Preparation of Surfactant-Free Pt and PtRu Nanoparticles with High Activity for Methanol Oxidation

A simple and green approach to synthesize highly active electro-catalysts for methanol oxi- dation reaction （MOR） without using any organic agents is described. Pt nanoparticles are directly deposited on the pre-cleaned and pre-oxidized multiwall carbon nanotubes （MWC- NTs） from Pt salt by using CO as the reductant. MOR activity has been characterized by both cyclic voltammetry and chronoamperometry, the current density and mass specific current at the peak potential （ca. 0.9 V vs. RHE） reaches 11.6 mA/cm^2 and 860 mA/mgpt, respectively. After electro-deposition of Ru onto the Pt/MWCNTs surface, the catalysts show steady state mass specific current of 20 and 80 mA/mgpt at 0.5 and 0.6 V, respectively.     

Single-Cu-atoms anchored on 3D macro-porous carbon matrix as efficient catalyst for oxygen reduction and Pt co-catalyst for methanol oxidation

Single metal atoms immobilized on a carbon substrate are of great potential for enhancing the catalytic activities for oxygen reduction and methanol oxidation reactions（ORR/MOR） owing to the maximized atom utilization. Herein, single copper atoms（SCAs） are loaded on macro-porous nitrogen-doped carbon（Cu-NC） derived from zeolitic imidazolate framework-8（ZIF-8）, which are used as catalysts for ORR and Pt-supports for MOR. For ORR, the catalyst marked as Cu-NC-3 exhibits a higher peak potential of ...     

Facile synthesis of N-doped carbon nanotubes grafted on N-doped carbon nanosheets co-encapsulating cobalt and molybdenum carbide nanoparticles for efficient methanol oxidation

Developing efficient electrocatalysts based on inexpensive and environment protection materials for methanol oxidation reaction (MOR) is crucial to new generation renewable energy storage and conversion processes, but it remains a major challenge. In our current research, N-doped carbon nanotubes grafted on N-doped carbon nanosheets co-encapsulating cobalt and Mo₂C nanoparticles (Co-Mo₂C/NCNT@NCN) are designed and synthesized by simple mixing and one-step annealing approach. After depositing Pt nanoparticles, Pt/Co-Mo₂C/NCNT@NCN exhibits superior catalytic activity and stability for MOR in acid medium; more precisely, it has a commendable mass activity of 842 mA/mg_Pt, which is 2.1 times of Pt/C-JM. And it is worth mentioning that its anti-CO poisoning ability and stability have also a visible improvement; the enhanced catalytic performance mainly benefits from the rich N doping, excellent structural features, and the synergistic effect of Co and Mo₂C. Therefore, this study opens up a new direction for designing and developing a favorable active multicomponent catalyst for MOR.     

A new insight into the promoting effects of transition metal phosphides in methanol electrooxidation

The construction of highly active catalysts for methanol oxidation reaction (MOR) is central to direct methanol fuel cells. Tremendous progress has been made in transition metal phosphides (TMPs) based catalysts. However, TMPs would be partially damaged and transformed into new substances (e.g., Pt-M-P composite, where M represents a second transition metal) during Pt deposition process. This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR. Herein, Co₂P co-catalysts (Pt-P/Co₂P@NPC, where NPC stands for N and P co-doped carbon) and Pt-Co-P composite catalysts (Pt-Co-P/NPC) were controllably synthesized. Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 mA/mg_Pt, significantly exceeding that of Pt-P/Co₂P@NPC (345 mA/mg_Pt). This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite, in sharply contrast to previous viewpoint that Co₂P itself improves the activity. Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co₂P@NPC and Pt/C. Moreover, Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO*, ultimately boosting the MOR performance.     

Small‐Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro‐oxidation

The anchoring of small‐sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H₄[SiO₄(W₃O₉)₄] (SiW₁₂) and CNTs modified with polyethylenimine (PEI‐CNTs) was ground to dryness. Small‐sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH₃. Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small‐sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro‐oxidation reaction. The mass activity of Pt‐WN/CNTs‐G‐70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg^?1_Pt, better that those of commercial Pt/C (340 mA mg^?1_Pt) and Pt/CNTs (162 mA mg^?1_Pt). The Pt‐WN/CNTs‐G also displayed good CO tolerance. In contrast, Pt‐WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg^?1_Pt, verifying the key role of grinding treatment in the preparation of WN/CNTs with good co‐catalytic effect.     

Ternary CoPtAu Nanoparticles as a General Catalyst for Highly Efficient Electro‐oxidation of Liquid Fuels

Efficient electro‐oxidation of formic acid, methanol, and ethanol is challenging owing to the multiple chemical reaction steps required to accomplish full oxidation to CO₂. Herein, a ternary CoPtAu nanoparticle catalyst system is reported in which Co and Pt form an intermetallic L1₀‐structure and Au segregates on the surface to alloy with Pt. The L1₀‐structure stabilizes Co and significantly enhances the catalysis of the PtAu surface towards electro‐oxidation of ethanol, methanol, and formic acid, with mass activities of 1.55 A/mg_Pt, 1.49 A/mg_Pt, and 11.97 A/mg_Pt, respectively in 0.1 m HClO₄. The L1₀‐CoPtAu catalyst is also stable, with negligible degradation in mass activities and no obvious Co/Pt/Au composition changes after 10 000 potential cycles. The in situ surface‐enhanced infrared absorption spectroscopy study indicates that the ternary catalyst activates the C?C bond more efficiently for ethanol oxidation.     

Electroanalytical Study of Methanol Oxidation and Oxygen Reduction at Carbon Nanohorns‐Pt Nanostructured Electrodes

This work reports a comprehensive electroanalytical study of carbon nanohorns (CNHs) in electrochemical applications. Compared to other types of carbons, the bare CNHs electrode exhibited higher peak current densities and lowest anodic peak‐to‐cathodic peak separation of less than 50 mV for the [Fe(CN)^4?]₆/[Fe(CN)^3?]₆ redox couple. Furthermore, CNHs exhibited excellent electrocatalyst supporting properties for porous Pt film towards methanol oxidation reaction reaching a peak current density of 127 mA cm^?2 or peak current mass activity 184 mA mg_Pt^?1. Regarding oxygen reduction reaction, an onset potential as positive as 0. 77 V vs. Ag/AgCl was achieved with CNHs/porous Pt film.     

Electrocatalytic oxidation of methanol on Pt-Pd nanoparticles supported on honeycomb-like porous carbons in alkaline media

Honeycomb-like porous carbons (PCs) were synthesized using a facile self-assembly method with phenolic resin as the carbon source and tetraethyl orthosilicate (TEOS) as the silica source. The PCs were found to have a large BET surface area of 458 m² g^?1 and a partially graphitized structure. The obtained PCs were used as a support for various Pt-Pd bimetallic alloy catalysts employed for methanol oxidation in alkaline media. Compared with Pt supported on commercial Vulcan XC-72R carbon (Pt/C) and with the other Pt-Pd bimetallic alloy catalysts on PCs, Pt₃Pd₁ on PCs displayed the most negative onset potential for methanol oxidation and the highest steady-state current (2.04 mA cm^?2). This may be because the Pt₃Pd₁/PCs catalyst has the largest electrochemical active surface area (ESA), and because adding Pd to the catalyst improves the ability of the intermediate species to tolerate oxidation. The results show that the prepared Pt-Pd/PCs is a potential candidate for application as a catalyst in alkaline direct methanol fuel cells.     

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation

Dilute alloy nanostructures have been demonstrated to possess distinct catalytic properties. Noble-metal-induced reduction is one effective synthesis strategy to construct dilute alloys and modify the catalytic performance of the host metal. Herein, we report the synthesis of ultrafine PtRu dilute alloy nanodendrites (PtRu NDs, molar ratio Ru/Pt is 1:199) by the reduction of Ru^III ions induced by Pt metal. For the methanol oxidation reaction, PtRu NDs showed the highest forward peak current density (2.66 mA cm⁻², 1.14 A/mg_Pt) and the best stability compared to those of pure-Pt nanodendrites (pure-Pt NDs), commercial PtRu/C and commercial Pt/C catalysts.     

Synthesis of Pt and Pt-Fe nanoparticles supported on MWCNTs used as electrocatalysts in the methanol oxidation reaction

This work reports a feasible synthesis of highly-dispersed Pt and Pt-Fe nanoparticles supported on multiwall carbon nanotubes (MWCNTs) without Fe and multiwall carbon nanotubes with iron (MWCNTs-Fe) which applied as electrocatalysts for methanol electrooxidation. A Pt coordination complex salt was synthesized in an aqueous solution and it was used as precursor to prepare Pt/MWCNTs, Pt/MWCNTs-Fe, and Pt-Fe/MWCNTs using FeCl₂·4NH₂O as iron source which were named S1, S2 and S3, respectively. The coordination complex of platinum (TOA)₂PtCl₆ was obtained by the chemical reaction between (NH₄)₂PtCl₆ with tetraoctylammonium bromide (TOAB) and it was characterized by FT-IR and TGA. The materials were characterized by Raman spectroscopy, SEM, EDS, XRD, TEM and TGA. The electrocatalytic activity of Pt-based supported on MWCNTs in the methanol oxidation was investigated by cyclic voltammetry (CV) and chronoamperometry (CA). Pt-Fe/MWCNTs electrocatalysts showed the highest electrocatalytic activity and stability among the tested electrocatalysts due to that the addition of ”Fe” promotes the OH species adsorption on the electrocatalyst surface at low potentials, thus, enhancing the activity toward the methanol oxidation reaction (MOR).     

高CO耐性的金属间PtBi纳米片用于甲醇电氧化

我们通过热注入的方法制备了一种高CO耐性的金属间PtBi纳米片。所制备的金属间PtBi纳米片在甲醇氧化反应(MOR)中展现出优异的催化性能和良好的稳定性能,最大的质量活性高达4.09 A·mg_Pt^-1,接近商业Pt/C的3.2倍。计时电流-时间(I-t)稳定性测试之后,活性仅仅衰减5.7%,远低于商业Pt/C。CO吸附-脱附(CO-Stripping)曲线和循环伏安演变(CV-Evolution)曲线证实了金属间PtBi纳米片高的CO耐受性。     

One-step synthesis of porous PtNiCu trimetallic nanoalloy with enhanced electrocatalytic performance toward methanol oxidation

Pt-based alloy nanoporous structures have attracted a lot of attention because of their high activity and stability toward alcohol oxidation reactions. Especially, Pt alloying with Earth-abundant metal can lower the cost of catalyst. Here, we introduce a one-pot approach to synthesize bimetallic PtCu and Ni-doped PtCu nanoalloy with porous structure. The as-synthesized Ni-doped Pt₆₀Ni₃Cu₃₇ nanoalloys exhibit excellent electrocatalytic properties toward methanol oxidation in acidic medium. The mass activity of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys is 3.6 times and 5.3 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black for methanol oxidation in 0.2?M methanol solution. Besides, the stability of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys was much better than Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. After 3600?s chronoamperometry test, the remaining values of the Pt₆₀Ni₃Cu₃₇ nanoalloys are 3.7 times and 11.0 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. And it is the first time to report that small amount of Ni dopants can boost the activity and stability of PtNiCu alloys toward methanol oxidation.     

Oxidation of carbon monoxide and formic acid on bulk and nanosized Pt–Co alloys

Bulk Pt₃Co and nanosized Pt₃Co and PtCo alloys supported on high area carbon were investigated as the electrocatalysts for the CO_ads and HCOOH oxidation. Pt₃Co alloy with Co electrochemically leached from the surface (Pt skeleton) was employed to separate electronic from ensemble and bifunctional effects of Co. Cyclic voltammetry in 0.1 M HClO₄ showed reduced amount of adsorbed hydrogen on Pt sites on Pt₃Co alloy compared to pure Pt. However, no significant difference in hydrogen adsorption/desorption and Pt-oxide reduction features between Pt₃Co with Pt skeleton structure and bulk Pt was observed. The oxidation of CO_ads on Pt₃Co alloy commenced earlier than on Pt, but this effect on Pt₃Co with Pt skeleton structure was minor indicating that bifunctional mechanism is stronger than the electronic modification of Pt by Co. The HCOOH oxidation rate on Pt₃Co alloy was about seven times higher than on bulk Pt when the reaction rates were compared at 0.4 V, i.e., in the middle of the potential range for the HCOOH oxidation. Like in the case of CO_ads oxidation, Pt skeleton showed similar activity as bulk Pt indicating that the ensemble effect is responsible for the enhanced activity of Pt₃Co alloy toward HCOOH oxidation. The comparison of CO_ads and HCOOH oxidation on Pt₃Co/C and PtCo/C with the same reaction on Pt/C were qualitatively the same as on bulk materials.     

高CO耐性的金属间PtBi纳米片用于甲醇电氧化

我们通过热注入的方法制备了一种高CO耐性的金属间PtBi纳米片。所制备的金属间PtBi纳米片在甲醇氧化反应(MOR)中展现出优异的催化性能和良好的稳定性能，最大的质量活性高达4.09 A·mg_Pt^-1，接近商业Pt/C的3.2倍。计时电流-时间(I-t)稳定性测试之后，活性仅仅衰减5.7%，远低于商业Pt/C。CO吸附-脱附(CO-Stripping)曲线和循环伏安演变(CV-Evolution)曲线证实了金属间PtBi纳米片高的CO耐受性。     

Structural and Electronic Effects of Carbon‐Supported PtxPd1−x Nanoparticles on the Electrocatalytic Activity of the Oxygen‐Reduction Reaction and on Methanol Tolerance

We report a systematic investigation on the structural and electronic effects of carbon‐supported Pt_xPd_1?x bimetallic nanoparticles on the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in acid electrolyte. Pt_xPd_1?x/C nanocatalysts with various Pt/Pd atomic ratios (x=0.25, 0.5, and 0.75) were synthesized by using a borohydride‐reduction method. Rotating‐disk electrode measurements revealed that the Pt₃Pd₁/C nanocatalyst has a synergistic effect on the ORR, showing 50 % enhancement, and an antagonistic effect on the MOR, showing 90 % reduction, relative to JM 20 Pt/C on a mass basis. The extent of alloying and Pt d‐band vacancies of the Pt_xPd_1?x/C nanocatalysts were explored by extended X‐ray absorption fine‐structure spectroscopy (EXAFS) and X‐ray absorption near‐edge structure spectroscopy (XANES). The structure–activity relationship indicates that ORR activity and methanol tolerance of the nanocatalysts strongly depend on their extent of alloying and d‐band vacancies. The optimal composition for enhanced ORR activity is Pt₃Pd₁/C, with high extent of alloying and low Pt d‐band vacancies, owing to favorable O? O scission and inhibited formation of oxygenated intermediates. MOR activity also shows structure dependence. For example, Pt₁Pd₃/C with Pt_rich?corePd_rich?shell structure possesses lower MOR activity than the Pt₃Pd₁/C nanocatalyst with random alloy structure. Herein, extent of alloying and d‐band vacancies reveal new insights into the synergistic and antagonistic effects of the Pt_xPd_1?x/C nanocatalysts on surface reactivity.     

Oxygen electroreduction at catalysts PtM (M = Co,Ni, or Cr)

Bimetallic catalysts PtM (M = Co, Ni, or Cr) are synthesized. They exceed purely platinum commercial catalyst E-TEK (20 wt % Pt) in its mass activity (mA/mg_Pt) and specific activity (mA/c_Pt²) in the oxygen reduction reaction. According to XRD data, the high-temperature synthesis involving metal N₄-complexes, chloroplatinic acid, and XC72 carbon black as precursors, yields alloys (or solid solutions) of the metals. The higher activity of the bimetallic catalyst PtCo/C is likely to be caused by the practically entire formation of solid solutions (Pt₃Co and PtCo), unlike PtNi and PtCr where nickel and chromium exist also as oxides that decorate the electrode surface and partly block active centers. It is shown that the mechanism of the oxygen reduction reaction at the synthesized catalysts is similar to that of oxygen reduction at the purely platinum catalyst. The slow stage in the process is transfer of the 1st electron; at potentials more positive than 0.6 V the reaction mainly yields water. The higher electrocatalytic activity of the bimetallic systems is caused by the alloy formation, which leads to changes in the bond length between platinum atoms. The achieving of the optimal bond length, as a result of the alloy formation, provides appropriate conditions for dissociative adsorption of oxygen molecules; the surface coverage with oxygen-containing particles adsorbed from water (which block active centers for O₂ adsorption) decreased. The increase in the activity may also be caused by the formation of the “core-shell” structures whose surface is enriched with platinum whose surface properties are changed under the ligand action of the core formed by the metal alloy     

CO and methanol oxidation at platinum-tin electrodes

Electrooxidation of dissolved CO and methanol at platinum-tin electrodes with different phase composition (a two-phase Sn/Pt-catalyst, Pt-Sn alloy, and Pt₃Sn intermetallic compound) is studied. All studied catalysts show higher catalytic activity in the CO oxidation at lower potentials (0.3–0.5 V against reversible hydrogen electrode (RHE)), as compared with platinum; no catalysis is observed at higher potentials (0.7 V); moreover, inhibiting is observed in some cases. The catalyst with the most strongly ordered structure (Pt₃Sn) demonstrated the highest catalytic activity; however, it appeared being less stable against oxidation at potentials more positive than 1.0 V. Catalytic effects were practically absent in the CO-adsorbate oxidation process. The sequence of catalyst activities in the methanol oxidation process differed from that in the CO oxidation; in particular, Pt3Sn appeared being the least active. The observed difference can be associated with the difference in the CO and methanol adsorption mechanisms. The effect of the carbonaceous support dispersion on the current-voltage curves is discussed.     

Porous carbon as electrode material in direct ethanol fuel cells (DEFCs) synthesized by the direct carbonization of MOF-5

Porous carbon (PC-900) was prepared by direct carbonization of porous metal-organic framework (MOF)-5 (Zn₄O(bdc)₃, bdc?=?1,4-benzenedicarboxylate) at 900 °C. The carbon material was deposited with PtM (M?=?Fe, Ni, Co, and Cu (20 %) metal loading) nanoparticles using the polyol reduction method, and catalysts PtM/PC-900 were designed for direct ethanol fuel cells (DEFCs). However, herein, we are reporting PtFe/PC-900 catalyst combination which has exhibited superior performance among other options. This catalyst was characterized by powder XRD, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and selected area electron diffraction (SAED) technique. The electrocatalytic capability of the catalyst for ethanol electrooxidation was investigated using cyclic voltammetry and direct ethanol single cell testing. The results were compared with those of PtFe and Pt supported on Vulcan XC72 carbon catalysts (PFe/CX-72 and Pt/XC-72) prepared via the same method. It has been observed that the catalyst PtFe/PC-900 developed in this work showed an outstanding normalized activity per gram of Pt (6.8 mA/g Pt) and superior power density (121 mW/cm² at 90 °C) compared to commercially available carbon-supported catalysts.     

镍/生物质衍生氮掺杂多孔碳纳米复合材料的制备及对甲醇氧化反应的电催化

以Ni （Ac）₂·4H₂O和生物质材料丝瓜络为原料,通过先浸渍后热解的方法制备了低成本的镍纳米颗粒/丝瓜络衍生氮掺杂多孔碳纳米复合材料（Ni/T-dNPCN）。研究复合材料对甲醇的电催化性能,并讨论热解温度对复合材料结构和性能的影响。结果表明,Ni/T-dNPCN修饰玻碳电极（GCE）在碱性条件下对甲醇氧化反应（MOR）具有良好的电催化活性。其中,800℃煅烧得到的Ni/T-dNPCN₈₀₀/GCE对1 mol·L^-1甲醇具有最低的起始电位（0.344 V （vs Ag/AgCl））、最高的催化电流密度（质量活性：1 902 mA·mg_Ni^-1;比活性：1.61 mA·cm^-2）和最快的动力学反应过程（Tafel斜率：50.23 mV·dec^-1）,其催化活性约为商业化Pt/C/GCE的3.92倍。且计时电流测试表明,Ni/T-dNPCN₈₀₀/GCE具有良好的稳定性。     

Geometric stability of PtFe/PdFe embedded in graphene and catalytic activity for CO oxidation

The direct methanol fuel cell (DMFC) is considered as a promising power source, because of its abundant fuel source, high energy density and environmental friendliness. Among DMFC anode materials, Pt and Pt group metals are considered to be the best electrocatalysts. The combination of Pt with some specific transition metal can reduce the cost and improve the tolerance toward CO poisoning of pure Pt catalysts. In this paper, the geometric stabilities of PtFe/PdFe atoms anchored in graphene sheet and catalytic CO oxidation properties were investigated using the density functional theory method. The results show that the Pt (Pd) and Fe atoms can replace C atoms in graphene sheet. The CO oxidation reaction by molecular O₂ on PtFe–graphene and PdFe–graphene was studied. The results show that the Eley–Rideal (ER) mechanism is expected over the Langmuir–Hinshelwood mechanism for CO oxidation on both PtFe–graphene and PdFe–graphene. Further, complete CO oxidation on PtFe–graphene and PdFe–graphene proceeds via a two‐step ER reaction: CO(gas) + O₂(ads) → CO₂(ads) + O(ads) and CO(gas) + O(ads) → CO₂(ads). Our results reveal that PtFe/PdFe commonly embedded in graphene can be used as a catalyst for CO oxidation. The microscopic mechanism of the CO oxidation reaction on the atomic catalysts was explored.