NMs) due to their abundant binding sites, intriguing self-assembly properties, and mild NM synthetic conditions. Tobacco mosaic virus coat protein (TMVCP) is a protein capable of self-assembly into distinct morphologies depending on the solution pH and ionic strength. Herein, we report the use of TMVCP as a building block to organize nanosized platinum into discrete nanorings and isolated nanoparticles by varying the solution pH to modulate the protein assembly state. Compared with a commercial Pt/C catalyst, the TMVCP-templated platinum materials exhibited significant promotion of the catalytic activity and stability toward methanol electrooxidation in both neutral and alkaline conditions. The enhanced catalytic performance is likely facilitated by the protein support. Additionally, Pt nanorings outperformed isolated nanoparticles, although they are both synthesized on TMVCP templates. This could be due to the higher mechanical stability of the protein disk structure and possible cooperative effects between adjacent nanoparticles in the ring with narrow interparticle spacing.

Influence of Electrochemical Pretreatment Conditions of PtCu/C Alloy Electrocatalyst on Its Activity.

A carbon supported PtCux/C catalyst, which demonstrates high activity in the oxygen electroreduction and methanol electrooxidation reactions in acidic media, has been obtained using a method of chemical reduction of Pt (IV) and Cu (2+) in the liquid phase. It has been found that the potential range of the preliminary voltammetric activation of the PtCux/C catalyst has a significant effect on the de-alloyed material activity in the oxygen electroreduction reaction (ORR). High-resolution transmission electron microscopy (HRTEM) demonstrates that there are differences in the structures of the as-prepared material and the materials activated in different potential ranges. In this case, there is practically no difference in the composition of the PtCux-y/C materials obtained after activation in different conditions. The main reason for the established effect, apparently, is the reorganized features of the bimetallic nanoparticles' surface structure, which depend on the value of the limiting anodic potential in the activation process. The effect of the activation conditions on the catalyst's activity in the methanol electrooxidation reaction is less pronounced.

Integrating Pt16 Te Nanotroughs and Nanopillars into a 3D "Self-Supported" Hierarchical Nanostructure for Boosting Methanol Electrooxidation.

To develop durable and low-price catalysts of methanol oxidation to commercialize direct methanol fuel cell, many attempts have been made at fabricating Pt-based hybrids by designing component-, morphology-, facet-, integration-pattern-varied nanostructures, and have achieved considerable successes. However, most of present catalysts still lack robust catalytic durability especially owing to the corrosion of mixed carbon and the poor mechanical stability of catalyst layer. Herein, Te nanowire array is transformed at an air/water interface into a 3D Pt16 Te hierarchical nanostructure via an interface-confined galvanic replacement reaction. As-formed Pt16 Te nanostructure has an asymmetrical architecture composed of nanotroughs and nanopillars, and nanopillars are perpendicular to nanotroughs with a loose arrangement. Pt16 Te hierarchical nanostructure has a "self-supported" feature and, when directly used as the catalyst of methanol electrooxidation, exhibits superior catalytic activity (>four times larger in mass activity than state-of-the-art Pt/C in either acidic or basic solution) and long-term durability (after 500 cycles of cyclic voltammetric measurement, more than 55% of the initial specific activity remains whereas Pt/C only remains 22.2% in acidic solution and almost loses all activity in basic solution). This study fully demonstrates that designing "self-supported" catalyst film may be the next promising step for improving the catalytic performance of Pt-based hybrids.