Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Reduction of carbon dioxide to methanol on the surface of adenine functionalized reduced graphene oxide at a low potential

In this study, the surface of reduced graphene oxide (rGO) was modified with adenine via diazonium reaction. Then, to prepare Pt@Adenine-rGO, Pt was deposited on the surface of adenine-rGO, using cyclic voltammetry in the range of ?0.30 to +1.30 V at a scan rate of 100 mV s^?1 in a solution containing Pt salt. Afterward, it was characterized by various techniques such as scanning electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. Electrochemical studies showed the efficient electrocatalytic behavior of Pt@Adenine-rGO for the reduction of CO₂ to methanol at ?0.30 V. The products formed on the surface of Pt@Adenine-rGO were monitored using different techniques including Raman spectroscopy, gas chromatography, gas chromatography-mass spectrometry, and ¹³C NMR spectroscopy. Our findings indicated that methanol with a reasonably high Faradaic efficiency up to 85% and a current density of 0.5 mA cm^?2 as the main product of CO₂ reduction on the surface of Pt@Adenine-rGO.     

Electrochemical conversion of CO2 to methanol using a glassy carbon electrode,modified by Pt@histamine-reduced graphene oxide

The electrochemical reduction of CO₂ to value-added products is one of the useful approaches to reducing the effects of global climate change. Herein, a novel electrocatalyst consisting of platinum nanoparticles on histamine-reduced graphene oxide plates (Pt@His-rGO) supported by a glassy carbon (GC) substrate for the electrochemical conversion of CO₂ to methanol has been developed. The nanocomposite was optimized in terms of pH, applied potential, CO₂ purging time and platinum loading for the highest current densities and faradaic efficiencies toward methanol production. The best results were obtained in a solution containing KNO₃ 0.1 mol L⁻¹ at the pH of 2.0, the applied potential of −0.3 V vs Ag/AgCl (KCl_sat), CO₂ purging duration of 30 min and Pt loading of 5.17 × 10⁻⁷ mol cm⁻². The faradaic efficiency of 37% was obtained for methanol production. The prepared nanocomposite requires a lower applied potential and serves as an intermediate stabilizer through the production of methanol.     

High electrocatalytic activity and stability of PtAg supported on rutile TiO2 for methanol oxidation

Rutile TiO₂ is used as a support for the PtAg nanoparticles, and the catalytic activity and stability of PtAg/TiO₂ for the electrooxidation of methanol are investigated. The PtAg nanoparticles with a Pt:Ag atomic ratio of 1:1 are prepared by the chemical co-reduction of the precursors of Pt and Ag, and physical characterizations reveal that the PtAg nanoparticles are evenly dispersed on TiO₂. PtAg/TiO₂ shows significantly higher catalytic activity and stability than PtAg/C, Pt/TiO₂ and Pt/C for methanol oxidation in both alkaline and acidic solutions, indicating that rutile TiO₂ is superior to carbon black as supports and PtAg is superior to Pt in achieving high catalytic activity. Rutile TiO₂ is also shown to be superior to anatase TiO₂ as supports for the PtAg nanoparticles. The results of this study suggest high potential of rutile TiO₂ as a support material for electrocatalysts.     

Catalytic activity of platinum/tungsten oxide nanorod electrodes towards electro-oxidation of methanol

Tungsten oxide (WO₃) nanorods are synthesized using an Anodisc alumina membrane as a template and platinum nanoparticles are supported on the nanorods. The nanorods, serving as platinum catalyst supports, are characterized by electron microscopy and by electrochemical analysis. Methanol oxidation on the prepared electrodes is studied by means of cyclic voltammetry and chronopotentiometry. A film of Pt/WO₃ nanorods on a glassy carbon electrode exhibits good electrocatalytic activity towards the oxidation of methanol. High electrocatalytic activities and good stabilities are attributed to a synergistic effect between Pt and WO₃ that avoids poisoning of the electrodes.     

Bimetallic AuPt alloy nanodendrites/reduced graphene oxide: One-pot ionic liquid-assisted synthesis and excellent electrocatalysis towards hydrogen evolution and methanol oxidation reactions

Herein, reduced graphene oxide supported well-dispersed bimetallic AuPt alloy nanodendrites (AuPt ANDs/rGO) were fabricated by a one-pot coreduction approach using ionic liquid (1-aminopropyl-3-methylimidazolium bromide, [APMIm]Br) as the stabilizer and capping agent. There is no any other polymer or seed involved. Characterized measurements include transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The typical samples displayed excellent electrocatalytic activity and durability towards hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR) in contrast with Pt nanocrystals/rGO and commercial Pt/C (50%) catalysts, which make it promising for practical catalysis in energy conversion and storage.     

MoS2 supported on MOF-derived carbon with core-shell structure as efficient electrocatalysts for hydrogen evolution reaction

In this work, the porous carbon polyhedra were firstly obtained by carbonizing the zeolite imidazole framework (ZIF-8). Then the carbon polyhedra and precursors of MoS₂ were successfully combined by a hydrothermal reaction, forming the C-MoS₂ composites with different carbon contents. The well-tuned C-MoS₂ sample possesses a core-shell morphology, in which the carbon substrate is well decorated by vertically aligned MoS₂ ultrathin nanosheets. The resulting composites can be used as electrocatalysts of hydrogen evolution reaction (HER), displaying significantly superior activities to pure MoS₂ and carbon. It's found that the carbon content largely affects the architectures and HER behaviors of catalysts. In particular, the optimized catalyst yields the best catalytic activity with the lowest onset potential (35 mV), smallest Tafel slope (53 mv dec^?1), lowest overpotential (200 mV at 10 mA cm^?2), as well as extraordinary long-term stability in H₂SO₄. The enhanced HER activity can be attributed to the unique core-shell structure, where abundant active edge sites of MoS₂ are exposed and the underlying carbon substrate effectively improves the conductivity of the electrode.     

Influence of carbon support properties on the electrocatalytic activity of PtRuCu nanoparticles for methanol and ethanol oxidation

This work set out to explore the influence of kind and surface condition of carbon supports on the electrocatalytic activity of trimetallic PtRuCu alloy nanoparticles. The structure, composition, particle size and catalyst loading were determined by XRD, EDX, XPS, TEM and ICP-AES analysis. XRD studies revealed that support physical characteristics and surface conditions have an important influence in lattice strain, while XPS pointed out that a strong electronic interaction exists between the particles and the carbon support. Electrochemical experiments showed that the activated carbon black supported PtRuCu catalyst exhibits the best performance for methanol and ethanol oxidation and the lowest poisoning rate. The superior catalytic activity of this electrode can be rationalized in terms of metal-support interaction, Pt utilization efficiency and electrical conductivity of the carbon support. Furthermore, the as-prepared electrode exhibits 13 and 7 times higher activity towards methanol and ethanol oxidation when compared with a PtRu/C commercial catalyst.     

Enhanced electrocatalytic activity of high Pt-loadings on surface functionalized graphene nanosheets for methanol oxidation

Here we report a simple one-pot microwave-polyol reduced method to anchor platinum nanoparticles on graphene with the aid of poly (diallyldimethylammonium chloride) (PDDA), forming a Pt/PDDA–G hybrid (Pt/PDDA–G). High Pt metal loadings, up to 85 wt.% with a mean size of 1.4 nm, were densely in situ decorated on PDDA-modified graphene surfaces. The electrochemical tests showed that the activity and stability of Pt supported on PDDA–graphene hybrid substrates for methanol oxidation were better than that of Pt supported on graphene sheets, also better than the widely used Pt/carbon black electrocatalysts with the same Pt content on the electrode. This improved activity indicates that PDDA plays a crucial role in the highly dispersion and stabilization of Pt nanoparticles on graphene and PDDA–G are able to an alternative support for Pt immobilization in direct methanol fuel cells.     

MOF-derived N-doped carbon coated CoP/carbon nanotube Pt-based catalyst for efficient methanol oxidation

Designing rational nanostructures of metal-organic frameworks to speed up the methanol oxidation reaction and promote their application in methanol oxidation is highly desired but still remains a great challenge. In this study, we report a novel N-doped carbon coated CoP nanoparticles/carbon nanotube Pt-based catalyst (Pt–CoP-NCZ/CNT). This composite is produced through in situ growth of CoZn-ZIF on carbon nanotubes, subsequent carbonization and phosphorization treatment and microwave-assisted Pt supporting synthesis. The high specific surface area and N-doped structure endow the prepared catalysts with ideal conditions for supporting of Pt as well as good electrical conductivity. In addition, the evaporation of Zn²⁺ in CoZn-ZIF not only makes a contribution to a higher specific surface area of the material but also is favorable for uniform distribution of CoP nanoparticles, which gives CoP nanoparticles an excellent co-catalysis effect. Thus, the composite exhibits wonderful mass activity in both acid (930 mA mg⁻¹) and alkaline (3622.5 mA mg⁻¹) environments. Furthermore, the Pt–CoP-NCZ/CNT catalyst also shows better CO tolerance and long-time stability compared with other catalysts in this study. Thereby, the fabrication of the composite catalyst makes wider application of metal-organic frameworks in methanol oxidation possible and provides inspiration for designing efficient catalysts for methanol oxidation.     

High efficient electrocatalytic oxidation of methanol on Pt/polyindoles composite catalysts

Novel composite catalysts have been fabricated by the electrodeposition of Pt onto the glassy carbon electrode (GC) modified respectively with polyindole (PIn) and poly(5-methoxyindole) (PMI) and used for the electrooxidation of methanol in acid solution of 0.5 M H₂SO₄ containing 1.0 M methanol. As-formed composite catalysts are characterized by SEM, XRD and the electrochemical methods. The results of the catalytic activity for methanol oxidation show that the two composite catalysts exhibit higher catalytic activity and stronger poisoning-tolerance than Pt/polypyrrole/GC (Pt/PPy/GC) and Pt/GC. Electrochemical impedance spectroscopy indicates that the methanol electrooxidation on the composite catalysts at various potentials shows different impedance behaviors. At the same time, the charge-transfer resistance for electrooxidation of methanol on Pt/PIn/GC and Pt/PMI/GC is smaller than those on Pt/PPy/GC and Pt/GC. The present study shows a promising choice of Pt/PIn and Pt/PMI as composite catalysts for methanol electrooxidation.     

PtGd/Gd2O3 alloy/metal oxide composite catalyst for methanol oxidation reaction

Pt-transition metal alloys are frequently used to improve the catalytic activity for methanol oxidation reaction. However, the severe dealloying strongly limits the applications of Pt-based alloy in fuel cells. Recently, Pt-rare earth metal alloys are considered to be the promising catalysts for electrocatalytic application in fuel cells. Metal oxide as the co-catalytic component of composite catalyst, is also applied to regulate the electronic structure and strengthen resistance to CO poisoning. In this work, we utilized hydrogen reduction method to prepare PtGd/Gd₂O₃ composite catalyst. X-ray diffraction result illustrates that both Gd₂O₃ and PtGd alloy co-exist in PtGd/Gd₂O₃ material. X-ray photoelectron spectroscopy data confirms that the main valence states of Pt and Gd are metal form in the PtGd/Gd₂O₃ catalyst and emerges obvious transfer of element binding energy. Transmission electron microscopy data presents that composite PtGd/Gd₂O₃ particles are uniformly dispersed on the carbon power with a typical core-shell structure. And upon the increase of Gd precursor in reduction process, the metal oxide layer becomes more thicker for PtGd/Gd₂O₃ composite material. Because of the synergistic contributions given by the Pt–Gd bimetals and alloy-metal oxide between PtGd alloy and Gd₂O₃ oxide, the PtGd/Gd₂O₃ composite catalysts exhibit superior catalytic performance toward methanol oxidation reaction. Specifically, the mass activity of Pt₁Gd₁/Gd₂O₃ is about 1.9 times that of commercial Pt/C; besides this, the optimal specific activity of Pt₁Gd₂/Gd₂O₃ is almost 4 times that of commercial Pt/C. More importantly, the Pt₁Gd₁/Gd₂O₃ emerged a 20.9% degradation after 8000 cycles test, while commercial Pt/C showed a 61.7% degradation. And this work provides an important insight for rare earth elements investigation on the electrocatalysis application in fuel cells.     

Influence of Sn content on the electrocatalytic activity of NiSn alloy nanoparticles-incorporated carbon nanofibers toward methanol oxidation

Improvement of the electrocatalytic activity of nickel toward methanol oxidation can be conducted by exploiting the synergetic influence of a co-catalyst and/or utilizing a proper support. In this study, utilizing tin as a co-catalyst and supporting on carbon nanofibers are proposed to enhance methanol oxidation in the alkaline media. Typically, NiSn nanoparticles alloy-incorporated carbon nanofibers could be prepared by calcination of electrospun nanofibers composed of poly (vinyl alcohol), nickel acetate tetrahydrate and tin chloride under argon atmosphere at a high temperature. The influence of the co-catalyst content and the calcination temperature on the morphology, composition and electrocatalytic activity of the proposed nanofibers was investigated. Smooth electrospun nanofibers can be prepared regardless the tin chloride content up to 35 wt%, and the calcination process did not distinctly affect the nanofibrous morphology. Mostly, Ni₃Sn and Ni₃Sn₂ nanoparticles-incorporated amorphous carbon nanofibers were obtained at all the utilized calcination temperatures (700, 850 and 1000 °C) and examined SnCl₂ contents. However, at 10 wt% SnCl₂ content and 850 °C calcination temperature, single metallic compound (Ni₃Sn₂)-incorporated carbon nanofibers were synthesized. Electrochemical measurements indicated that the electrocatalytic activity depends strongly on the tin content as well as the calcination temperature. The nanofibers obtained from electrospun solution containing 10 wt% SnCl₂ and calcined at 850 °C showed very good performance compared to the other formulations. Typically, the corresponding onset potential of the methanol oxidation reaction using these nanofibers catalyst is 315 mV (vs. Ag/AgCl) while it was 405 mV for the nanofibers obtained from electrospun solution containing 0, 5, 15, 25 and 35 wt% SnCl₂. Moreover, the best nanofibers reveal the highest current density. Kinetic study indicated that the corresponding activation energy is 15.6 kJ/mol.     

Enhanced electrocatalytic performance for methanol oxidation on Pt–TiO2/ITO electrode under UV illumination

Pt is one of the most important electrode materials employed in direct methanol fuel cell, and many efforts have been directed to improving its electrocatalytic performance. In this work, Pt–TiO₂ nanocomposites are successfully prepared by a sol–gel method. As revealed by TEM, Pt nanoparticles with an average size of 2.6 nm are well uniformly dispersed on porous TiO₂. XRD structural characterization indicates that Pt possesses a face centered cubic crystal structure while TiO₂ is in the format of both rutile and anatase phases. The electrochemical performance of as-prepared nanocomposite electrode (Pt–TiO₂/ITO) is evaluated by studying the electrocatalytic oxidation of methanol in an alkaline medium with or without UV illumination. Comparative experiments evince that the electrochemical performance of Pt–TiO₂/ITO for methanol electrooxidation is markedly improved under UV illumination. Under UV illumination, moreover, the poisoning resistance of Pt–TiO₂/ITO for methanol electrooxidation is significantly improved, as supported by the results of time-coursed current measurements.     

Zn-substituted MnCo2O4 nanostructure anchored over rGO for boosting the electrocatalytic performance towards methanol oxidation and oxygen evolution reaction (OER)

Mixed valence spinel oxides have emerged as an attractive and inexpensive anode electrocatalyst for water oxidation to replace noble metals based electrocatalysts. The present work demonstrates the facile synthesis of Zn substituted MnCo₂O₄ supported on 3D graphene prepared by simple hydrothermal technique and its application as an electrocatalyst for water oxidation and methanol oxidation. The physico-chemical properties of the nanocatalyst were studied using various microscopic, spectroscopic and diffraction analyses confirming the formation of the composite. The electrocatalytic performance of the prepared electrocatalyst was evaluated using potentiodynamic, potentiostatic and impedance techniques. The synthesized Zn_1-xMn_xCo₂O₄/rGO electrocatalyst with x = 0.2 and 0.4 offered the same onset potential and overpotential at 10 mA/cm². However, catalyst x = 0.4 delivered a higher current density indicating the superiority of the same over other compositions which is attributed to better kinetics that it possessed for OER as revealed by the smallest Tafel slope (80.6 mV dec⁻¹). The prepared electrocatalysts were tested for methanol oxidation in which electrocatalyst Zn_1-xMn_xCo₂O₄/rGO with x = 0.4 shows a better electrochemical performance in oxidizing methanol with the higher current density of 142.3 mA/cm². The above catalyst also revealed excellent stability and durability during both MOR and OER, suggesting that it can be utilized in practical applications.     

Fabrication and characterization of gold nanoparticles and fullerene-C60 nanocomposite film at glassy carbon electrode as potential electro-catalyst towards the methanol oxidation

Development of low cost anodic materials and high efficient electro-kinetics of methanol in direct methanol fuel cell (DMFC) has been a promising approach. However it has not been successfully reached to market from laboratory due to its high cost and low kinetic oxidation. Both issues encounter from one of its main components, the catalyst. Therefore, present work focuses upon the development of new catalyst material and optimization of various most significant influencing parameters of a high performance DMFC. We have developed a nanocomposite material employing gold nanoparticles and fullerene-C₆₀ at glassy carbon electrode (AuNP@reduced-fullerene-C₆₀/GCE) as anode for high performance oxidation of methanol. Fullerene-C₆₀ was manually dropped on pre treated GCE and partially electro-reduced in KOH to make it more conductive. Gold nanoparticles (AuNPs) were deposited on reduced-fullerene-C₆₀ modified electrode using cyclic voltammetry (CV). Electrochemical characterization techniques such as CV, electrochemical impedance spectroscopy (EIS) and chronocoulometry were used to characterize modified electrode. Modified electrode was also characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) for morphological properties. The electrochemical behavior of methanol was performed in alkaline medium using CV and chronoamperometry methods. The results revealed good electrocatalytic performance and better stability than previously reported catalysts using AuNP@reduced-fullerene-C₆₀ catalyst, suggesting making promising anodic material for direct methanol oxidation fuel cell.     

A remarkable three-component RuO2-MnCo2O4/rGO nanocatalyst towards methanol electrooxidation

A three-part nano-catalyst including ruthenium oxide, manganese cobalt oxide, and reduced graphene oxide nanosheet in form of RuO₂-MnCo₂O₄/rGO is synthesized by one-step hydrothermal synthesis. The material is placed on a glassy carbon electrode (GCE) for electrochemical studies. The ability of these nano-catalysts in the oxidation process of methanol in an alkaline medium for usage in direct methanol fuel cells (DMFC) was examined with electrochemical tests of cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The effect of the addition of rGO to the nanocatalyst structure in the methanol oxidation reaction (MOR) process was investigated. We introduced the RuO₂-MnCo₂O₄/rGO as a nanocatalyst with excellent cyclic stability of 97% after 5000 cycles in the MOR process. Besides, the study of the Tafel plots and the effect of temperature and scan rate in the MOR process showed that RuO₂-MnCo₂O₄/rGO nanocatalyst has better electrochemical properties than MnCo₂O₄ and RuO₂-MnCo₂O₄. This high electrocatalytic activity could be related to the synergistic effect of placement of metal oxides of ruthenium, manganese, and cobalt near each other and putting them on rGO, which enhances conductivity and surface area and improve electron transfer. The decrease in the resistance against charge transfer and the increment in the anodic current density illustrated that the reaction rate is enhanced at higher temperature. Thus RuO₂-MnCo₂O₄/rGO shows robust stability and superior performance for MOR.     

HxMoO3-assisted deposition of platinum nanoparticles on MWNTs for electrocatalytic oxidation of methanol

Platinum nanoparticles were loaded on multi-walled carbon nanotubes (MWNTs) by using ethylene glycol as reductant and with the assistance of hydrogen molybdenum bronze (H_xMoO₃, 0 < x ≤ 2) for the electrocatalytic oxidation of methanol. In this approach, MWNTs were modified by H_xMoO₃ and used as the support for platinum nanoparticles. The XRD and TEM characterizations indicate that the average particle size of platinum supported by the modified MWNTs (Pt/H_xMoO₃-modified-MWNTs) is 3.4 nm, smaller than that (4.3 nm) of the platinum supported by the unmodified MWNTs (Pt/MWNTs). The voltammetric and chronoamperometric experiments show that Pt/H_xMoO₃-modified-MWNTs exhibits better electrocatalytic activity toward methanol oxidation than Pt/MWNTs, although the former has a less platinum loading (4.6 wt%) than the latter (6.0 wt%). The mechanism on the assistance of H_xMoO₃ to the platinum deposition was discussed.     

Facile synthesis of well dispersed Pd nanoparticles on reduced graphene oxide for electrocatalytic oxidation of formic acid

In present study, we report a facile synthesis of crystalline, small size Pd nanoparticles (NPs) on reduced graphene oxide (RGO) abbreviated as Pd/RGO for electrocatalytic oxidation of formic acid (FA). Here, first graphene oxide (GO) was reduced by the green method using l-ascorbic acid and citric acid and further Pd NPs were decorated on RGO by a facile method without using any reducing agents. The reduction of GO to RGO and synthesis of Pd NPs was confirmed by the X-ray diffraction (XRD) and X-ray photoelectrons (XPS) techniques. Surface morphology of Pd/RGO nanocomposite was evaluated by the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The electrocatalytic behavior of Pd/RGO nanocomposite was tested by using of cyclic voltammetric (CV) technique for electro-oxidation of FA in mixed solution of 0.5 M HCOOH + 0.5 H₂SO₄ at RT. Results shows that the higher electrocatalytic activity of Pd/RGO nanocomposite compare to Pd NPs.     

Preparation of flexible composite electrode with bacterial cellulose (BC)-derived carbon aerogel supported low loaded NiS for methanol electrocatalytic oxidation

In this study, carbon aerogel (CA) were obtained by inexpensive bacterial cellulose (BC) hydrogel freeze-dried and carbonized under N₂ atmosphere. Then nickel sulfide (NiS)/CA composite aerogel electrodes with different contents were successfully prepared by a one-step solvothermal method. The morphology, phases and surface electronic state of these electrodes were characterized by SEM/TEM, XRD and XPS, respectively, and their electrocatalytical properties for methanol oxidation were investigated by cyclic voltammetry (CV) in the alkaline media of methanol. The NiS particles dispersed uniformly on CA, and the obtained material maintained the reticulated porous structure of BC. The methanol oxidation peak current density of CNS-0.5 at 0.8 V reached 43 mA/cm² (263 mA/mg). After 1000 cycles, the peak current density retained 92% of the initial state. The composite electrode has good catalytic activity and good cycle performance for methanol catalysis. Nickel sulfide with high crystallinity transforms to nickel oxide with low crystallinity after a long cycle test, which results in excellent cycle performance of the composite. NiS/CA electrodes have the potential for application in portable or wearable devices.