Performance For Methanol Oxidation Research Articles

Well-defined Pt-Fe alloy with enhanced catalytic performance for methanol oxidation and formic acid oxidation

Well-defined Pt-Fe alloy with enhanced catalytic performance for methanol oxidation and formic acid oxidation

Methanol electrooxidation performance of nickel-modified polyaniline thin films for direct methanol fuel cells

A metal–organic composite thin film composed of polyaniline (PANI) and Ni was prepared and characterized for methanol electrooxidation reaction. First, PANI thin films were electrodeposited on a fluorine-doped tin oxide (FTO) coated glass support in an aqueous acidic solution. Subsequently, the polymer film was modified with Ni particles (FTO/PANI-Ni) by chronoamperometric (CA) technique. The composite film was characterized by structural, morphological and electrocatalytic analyses. X-ray diffraction (XRD) results confirmed the crystallization of Ni according to the cubic structure. Scanning electron microscopy (SEM) images showed that the Ni nanoparticles were uniformly dispersed on the PANI surface. The electrocatalytic performance of the FTO/PANI-Ni composite electrode for the methanol electrooxidation reaction was investigated in 0.5 M KOH solution containing methanol using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) techniques. The effects of temperature and methanol concentration on the methanol electrooxidation performance were also studied. The modified composite catalyst exhibited an electrochemically active surface area of 0.5235 cm2. The presence of Ni nanoparticles on the polymer surface promoted the adsorption of methanol molecules and facilitated the oxidation process, leading to higher current densities and better overall performance. The maximum current density was 14 mA cm-2 and the electrode maintain 68 % of its initial activity even after 200 cycles, indicating that the FTO/PANI-Ni electrode exhibited good stability. The high methanol oxidation performance of the composite electrode was associated with large real surface area, a possible synergistic effect between the polymer moleucles and Ni particles as well as high intrinsic activity of Ni for this process.

Constructing Zn-based MOF-MXene nanoarchitectures to stabilize ultrafine Pt nanocrystals with enhanced methanol oxidation performance

Although the development of direct methanol fuel cell technology is regarded as one rational option to against severe energy crises and environmental pollution, the low efficiency and considerable costs of current Pt-based anode catalysts largely impede the broad-scale commercialization. Herein, a convenient bottom-up approach is developed to the spatial construction of ultrafine Pt nanocrystals stabilized on a porous heterojunction matrix built from Zn-based metal organic frameworks and Ti3C2Tx MXene nanolamellas (Pt/ZIF-Ti3C2Tx) through the stepwise solvothermal reactions. The intercalation of metal organic frameworks produces plentiful cavities and channels for the dispersion and immobilization of small-sized Pt nanoparticles, while the incorporation of Ti3C2Tx nanosheets optimizes the Pt electronic structure and ensures a high electron conductivity. As a consequence, the as-acquired Pt/ZIF-Ti3C2Tx nanoarchitectures manifest exceptional electrocatalytic methanol oxidation abilities in terms of a large electrochemically active surface area of 110.5 m2 g−1, a high mass activity of 1900.1 mA mg−1, and preferable long-term stability, all of which are significantly superior to those of conventional Pt/carbon and Pt/unmodified Ti3C2Tx catalysts.

Employing Piper longum extract for eco-friendly fabrication of PtPd alloy nanoclusters: advancing electrolytic performance of formic acid and methanol oxidation.

Advancement in bioinspired alloy nanomaterials has a crucial impact on fuel cell applications. Here, we report the synthesis of PtPd alloy nanoclusters via the hydrothermal method using Piper longum extract, representing a novel and environmentally friendly approach. Physicochemical characteristics of the synthesized nanoclusters were investigated using various instrumentation techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, and High-Resolution Transmission electron microscopy. The electrocatalytic activity of the biogenic PtPd nanoclusters towards the oxidation of formic acid and methanol was evaluated chronoamperometry and cyclic voltammetry studies. The surface area of the electrocatalyst was determined to be 36.6 m2g-1 by Electrochemical Surface Area (ECSA) analysis. The biologically inspired PtPd alloy nanoclusters exhibited significantly higher electrocatalytic activity compared to commercial Pt/C, with specific current responses of 0.24mAcm - 2 and 0.17mAcm - 2 at synthesis temperatures of 180°C and 200°C, respectively, representing approximately four times higher oxidation current after 120min. This innovative synthesis approach offers a promising pathway for the development of PtPd alloy nanoclusters with enhanced electrocatalytic activity, thereby advancing fuel cell technology towards a sustainable energy solution.

Hierarchical PtCuMnP Nanoalloy for Efficient Hydrogen Evolution and Methanol Oxidation.

The higher amount of Pt usage and its poisoning in methanol oxidation reaction in acidic media is a major setback for methanol fuel cells. Herein, a promising dual application high-performance electrocatalyst has been developed for hydrogen evolution and methanol oxidation. A low Pt-content nanoalloy co-doped with Cu, Mn, and P is synthesized using a modified solvothermal process. Initially, ultrasmall ≈2.9 nm PtCuMnP nanoalloy is prepared on N-doped graphene-oxide support and subsequently, it is characterized using several analytical techniques and examined through electrochemical tests. Electrochemical results show that PtCuMnP/N-rGO has a low overpotential of 6.5 mV at 10 mA cm-2 in 0.3m H2 SO4 and high mass activity for the hydrogen evolution reaction. For the methanol oxidation reaction, the PtCuMnP/N-rGO electrocatalyst exhibits robust performance. The mass activity of PtCuMnP/N-rGO is 6.790mA mg-1 Pt , which is 7.43 times higher than that of commercial Pt/C (20% Pt). Moreover, in the chronoamperometry test, PtCuMnP/N-rGO shows exceptionally good stability and retains 72% of the initial current density even after 20,000 cycles. Furthermore, the PtCuMnP/N-rGO electrocatalyst exhibits outstanding performance for hydrogen evolution and methanol oxidation along with excellent anti-poisoning ability. Hence, the developed bifunctional electrocatalyst can be used efficiently for hydrogen evolution and methanol oxidation.

Carbon nanotube-bridged MXene nanoarchitectures decorated with ultrasmall Rh nanoparticles for efficient methanol oxidation

Rational design and precise synthesis of cost-effective and highly-active Pt-alternative anode catalysts are important paths to accelerate the application and promotion of direct methanol fuel cell. Herein, a robust and controllable synthetic strategy is developed to bottom-up construction of carbon nanotube-bridged Ti3C2Tx MXene nanoarchitectures decorated with ultrasmall Rh nanoparticles (denoted as Rh/CNT-MX) through a facile co-assembly process. The existence of MXene nanosheets with abundant anchoring sites can immobilize nano-sized Rh crystals and facilitate their dispersion, while the integration of CNT skeletons effectively separates the neighboring MXene layers and offers unimpeded electron transport channels, which are conducive to making full use of respective catalytic functions for each component. As a consequence, the optimized Rh/CNT-MX catalyst expresses superior methanol oxidation performance with a considerable electrochemically active surface area of 89.4 m2/g, high mass/specific activity of 911.0 mA/mg/1.02 mA/cm2, and reliable long-term durability, which has obvious competitive advantages over the conventional Rh/carbon black, Rh/CNT, Rh/MXene, as well as commercial Pt/carbon black and Pd/carbon black catalysts.

Preparation of MOF-derived molybdenum-carbide-modified PtCu nano-alloy catalysts and their methanol oxidation performance

The catalytic performance of Pt0.10/Cu-MoC catalyst is higher than that of commercial Pt/C. After stability test, the performance has reserved to 79.2% of the initial value, and the onset potential for CO oxidation is lower than that of commercial Pt/C.

Effect of molybdenum valence in low Mo/Sn ratio catalysts for the oxidation of methanol to dimethoxymethane

A series of Mo/Sn (1:20, molar ratio) catalysts were prepared by two-step hydrothermal synthesis method, and the effect of calcination temperature of tin precursors on the reaction performance of methanol oxidation to dimethoxymethane (DMM) was investigated. The crystal structure, surface properties, redox property and valence change of molybdenum species of the catalyst were characterized by XRD, Raman, FT-IR, XPS, NH3-TPD and H2-TPR. The results showed that Mo1Sn20-600°CSn catalyst exhibited better performance than other catalysts, achieving DMM selectivity of 90% with methanol conversion of 30% at 140 °C. From the characterization results, the surface properties of the tin precursors affected the structure of catalyst, the degree of molybdenum oxide dispersion and valence of molybdenum species, and further influenced the performance of the catalysts. The high temperature calcination of tin precursors is more favorable for the generation of Mo6+ in the Mo1Sn20 catalyst.

Lattice Strain and Composition Effects on the Methanol Oxidation Performance of Platinum-Ruthenium-Nickel Ternary Nanocatalysts.

Ternary Pt-based structures are a positive progress in addressing the disadvantages of monometallic and bimetallic Pt-based alloys for the electrochemical oxidation process of simple alcohols, which is a vital half-reaction in fuel cell technologies. We herein report a facile NaBH4-assisted ethylene glycol reduction process for fabricating a series of nanosized PtRuNi ternary alloys to explore the relationship between physicochemical properties and electrocatalytic behaviors for the acidic methanol oxidation reaction (MOR). Owing to a balance between lattice strain and synergistic effects, the Pt60Ru20Ni20/C electrocatalyst shows the highest MOR efficiency with the mass activity/specific activity of 844.48 mA mgMetal-1/1.93 mA cm-2, being a 1.94 and 2.38 times increase compared to those of the PtRu catalyst, respectively. Also, the Pt60Ru20Ni20/C catalyst possesses superior CO-tolerance and durability in strongly acidic electrolytes. This work suggests that optimizing the surface strain and electronic effects can boost the overall MOR efficiency of multicomponent Pt-based materials, which can help to further develop next-generation catalysts for energy conversion-related technologies.

NiSe integrated with polymerized reduced carbon sheet: As an effective electrocatalyst for methanol oxidation reaction

A low-energy approach was used to create ternary composites of hollow tubular Poly-N-methyl pyrrole (P-NMPy) and NiSe nanoparticles decorated onreduced graphene oxide (RGO). On the surface of RGO, P-NMPy, and NiSe nanoparticles were uniformly disseminated. The RGO/NiSe@P-NMPy (RNP) polymer nanocomposite was made utilizing a straightforward chemical oxidative process. The RGO/NiSe@P-NMPy nanocomposite was studied using FTIR spectroscopy, UV–visible, XRD, FE-SEM with EDAX, AFM, TEM and electrochemical investigations. The electrocatalytic activity of this polymer nanocomposite for the methanol oxidation reaction in alkaline environments was validated using cyclic voltammetry. The RGO/NiSe@P-NMPy electrocatalyst shows excellent electrocatalytic activity, lower oxidation potential (0.1 V), improved current density (127 mA/cm2), excellent stability and longevity (900 s) towards methanol oxidation reaction (MOR) in alkaline medium. It was observed RGO/NiSe@P-NMPy electrocatalyst, the ECSA value is 70.83 m2/g. This result clearly depicts that RGO/NiSe@P-NMPy electrocatalyst has more active sites for MOR reaction. According to the results, the P-NMPy introduction in RGO/Nickel Selenide structure can enhance the performance of methanol oxidation and increase the resistance to CO in comparison with monometallic catalysts.

Facile Synthesis of Multifunctional Ni(OH)2-supported Core-shell Ni@Pd Nanocomposites for the Electro-oxidation of Small Organic Molecules.

In the domain of proton exchange membrane fuel cells (PEMFCs), the development of efficient and durable catalysts for the electro-oxidation of small organic molecules, especially of alcohols (methanol, ethanol, ethylene glycol, et al.) has always been a hot topic. A large number of related electrocatalysts with splendid performance have been designed and synthesized till now, while the preparation processes of most of them are demanding on experimental operations and conditions. Herein, we put forward a facile and handy method for the preparation of multifunctional Ni(OH)2-supported core-shell Ni@Pd nanocomposites (Ni(OH)2/Ni@Pd NCs) with the assistance of galvanic replacement reaction (GRR) at room temperature and ambient pressure. As expected, the Ni(OH)2 substrate can prevent the aggregation of core-shell (CS) Ni@Pd nanoparticles (NPs) and inhibit the formation of COads and further prevent Pd from being poisoned. The synergistic effect between CS Ni@Pd NPs and Ni(OH)2 substrate and the electronic effect between Pd shell and Ni core contribute to the outstanding electrocatalytic performance for methanol, ethanol, and ethylene glycol oxidation in alkaline condition. This study provides a succinct method for the design and preparation of efficient Pd-based electrocatalysts for alcohol electro-oxidation.

Insights on the Roles of Nitrogen Configuration in Enhancing the Performance of Electrocatalytic Methanol Oxidation over Pt Nanoparticles.

Stabilization of the Pt in N-doped carbon materials is an effective method to improve the performance of electrocatalytic methanol oxidation reaction (MOR). Nevertheless, the roles of different N configurations (pyridinic N, pyrrolic N, and graphitic N) toward the electrochemical performance of Pt-based catalysts remain unclear. Herein, Density Functional Theory calculations are adopted to elucidate the synergistic promotion of MOR by different N-configurations with Pt nanoparticles (NPs). Guided by the theoretical study, a series of MOR electrocatalysts with different ratios of pyridinic N and pyrrolic N (denoted as Pt/N-CNT-X (500, 600, 700, 800, and 900)) are designed and synthesized. Surprisingly, the electrocatalytic activity of Pt/N-CNT-600 with a suitable ratio of pyrrolic-N and pyridinic-N for MOR reaches 2394.7mAmg-1 Pt and 5515.8mAmg-1 Pt in acidic and alkaline media, respectively, which are superior to the Pt/CNTs, commercial Pt/C, and the ever-reported Pt-based electrocatalysts. The strong metal-support interaction induced by the N-doping is the crucial reason for the superior electrocatalytic performance. More importantly, the ability of pyrrolic-N and pyridinic-N in promoting the adsorption and oxidation of CH3 OH and the oxidation of CO* is substantiated for the first time in methanol oxidation. This work provides new insights on the design of efficient electrocatalysts for MOR.

Electrooxidation Performance of a Cotton-Cloth-Derived, Ni-Based, Hollow Microtubular Weave Catalytic Electrode for Methanol and Urea

Increasing consumption produces a large amount of cotton textile waste, the conversion of which into porous metals used for energy purposes is of practical value. In this paper, a porous, Ni-based, hollow microtubular weave (Ni-HTW) is obtained from cotton weave by high-temperature carbonization and hydrothermal synthesis with high-temperature reduction. The Ni-based, hollow microtubules in this weave have a diameter of 5–10 μm and a wall thickness of about 1 μm, and every 15 microtubules form a loose bundle with a diameter of 150–200 μm. For improved performance, Ni(OH)2 nanosheets are further electrodeposited on the fibers’ surface of the Ni-HTW to form a nano-Ni(OH)2/Ni-HTW composite electrode with a core–shell heterostructure where Ni is the core and Ni(OH)2 the shell. The combination of hollow microtubule weave morphology and nanosheet structure results in a large specific surface area and abundant active sites, and the composite electrode shows excellent electrocatalytic performance and long-term stability for methanol oxidation (MOR) and urea oxidation (UOR). The current densities can reach 303.1 mA/cm2 and 342.5 mA/cm2 at 0.8 V, and 92.29% (MOR) and 84.41% (UOR) of the pre-cycle current densities can be maintained after 2000 consecutive cycles.

Vesicular AuPd alloy nanowires for enhanced electrocatalytic activity

Developing excellent fuel cells requires complex design and precise tuning of catalyst structure and composition. This paper presents a simple approach to fabricate AuPd vesicular nanowires (VNWs) with controlled composition. The method uses homogeneous Te nanowires (NWs) as templates and reducing agents in the replacement reaction and NaClO as etching agent. Bimetallic synergism and rich catalytic sites in the vesicular nanowires give AuPd catalysts the excellent electrocatalytic performance for methanol oxidation. In particular, the Au28Pd71 VNWs showed the highest electrocatalytic activity for methanol oxidation, and its highest mass current density was1.278 A mg−1, which was 1.22 and 1.65 times that of Pt VNWs and commercial Pt/C, separately. Furthermore, Au28Pd71 VNWs exhibited good stability after 2000 cycles, maintaining an initial mass current density of 85.2%. As the optimal component ratio, Au28Pd71 exhibited superior electrocatalytic performance for methanol oxidation. This discovery demonstrated a new approach for the programming and fabrication of senior methanol fuel cells electrocatalysts.

Flower-like Layered NiCu-LDH/MXene Nanocomposites as an Anodic Material for Electrocatalytic Oxidation of Methanol

Direct methanol fuel cell (DMFC) technology has grabbed much attention from researchers worldwide in the realm of green and renewable energy-generating technologies. Practical applications of DMFCs are marked by the development of highly active, efficient, economical, and long-lasting anode catalysts. Layered double hydroxide (LDH) nanohybrids are found to be efficient electrode materials for methanol oxidation. In this study, we synthesized NiCu-LDH/MXene nanocomposites (NCMs) and investigated their electrochemical performance for methanol oxidation. The formation of NCM was verified through field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET), and X-ray photoemission spectroscopy (XPS) analyses. The cyclic voltammetry, chronoamperometry, and electron impedance spectroscopy techniques were carried out to assess the electrocatalytic ability of the methanol oxidation reaction. The incorporation of MXene enhanced the methanol oxidation 2-fold times higher than NiCu-LDH. NCM-45 exhibited high peak current density (86.9 mA cm-2), enhanced electrochemical active surface area (7.625 cm2), and long-term stability (77.8% retention after 500 cycles). The superior performance of NCM can be attributed to the synergistic effect between Ni and Cu and, further, the electronic coupling between LDH and MXene. Based on the results, NCM nanocomposite is an efficient anodic material for the electrocatalytic oxidation of methanol. This study will open the door for the development of various LDH/MXene nanocomposite electrode materials for the application of direct methanol fuel cells.

Insights into the Role of Nanorod-Shaped MnO2 and CeO2 in a Plasma Catalysis System for Methanol Oxidation.

Published papers highlight the roles of the catalysts in plasma catalysis systems, and it is essential to provide deep insight into the mechanism of the reaction. In this work, a coaxial dielectric barrier discharge (DBD) reactor packed with γ-MnO2 and CeO2 with similar nanorod morphologies and particle sizes was used for methanol oxidation at atmospheric pressure and room temperature. The experimental results showed that both γ-MnO2 and CeO2 exhibited good performance in methanol conversion (up to 100%), but the CO2 selectivity of CeO2 (up to 59.3%) was much higher than that of γ-MnO2 (up to 28.6%). Catalyst characterization results indicated that CeO2 contained more surface-active oxygen species, adsorbed more methanol and utilized more plasma-induced active species than γ-MnO2. In addition, in situ Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR) were applied with a novel in situ cell to reveal the major factors affecting the catalytic performance in methanol oxidation. More reactive oxygen species (O22-, O2-) from ozone decomposition were produced on CeO2 compared with γ-MnO2, and less of the intermediate product formate accumulated on the CeO2. The combined results showed that CeO2 was a more effective catalyst than γ-MnO2 for methanol oxidation in the plasma catalysis system.

Investigation of the Electrochemical Performance of Titanium-Based MXene Hybridisation with Rice Husk Ash (RHA) as an Anode Catalyst Support Material

MXenes possess unique features that are useful for broader industrial development. However, although many different compositions of MXenes have been discovered, little research has been conducted on the optimal synthesis strategy for producing the best MXenes yield. Therefore, substantial work is performed on the synthesis’ structure and property relationship for direct methanol fuel cell (DMFC) applications since MXenes have been successfully hybridised with rice husk ash (RHA). In this study, to produce titanium-based MXene, Ti3C2 nanopowders are added to the rice husk ash matrix to synthesise hybrid RHA/MXene composites (R-MX). Using different weight percentages of MXene hybridised with rice husk ash (2 wt. % R-MX, 4 wt. % R-MX and 6 wt. % R-MX), different electrochemical properties are obtained. Meanwhile, electrochemical analysis is undertaken to investigate the methanol oxidation performance using Linear Sweep Voltammetry (LSV). The highest percentage of the R-MX hybrid composite, 6 wt. % MXene, showed the lowest Tafel slope (148 mV/dec) and the highest ionic exchange current density in the same Tafel analysis. Moreover, the incorporation of MXene into RHA produced good results from the chronoamperometry analysis (CA), with the highest percentage of the hybrid composite, R-6MX, showing the highest retention rate of 97.28%. Meanwhile, the Nyquist plot analysis showed an increasing semicircle arc diameter at the lower-frequency region, implying a lower interfacial charge resistance upon the addition of MXene into RHA. This outcome corresponded to the CA and LSV analysis findings, R-6MX showed a remarkable performance in terms of having the highest peak current density of 0.9454 mA/cm2 and retention rate of 97.28%. Both of these values show that hybrid R-6MX was able to maintain a high current for the entire duration. The current is maintained in a stable form for some time, proving that R-6MX was the most stable, with a minimal corrosion reaction and tolerance in a methanol medium. The results from this study enabled an evaluation of the possibility of utilising low-cost, green RHA material for fuel cell applications to promote sustainability. The novelty of this work is that a cheap source of silica-based RHA, a type of waste material, is incorporated with MXene through hybridisation processes.

Stereoassembly of ultrasmall Rh-decorated zeolite imidazolate framework–MXene heterostructures for boosted methanol oxidation reaction

A bottom-up stereoassembly strategy is developed for the fabrication of ultrasmall Rh-decorated heterostructures from ZIF-8 and MXene nanosheets, which exhibit exceptional electrocatalytic performance in methanol oxidation.

Boosting nucleophilic attack to realize high current density biomass valorization on a tunable Prussian blue analogue.

Electrochemical biomass valorization provides a promising approach to generating value-added chemicals. Herein, we have creatively utilized a Prussian blue analogue as a structure template of the anodic catalyst and improved its catalyst capacity by adjusting its electronic structure. The nickel-based Prussian blue analogue/Ni foam (NiFe-PBA/NF) exhibits excellent performance for methanol (MeOH) oxidation and achieves almost 94.1% FE of formic acid at a high current density of 500 mA cm-2. Apart from formic acid, NiFe-PBA/NF also has good catalytic ability for ethanol, glycerol, glucose, and 5-hydroxymethylfurfural (HMF). In short, this work has developed a promising class of catalysts for biomass valorization.

Synthesis and characterization of Pt/ZnO@SWCNT/Fe3O4 as a powerful catalyst for anodic part of direct methanol fuel cell reaction

Platinum is a preferred metal in fuel cell applications owing to its superior catalytic activity; Platinum's high cost and CO poisoning in oxidation processes, limit its usage as a standalone catalyst. At this point, it is important to develop new intermediate tolerant electrocatalysts. In this study, Zinc Oxide/Single Wall Carbon Nanotube/Iron oxide (ZnO@SWCNT/Fe3O4) catalyst was obtained by using ZnO, SWCNT/Fe3O4 support material, and Zinc Oxide/Single Platinum/Wall Carbon Nanotube/Iron oxide (Pt/ZnO@SWCNT/Fe3O4) catalyst was obtained by chemical synthesis method by adding Pt metal. With these catalysts, the efficiency of the use of Pt was examined within the scope of the study, and reducing limiting factors by using a low amount of Pt, at the same time, it is aimed to prepare a high electrocatalyst. The morphological structure of the obtained catalysts was characterized by scanning electron microscope (SEM), and X-ray diffraction (XRD). Methanol oxidation reactions (MOR) were conducted to determine the electrochemical performance of the catalysts. In the results obtained, it was observed that the current value obtained as a result of the Cyclic Voltammetry (CV) of the ZnO@SWCNT/Fe3O4 catalyst was 103.36 mA/cm2, and the current value obtained as a result of the CV of the Pt/ZnO@SWCNT/Fe3O4 catalyst was 362.46 mA/cm2. The results showed high stability for both catalysts, and it was seen that Pt increased the conductivity, methanol oxidation performance, and stability in the catalyst. The obtained catalysts showed high potential for methanol oxidation and are promising for fuel cell applications.