Screening of electrocatalysts for direct ammonia fuel cell: Ammonia oxidation on PtMe (Me: Ir,Rh, Pd,Ru) and preferentially oriented Pt(1 0 0) nanoparticles

Ammonia has attracted attention as a possible fuel for direct fuel cells since it is easy to handle and to transport as liquid or as concentrated aqueous solution. However, on noble metal electrodes ammonia oxidation is a sluggish reaction and the electrocatalyst needs to be improved for developing efficient ammonia fuel cells. In this work, ammonia electrooxidation reaction on 3–4-nm bimetallic PtMe (Ir, Rh, Pd, Ru) and on preferentially oriented Pt(1 0 0) nanoparticles is reported. PtMe nanoparticles have been prepared by using water-in-oil microemulsions to obtain a narrow size distribution whereas preferentially oriented Pt nanoparticles have been prepared through colloidal routes. Among all the bimetallic samples tested, only Pt₇₅Ir₂₅ and Pt₇₅Rh₂₅ nanoparticles show, at the low potential range, an enhancement of the oxidation density current with respect to the behaviour found for pure platinum nanoparticles prepared by the same method. In addition, two Pt(1 0 0) preferentially oriented nanoparticles of different particle size (4 and 9 nm) have been also studied. These oriented nanoparticles show higher current densities than polycrystalline Pt nanoparticles due to the sensitivity of ammonia oxidation toward the presence of surface sites with square symmetry. The reactivity of the different 4-nm nanoparticles parallels well with that expected from bulk PtMe alloys and Pt single crystal electrodes.     

Pt and Ru dispersed on LiCoO2 for hydrogen generation from sodium borohydride solutions

Nano-sized platinum and ruthenium dispersed on the surface LiCoO₂ as catalysts for borohydride hydrolysis are prepared by microwave-assisted polyol process. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). Very uniform Pt and Ru nanoparticles with sizes of <10 nm are dispersed on the surface of LiCoO₂. XRD patterns show that the Pt/LiCoO₂ and Ru/LiCoO₂ catalysts only display the characteristic diffraction peaks of a LiCoO₂ crystal structure. Results obtained from XPS analysis reveal that the Pt/LiCoO₂ and Ru/LiCoO₂ catalysts contain mostly Pt(0) and Ru(0), with traces of Pt(IV) and Ru(IV), respectively. The hydrogen generation rates using low noble metal loading catalysts, 1 wt.% Pt/LiCoO₂ and 1 wt.% Ru/LiCoO₂, are very high. The hydrogen generation rate using Ru/LiCoO₂ as a catalyst is slightly higher compared with that of Pt/LiCoO₂.     

Tailoring a Pt–Ru catalyst for enhanced methanol electro-oxidation

A carbon-supported (1:1) Pt–Ru (Pt–Ru/C) alloy catalyst has been prepared in-house by the sulfito-complex route, and has been tailored to achieve enhanced activity towards methanol electro-oxidation by annealing it at varying temperatures in air. The catalyst samples annealed between 250 and 300 °C in air for 30 min exhibit superior catalytic activity towards methanol electro-oxidation in a solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFCs) operating at 90 °C. Both the as-prepared and annealed Pt–Ru/C catalysts have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and cyclic voltammetry. It is conjectured that while annealing the Pt–Ru/C catalysts, both PtPt and PtRu bonds increase whereas the PtO bond shrinks. This is accompanied with a positive variation in Ru/Pt metal ratio suggesting the diffusion of Ru metal from the bulk catalyst to surface with an increase in oxidic ruthenium content. Such a treatment appears seminal for enhancing the electrochemical activity of Pt–Ru catalysts towards methanol oxidation.     

Polyol-synthesized PtRu/C and PtRu black for direct methanol fuel cells

PtRu/C and PtRu black catalysts with nominal Pt:Ru atomic ratio of 1:1 are prepared by a modified polyol process (co-reduction of metal precursor salts) as anode catalysts for direct methanol fuel cells (DMFCs). Without the carbon support, PtRu nanoparticles tend to agglomerate, while the PtRu nanoparticles in PtRu/C have a good dispersion as shown by TEM. Both PtRu black and PtRu/C have the almost same alloy degree indicated by XRD, but PtRu supported on carbon could improve the influence of Ru on Pt toward methanol oxidization as shown by cyclic voltammetry. The microstructure of PtRu/C is further studied by high-resolution transmission electron microscopy (HRTEM), and the results indicate that the lattice constant of Pt in PtRu electrocatalyst has contracted despite a few parts of Pt not alloyed with Ru due to the lattice constant of Pt without contracting, which is further proved by the results of temperature-programmed reduction (TPR). Such parts of unalloyed Ru are further proved to have ability to reduce the methanol oxidation potential on Pt by comparing the catalytic behaviors of Pt/C and Pt + Ru/C prepared by mixing carbon with separately prepared Pt and Ru colloids. Moreover, the catalytic behaviors of PtRu black and PtRu/C are also compared with those of commercial ones.     

Rapid preparation of Ru(0) nanoparticles stabilized with water-soluble biopolymer for hydrogen production from ammonia borane: Development of battery-like hydrolysis media

The biohybrid Na-Alg@Ru catalyst was prepared as a result of stabilizing Ru(0) nanoparticles with biopolymer chains of sodium alginate. The in-situ prepared Ru(0) nanoparticles had an average particle size of 1.023 ± 0.097 nm. The monodisperse Ru(0) nanoparticles prepared with a very practical, inexpensive and rapid method were used as a catalyst in hydrogen production by the hydrolysis reaction of ammonia borane (AB). The Na-Alg@Ru catalyst containing 3 mg Ru(0) metal catalyzed the hydrolysis of 50 mM AB with 100% yield, and the activation energy (E_a) of the reaction was estimated as 61.05 kJ mol⁻¹. In addition, the Na-Alg@Ru nanoparticles were prepared with acrylamide as p(AAm)/Na-Alg@Ru hydrogel films suitable for use in hydrogen production in fuel cells, which represents a battery-like environment, and used for hydrogen production from AB. Thus, it was shown that the catalysts prepared in a few nm size could easily be used in battery-like environments.     

Enhanced hydrogen production with photo‐induced phase transformation and cocatalyst loading

In this study, reduced graphene oxide (RGO)‐Cd_{(1 ? x)}Zn_xS nanocomposites have been synthesized with the solvothermal method in one pot. Moreover Pt, Ru, and Rh nanoparticles have been loaded on the RGO‐Cd_{(1 ? x)}Zn_xS nanocomposites as cocatalysts with the aim of increasing the photocatalytic (PC) performance for hydrogen evolution reaction. The structure of Cd_{(1 ? x)}Zn_xS blend transforms from cubic to hexagonal structure during the PC hydrogen evolution reaction (PCHER) at the room temperature. This photo‐induced phase transformation (PIPT) enhances not only the hydrogen evolution rate, but also the stability of the photocatalysts. Interestingly, RGO triggers the PIPT process only during the PCHER under solar light illumination. On the other hand, the loading of Pt, Ru, and Rh cocatalysts do not affect the PIPT process. However, they enhance the PC and photoelectrochemical (PEC) hydrogen production activity of RGO‐Cd_{(1 ? x)}Zn_xS photocatalyst. PEC performance increases about 5.5 times when Pt (5%) and RGO are added to the Cd_0.60Zn_0.40S catalyst. RGO‐Cd_0.60Zn_0.40S including 1.5% Rh photocatalyst reaches a remarkable PC hydrogen production rate of 135 μmolh^?1 with QE of 23.3% at 460 nm. Therefore, Rh cocatalyst appears as a good alternative to Pt.     

Non-noble-metal Ni nanoparticles modified N-doped g-C3N4 for efficient photocatalytic hydrogen evolution

The use of non-noble-metal to replace precious metal as co-catalyst in solar-driven hydrogen evolution reaction (HER) is important for lowering hydrogen production cost. In this work, nickel metal nanoparticles loaded nitrogen-doped graphite carbon nitride (NiNCN3) was prepared, which significantly enhanced the HER activity of nitrogen-doped graphite carbon nitride. The hydrogen evolution rate of NiNCN3 can reach to 1507 μmol g⁻¹ h⁻¹, much higher than that of 3 wt % Pt/NCN (1055 μmol g⁻¹ h⁻¹). The distinguished photocatalytic performance is due to the accelerated electron transfer efficiency and inhibited photogenerated electron-hole recombination. Our study offers an alternative method to achieve the low-cost and effective noble-metal-free photocatalyst for HER.     

An electrocatalyst for methanol oxidation based on tungsten trioxide microspheres and platinum

Tungsten trioxide microspheres of 2–4 μm diameter have been prepared by controlled oxidation of tungsten carbide microspheres. These microspheres are characterized by XRD, SEM, and HRTEM. The microspheres are made of WO₃ nanoparticles with an average diameter of around 15 nm. Platinum supported on these WO₃ microspheres exhibits higher and stable electrocatalytic activity for methanol oxidation by a factor of around two, than commercial 20 wt.% Pt–Ru/Vulcan-XC72 carbon and 20 wt.% Pt–Ru/carbon microspheres even without Ru. The higher activity is attributed to the better tolerance to carbon monoxide of the Pt/WO₃ catalyst. These Pt/WO₃ microspheres appear to be a promising alternative anode material for direct methanol fuel cells. They replace Ru entirely and save a substantial amount of Pt in the Pt–Ru electrode that is presently employed in fluel cells.     

Platinum–ruthenium nanoparticles in poly(2,5-dimethoxyaniline)-poly(styrene sulfonic acid) via one-step synthesis route for methanol oxidation

Platinum–Ruthenium (Pt–Ru) nanoparticles were generated along with the simultaneous formation of poly(2,5-dimethoxyaniline) (PDMA) in the presence of poly(styrene sulfonic acid) (PSS) using a one-step UV-assisted method. The existence of Pt–Ru nanoparticles was verified through characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The latter two confirmed that the surface state of Ru in the Pt–Ru nanoparticles not only has metallic characteristics but is also present in oxidized form. The existence of PDMA in PSS was also identified using ultraviolet–visible (UV–vis) spectroscopy. Based on electrochemical measurements, PDMA–PSS–Pt–Ru exhibited a much higher electrocatalytic activity than PDMA–PSS–Pt and bulk Pt in methanol oxidation. Under the appropriate conditions, these particles can potentially serve as robust electrocatalysts in fuel cell applications.     

Carboxymethyl cellulose gel membrane loaded with nanoparticle photocatalysts for hydrogen production

Carboxymethyl cellulose (CMC) gel membranes were prepared by a chemical crosslinking method and an in situ method was used to load CdS nanoparticles with an average size of about 3 nm into the CMC gel. The negative ion groups in the CMC serve as strong binding sites for the metal ions and help prevent aggregation of the CdS nanoparticles during their growth process. This results in a CMC gel matrix loaded with stable and well-dispersed CdS nanoparticles (CdS-CMC). Pt co-catalyst particles were also loaded into the gel membrane to give CdS/Pt-CMC and both materials were used as photocatalysts for the production of hydrogen. The CdS/Pt-CMC catalyst with 5 wt % Pt exhibited a H₂ evolution rate of 1365 μmol h⁻¹ g⁻¹, which is 81 times that of pure CdS. This improvement can be attributed to the separation of the CdS photo-generated electron-hole pairs. The photo-electrons are transferred to Pt and the formed aqueous H⁺ ions are then rapidly converted to H₂. The incorporation of the photocatalyst into a gel matrix makes the photocatalyst easily recoverable which can help avoid environmental pollution caused by free CdS nanoparticles.     

Effects of cocatalysts on photocatalytic properties of La doped Cd2TaGaO6 photocatalysts for hydrogen evolution from ethanol aqueous solution

La doped Cd₂TaGaO₆ photocatalyst was successfully synthesized for the first time by a sol–gel method. Several metal oxides and noble metals involving NiO, CuO, Cr₂O₃, Pt, and Ru were respectively loaded onto La doped Cd₂TaGaO₆ as cocatalyst. NiO and noble metal co-loaded photocatalyst was also prepared. The obtained products were characterized by X-ray diffraction (XRD), ultraviolet–visible spectra (UV–Vis), scanning electron microscope (SEM), etc. The results showed that most of cocatalyst loaded photocatalysts exhibited much higher activities for hydrogen evolution from ethanol aqueous solution than single La doped Cd₂TaGaO₆. Compared with sole NiO or noble metal loaded photocatalyst, NiO and noble metal co-loaded La doped Cd₂TaGaO₆ showed superior activity. It is revealed that the loaded NiO and noble metal can interact with each other and cooperate on improving the photocatalytic activity. The effect of the cocatalyst loading amount on photocatalytic properties was discussed. Especially, 0.5 wt% NiO and 0.5 wt% Pt co-loaded La doped Cd₂TaGaO₆ displayed the highest hydrogen production rate of 2.93 mmol h⁻¹, which was ca. 33 times that of single La doped Cd₂TaGaO₆.     

Catalytic dehydrogenation of cyclohexane over Ag-M/ACC catalysts for hydrogen supply

Dehydrogenation of cyclohexane to benzene has been carried out over Ag supported on activated carbon cloth (Ag/ACC) catalysts using a spray- pulse reactor. Hydrogen evolution was studied for hydrogen storage and supply system applications. The maximum rate of hydrogen evolution rate using monometallic Ag/ACC catalysts was 6.9 mmol/g_met/min for Ag loading of 10 wt%. An enhanced hydrogen evolution was observed by adding a small amount of noble metal (1 wt% Pt, Pd, Rh) to the Ag based catalysts. A synergistic effect was observed in the case of the Pt promoted catalysts on the hydrogen production were twice as compared to 10 wt% Ag catalyst only.     

Pt and PtRu nanoparticles deposited on single-wall carbon nanotubes for methanol electro-oxidation

Platinum (Pt) and platinum–ruthenium (PtRu) nanoparticles supported on Vulcan XC-72 carbon and single-wall carbon nanotubes (SWCNT) are prepared by a microwave-assisted polyol process. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which are uniformly dispersed on carbon, have diameters of 2–6 nm. All the PtRu/C catalysts display the characteristic diffraction peaks of a face centred cubic Pt structure, excepting that the 2θ values are shifted to slightly higher values. The results from XPS analysis reveal that the catalysts contain mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV) and Ru(IV). The electrooxidation of methanol is studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. Both PtRu/C catalysts have high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a single direct methanol fuel cell using the SWCNT supported PtRu alloy as the anode catalyst delivers high power density.     

Fabrication of noble-metal-free Cd0.5Zn0.5S/NiS hybrid photocatalyst for efficient solar hydrogen evolution

Up to now, most of the semiconductor photocatalysts can only achieve their high photocatalytic activity for hydrogen production with the loading of noble metals, such as Pt or Ru, as cocatalysts, which drastically increases the total cost of the designed photocatalyst. Herein, we report the design and fabrication of a highly efficient Cd_0.5Zn_0.5S photocatalyst decorated with nanosized NiS surface heterojunctions. The hydrogen evolution rate over this photocatalyst reached 1.4 mmol/h, with a remarkable quantum yield of 33.9%. This efficiency is even much higher than many noble metal loaded photocatalysts. In this hybrid photocatalyst, the nanosized NiS on the surface can serve as electron trapping sites, by which, photogenerated electrons were extracted from Cd_0.5Zn_0.5S substrate, leading to spatially separated photoreduction and oxidation reactions. More interestingly, it was found that NiS played a similar role as noble metal, providing active sites for proton reduction, and hence efficiently enhancing the overall hydrogen production rate. Our work demonstrates the possibility of substitution of noble metal cocatalyst by a properly engineered surface hetero-junction to achieve efficient and low cost photocatalytic hydrogen production.     

Electrostatic self-assembly of Pt nanoparticles on hexagonal tungsten oxide as an active CO-tolerant hydrogen oxidation electrocatalyst

Developing CO-tolerant electrocatalysts is of great importance for the practical use of proton exchange membrane fuel cells (PEMFCs) fed with reforming hydrogen. Transitional metal oxides are a class of promising component to (i) alleviate the CO adsorption on Pt and (ii) provide as a stabilized support for Pt nanoparticles. Herein, we developed an electrostatic assembly strategy to deposit Pt nanoparticles uniformly on the hexagonal tungsten oxides (hex-WO₃) modified by polyethleneimine (PEI). It is the first time employing hex-WO₃ with biomimetic proton channels and mixed ionic electronic conductivity as supports in PEMFCs. Also, this work is the first report using PEI as a linker to assemble Pt nanoparticles and metal oxide supports. The Pt/PEI-hex-WO₃ composites possess excellent dispersion of Pt nanoparticles with average size less than 3 nm even at Pt loadings as high as 40 wt%. The Pt/PEI-hex-WO₃ catalysts exhibit superior catalytic activity and electrochemical stability for the hydrogen electro-oxidation (HOR) in the presence of CO, and good PEMFC performance compared to the conventional carbon-supported Pt catalysts, attributed to the bifunctional mechanism and a strong metal-support interaction (SMSI).     

Preparation, characterization and application of Pt-Ru-Sn/C trimetallic electrocatalysts for ethanol oxidation in direct fuel cell

This work aimed to develop a method for the preparation of carbon-supported platinum nanocatalysts modified with Ruthenium and Tin, which were then evaluated for ethanol eletrooxidation in direct fuel cells. The Pechini method was employed to obtain these catalysts. This method consists in the decomposition of a polymeric precursor of metal salts. Nanocatalysts containing different Pt/Ru/Sn molar ratios were prepared by keeping the carbon/metal ratio at a constant value of 60/40%. The obtained nanoparticles were physico-chemically characterized by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Energy Dispersive X-ray Spectroscopy (EDX). Crystallite size of around 7.0 nm and 5.8 nm were achieved for the bimetallic and trimetallic nanocatalysts, respectively. The experimental composition was close to the nominal one, but the metal particles were not evenly distributed on the carbon surface. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry. High Performance Liquid Chromatography (HPLC) was carried out after ethanol electrolysis for determining the products generated. Acetaldehyde was the main electrolysis product and traces of CO₂ and acetic acid were also detected. Addition of Ru and Sn to the pure Pt nanoelectrocatalyst significantly improved its performance in ethanol oxidation. The onset potential for ethanol electrooxidation was 0.2 V vs. RHE, in the case of the trimetallic nanocatalyst Pt_0.8Ru_0.1Sn_0.1/C, which was lower than that obtained for the pure Pt catalyst (0.45 V vs. RHE).     

Atomic interface engineering: Strawberry-like RuO2/C hybrids for efficient hydrogen evolution from ammonia borane and water

Efficient hydrogen production plays a key role in establishing hydrogen economy in the current world. In this study, we fabricated ultrafine RuO₂ nanoparticles on carbon black to form a strawberry-like RuO₂/C hybrid, using by a solid-phase grinding and subsequent low-temperature annealing. The synthesized hybrid displays very low reaction activation energy (28.5 KJ mol^?1) for hydrogen evolution from ammonia borane. In case of hydrogen evolution from alkaline water, it also exhibits a remarkably improved electrocatalytic activity than a commercial Pt/C, with an ultra-low overpotential of 8 mV (at 10 mA cm^?2). For the above bifunctional catalyst, the formed C–Ru–C bonds between the ruthenium oxide and carbon result in the ultrahigh activity of the hybrid, as evidenced by DFT results. This work offers a guideline to synthesize efficient metal-based (Ru, Pd, Rh, Ir, Au, etc.) catalysts with smart structures for catalysis.     

Electrochemical synthesis and characterization of carbon-supported Pt and Pt–Ru nanoparticles with Cu cores for CO and methanol oxidation in polymer electrolyte fuel cells

Pt and Pt–Ru shells on Cu cores supported on Vulcan carbon XC72R have been synthesized and tested as possible anode electrocatalysts for polymer electrolyte fuel cells. Pt(Cu)/C was prepared by Cu electrodeposition on the black carbon support at constant potential followed by Pt deposition on Cu by galvanic exchange, whereas Pt–Ru(Cu)/C was prepared by spontaneous deposition of Ru species on Pt(Cu)/C. The corresponding cyclic voltammograms in 0.5 M H₂SO₄ solution showed the hydrogen adsorption/desorption peaks and no Cu oxidation. The respective CO stripping peak potentials of Pt(Cu)/C and Pt–Ru(Cu)/C were about 0.1 and 0.2 V more negative than those corresponding to Pt/C and Ru-decorated Pt/C. The best conditions for CO oxidation were found for Cu deposition potentials between −0.2 and −0.4 V vs. Ag/AgCl/KCl(sat). The Pt economy of the Pt–Ru(Cu)/C system was proved for the methanol oxidation, with specific currents more than twice those obtained on the Ru-decorated commercial Pt/C catalysts.     

Facetted platinum electrocatalysts for electrochemical energy converters

The preparation and characterisation of Pt nanoparticles electrodeposited on carbon substrates by pulsating electrolysis are presented. The characterisation studies of metal electrodeposits by using SEM, TEM, XRD and cyclic voltammetry revealed the presence of facetted Pt nanoparticles having a predominant (111) preferential crystal orientation. The amount of electrodeposited Pt was determined by means of a spectrophotometric technique. An improvement in performance of the hydrogen/oxygen PEM fuel cell with (111)-type Pt nanoparticles incorporated in the cathode was observed, which was assigned to the decrease of the blocking effect of the cathode electrode surface by intermediate peroxide species produced during the overall oxygen electroreduction process.