Search Results (99)

This study examines the surface chemistry of platinum, palladium, rhodium, and ruthenium-substituted lanthanum strontium cobaltate perovskite catalysts in the context of the dry reforming of methane (DRM). The catalysts were synthesized by the solution combustion method and characterized by using a series of techniques. To explore the effect of noble metal ion substitution on the DRM, surface reaction was probed by CH₄/CO₂ TPSR using mass spectroscopy. It was recognized that La_1−xSr_xCo_1−yPd_yO₃ show the best activities for the reaction in terms of the temperature but became deactivated over time. CH₄/CO₂ temperature-programmed surface reactions (TPSRs) were set up to unravel the details of the surface phenomena responsible for the deactivation of the DRM activity on the LSPdCO. The CH₄/CO₂ TPSR analysis conclusively demonstrated the importance of lattice oxygen in the removal of carbon, which is responsible for the stability of the catalysts on the synthesized perovskites upon noble metal ion substitution. Full article

To ensure the sustainable use of limited resources, it is essential to establish selective and efficient recycling technologies for platinum group metals (PGMs). This study focused on the selective precipitation-based separation of Pt(IV) from hydrochloric acid (HCl) solutions in the presence of various metal ions, using trans-1,4-bis(aminomethyl)cyclohexane (BACT) as a precipitating agent. By using BACT, we succeeded in the selective separation of Pt(IV) by precipitation from HCl solutions containing Pd(II) and Rh(III). Notably, selective and efficient recovery of Pt(IV) was accomplished across various HCl concentrations, with a small amount of BACT and within a short shaking time. To evaluate the practical applicability of the method, Pt(IV) was recovered and purified from the HCl leachate of spent automotive exhaust gas purification catalysts using BACT. As a result, a high Pt recovery of 95.6% and a high purity of 99.3% were achieved. Although Pt(IV) was recovered as a precipitate containing BACT, it was found that Pt black could be readily obtained by dissolving the precipitate in HCl solution followed by reduction with sodium borohydride. Detailed structural analysis of the Pt(IV)-containing precipitate revealed that it is an ionic crystal composed of [PtCl₆]²⁻ and protonated BACT. The selective formation of this ionic crystal in HCl solution, along with its stability under such conditions, is the key to the selective recovery of Pt(IV) using BACT. Full article

The electrocatalytic hydrogenation (ECH) of biomass-derived phenolic compounds is a promising approach to the production of value-added chemicals and biofuels in a sustainable way under moderate reaction conditions. This study provides a comprehensive comparison of electrochemical and thermochemical hydrogenation processes, highlighting their relative advantages in terms of energy efficiency, product selectivity, and environmental impact. Several electrocatalysts (Pt, Pd, Rh, Ru), membranes (Nafion, Fumasep, GO-based PEMs), and reactor configurations are tested for the selective conversion of model compounds such as phenol, guaiacol, furfural, and levulinic acid. The contributions made by the electrode material, electrolyte composition, membrane nature, and reaction conditions are critically evaluated in relation to Faradaic efficiency, conversion rates, and product selectivity. The enhancement in the performance achieved by a new catalyst architecture is emphasized, such as MOF-based systems and bimetallic/trimetallic catalysts. In addition, a demonstration of graphite-based membranes and membrane-separated slurry reactors (SSERs) is provided, for enhanced ion transport and reaction control. The results illustrate the potential of using ECH as a low-carbon, scalable, and tunable method for the upgrading of biomass. This study offers valuable insights and guidelines for the rational design of next-generation electrocatalytic systems toward green chemical synthesis and emphasizes promising perspectives for the strategic development of electrochemical technologies in the pathway of a sustainable energy economy. Full article

This study explores the selective hydrogenation of cinnamaldehyde using a series of metal catalysts supported on reduced graphene oxide (rGO) and conventional activated carbon (AC). Catalysts based on Pt, Pd, Rh, Ru, and Co were synthesized with controlled metal loading and characterized by XRD, SEM-EDS, XRF, and TEM. Among all tested materials, Pd supported on rGO synthesized via the Tour method (Pd/rTOGO) exhibited the highest catalytic activity, achieving 62% conversion of cinnamaldehyde and superior selectivity toward hydrocinnamaldehyde (HCAL). The support material had a significant influence on performance, especially for Pd catalysts, where 2D rGO outperformed 3D AC in both conversion and selectivity. In contrast, other metals (Pt, Rh, Ru, Co) showed only modest activity and limited selectivity tuning via support choice. Notably, GC-MS analysis revealed the formation of a previously underreported side product, 3-isopropoxy-propan-1-yl benzene (ether), likely formed via reductive etherification in isopropanol. The combined kinetic and selectivity data enabled the proposal of reaction pathways, including rapid transformation of cinnamylalcohol (COL) to hydrocinnamal alcohol (HCOL) and HCAL to ether. These findings emphasize the importance of support structure and surface functionality, particularly in 2D carbon materials, for designing efficient and selective hydrogenation catalysts. Full article

Carbon monoxide (CO) is an important air pollutant generated from the incomplete combustion of fossil fuels, particularly in industrial processes such as iron and steel smelting, power generation, and waste incineration, posing environmental challenges that demand effective removal strategies. Recent advances in noble metal catalysts for catalytic oxidation of CO, particularly Pt-, Pd-, and Rh-based systems, have been extensively studied. However, there is still a lack of systematic review on noble metal-based catalytic oxidation of CO, especially regarding the effects of different active components of the catalysts and the mechanism of sulfur resistance. Based on extensive research and literature findings, this study comprehensively concluded the advances in noble metal-based catalytic oxidation of CO. The effects of preparation methods, supports, and physicochemical properties on the catalytic performance of CO were explored. In addition, the mechanism of the catalytic oxidation of CO were further summarized. Furthermore, given the prevalence of SO₂ in the flue gas, the mechanism of sulfur poisoning deactivation of catalysts and the anti-sulfur strategies were further reviewed. Exploration of new supporting materials, catalyst surface reconstruction, doping modification, and other catalyst design strategies demonstrate potential in improving sulfur resistance and catalytic efficiency. This study provides valuable insights into the design and optimization of noble metal-based catalysts for the catalytic oxidation of CO. Full article

Compressed natural gas (CNG) in dual-fuel diesel engines offers environmental benefits but significantly increases unburned methane (CH₄) emissions, especially at low engine loads. This study investigates the effectiveness of different catalytic converters in methane oxidation under transient test conditions (WHTC). Three types of catalysts (Pt-, Rh-, and Pd-based) were evaluated using a combined approach of empirical engine bench tests and mathematical modelling. The results showed that, under actual exhaust gas temperature conditions, the average methane conversion efficiencies were 3.7% for Pt, 17.7% for Rh, and 31.3% for Pd catalysts. Increasing the exhaust gas temperature by 50% improved the conversion efficiencies to 7.3%, 51.8%, and 69.2%, respectively. Despite this enhancement, none of the catalysts reached the 90% efficiency threshold required to increase the CNG content of the fuel beyond 6% without exceeding emission limits. The results highlight the need for high-activity Pd-based catalysts and optimised thermal management strategies to enable the broader adoption of dual-fuel engines, while complying with Euro VI standards. Full article

Strict gaseous emission standards are applied globally to regulate the maximum amounts of pollutant emissions that can be produced from all vehicles. The exhaust aftertreatment systems used by automotive manufacturers rely on the utilization of precious metals (Pt, Pd, Rh). However, much effort has been devoted on the reduction or the replacement of the amount of Platinum Group Metals (PGMs) in three-way catalysts (TWC), both from a cost-effectiveness as well as an environmental point of view. PROMETHEUS catalyst, which was recently homologated for Euro 6 applications, is a low-cost, Cu-based TWC, which consists of a significantly lower quantity of PGMs compared to conventional state-of-the-art catalysts and achieves similar or even better catalytic efficiencies. In this review paper, a complex reaction scheme is proposed for the first time for a catalytic converter utilizing Cu and PGMs, following an extensive literature investigation of the available models. The scheme also accounts for the surface reaction mechanisms of the main processes and the side reactions potentially taking place during the TWC operation in the presence of Cu and at least one of the following PGMs: Pt, Pd or Rh. At a next step, the proposed reaction scheme will be validated based on experimental data, using mathematical modelling of a PROMETHEUS catalytic converter incorporating Cu and PGM nanoparticles. Full article

Metallic Pd/Ni gauzes, located downstream of the Pt/Rh ammonia oxidation catalyst nets in the Ostwald process, is the current technology for capturing volatile gas phase platinum and rhodium species lost from the Pt/Rh combustion catalyst through evaporation. In this screening study, we explore four oxide families, ABO₃ perovskites, (ABO₃)_n(AO) Ruddlesden–Popper (RP) phases, AO rock salt, and A₂O₃ sesquioxide type oxides, as alternative materials for platinum capture. It was found that all the tested nickelates, LaNiO₃, NdNiO₃, La₂NiO₄, and La₄Ni₃O₁₀, captured platinum well and formed A₂NiPtO₆. In contrast, La_0.85Sr_0.15FeO₃, LaFeO₃, and LaCoO₃ did not capture platinum. CaO, SrO, and Nd₂O₃ formed low-dimensional platinates such as Ca_xPt₃O₄, Sr₄PtO₆, and a newly discovered neodymium platinate, Nd_10.67Pt₄O₂₄. Gd₂O₃ did not capture platinum in bench-scale experiments in dry air, but did, however, seem to capture platinum under pilot plant conditions, likely due to the co-capture of Co lost from the N₂O abatement catalyst. The catalytic activity of both oxides and platinum-containing products were studied, toward NO_x and N₂O decomposition. None of the oxides showed significant activity toward NO_x decomposition, and all showed activity toward N₂O decomposition, but to different extents. An overall assessment of the screened oxides with respect to potential use in industrial Ostwald conditions is provided. All tested oxides except CaO and SrO withstood industrial conditions. From our assessments, the nickelates and A₂O₃ (A = Nd, Gd) stand out as superior oxides for platinum capture. Full article

The development of a selective separation and recovery method for platinum-group metals (PGMs) is in high demand to establish efficient and practical recycling technologies for different secondary materials such as industrial automobile catalysts. In this study, the highly selective precipitation of Pt(IV) from hydrochloric acid (HCl) solutions containing Pd(II), Pt(IV), and Rh(III) was successfully achieved using m-phenylenediamine dihydrochloride (MPDA) as a precipitant. Pt(IV) selectivity was observed at HCl concentrations higher than 7 M, whereas the co-precipitation of Rh(III) could not be suppressed using 3–7 M HCl solutions. Successful recovery of Pt(IV)-containing precipitates with high Pt yield (94.6%) and Pt purity (98.5%) was also achieved using an actual catalyst leaching solution with a complex composition containing PGMs, base metals, and rare metals. Structural analyses revealed that the Pt(IV)-containing precipitate forms ionic crystals composed of [PtCl₆]²⁻/protonated m-phenylenediamine (MPDA-2H⁺) in a 1:1 ratio. The high stability and insolubility of the Pt(IV)-containing ionic crystals, owing to their highly packed structure, resulted in the highly selective precipitation of Pt(IV) at high HCl concentrations. Full article

Hydrogen peroxide is inevitably produced at the hydrogen electrode in both the proton exchange membrane fuel cell (PEMFC) and the proton exchange membrane water electrolyzer (PEMWE) when platinum-based catalysts are used. This peroxide attacks and degrades the membrane, seriously limiting its lifetime. Here we review some of our previous efforts to suppress peroxide production using PtFe as a hydrogen evolution reaction (HER) catalyst and PtCo as a hydrogen oxidation reaction (HOR) catalyst. The mechanisms, which involve the chemical reaction of adsorbed hydrogen with oxygen, are examined using density functional theory. The onset of excess peroxide production at 0.1 V above the reversible potential has not been adequately explained thus far, and therefore a new mechanism is proposed here. This involves a unique reaction site including hydrogen adsorbed at (110) step edges adjacent to (111) terraces on the Pt surface, as well as on Pt alloys and other metals such as Rh and Ir. This mechanism helps explain the recent finding of the Wadayama group that Ir single crystal surfaces such as Ir(111) and Ir(110) produce little peroxide during the HOR. It also points the way toward the design of new catalysts for the hydrogen electrode that suppress peroxide production while retaining high HOR and HER activity. Full article

The combination of electronic and catalytic features, in conjunction with empirical investigation, provides enriched perspectives on the analysis of catalysts, thus propelling progress and design. This study employs computational methods to deduce electronic characteristics, including properties such as bandgap, Fermi energy, and magnetic moment, for known catalysts involved in the oxidative coupling of methane (OCM) reaction. Through the comparison of these attributes with existing experimental OCM data, the ability to forecast the effectiveness of catalysis and subsequent reaction results is achieved, spanning CH₄, C₂H₄, C₂H₆, and CO₂ production. Transition metals, including Pt, Rh, Ru, and Ir, turn out to be promising catalyst promoters of OCM reactions. This study identified 58 innovative blends of metallic oxides and 3480 new catalytic configurations specifically designed for methane conversion at a moderately low temperature of 700 °C, placing them as effective catalysts for the OCM reaction. These emerging catalysts are projected to result in a rise in methane conversion extending from ±38.5% to ±95%, presenting a significant increase from the upper limit methane conversion of 36% reported in previous investigations. Full article

This paper reports the development of a process for leaching Pt, Pd, and Rh from simulated spent auto-catalyst material using ozone and hydrochloric acid in order to produce a pregnant leach solution that could be fed to an industrial precious metal refinery. The effects of O₃ mass flow, initial acid concentration, and temperature were investigated using a Box–Behnken experimental design with three centre-point runs and a total leach time of 6 h. Set points of 3.34, 5.01, and 6.68 g/h; 1.0 M, 3.0 M, and 5.0 M; and 30, 60, and 90 °C were used for O₃ mass flow, hydrochloric acid concentration, and temperature, respectively. The optimal extractions for Pt, Pd, and Rh were 80%, 85%, and 42%, respectively, at 5.01 g/h O₃, 5.0 M HCl, and 90 °C. Statistical analyses indicated high dependencies of Pd and Rh on hydrochloric acid concentration and temperature, with only Pt displaying a significant dependence on O₃ mass flow. Full article

To improve the stability of high-temperature water electrolysis, I prepared membrane electrode assemblies (MEAs) using a decal method and investigated their water electrolysis properties. Nafion 115 and crosslinked sulfonated polyphenylsulfone (CSPPSU) membranes were used. IrO₂ was used as the oxygen evolution reaction (OER) catalyst, and Pt/C was used as the hydrogen evolution reaction (HER) catalyst. The conductivity of the CSPPSU membrane at 80 °C and 90% RH (relative humidity) is about four times lower than that of the Nafion 115 membrane. Single-cell water electrolysis was performed while measuring the current density and performing electrochemical impedance spectroscopy (EIS) at cell temperatures from 80 to 150 °C and the stability of the current density over time at 120 °C and 1.7 V. The current density of water electrolysis using Nafion 115 and CSPPSU membranes at 150 °C and 2 V was 1.2 A/cm² for both. The current density of the water electrolysis using the CSPPSU membrane at 120 °C and 1.7 V was stable for 40 h. The decal method improved the contact between the CSPPSU membrane and the catalyst electrode, and a stable current density was obtained. Full article

Zinc-included intermetallic compound catalysts of RhZn, PtZn, and PdZn with a molar ration of Zn/metal = 1/1, which are generally prepared using a hydrogen reduction approach, are known to show excellent catalytic performance in some selective hydrogenations of organic compounds. In this study, in order to reduce the incorporated mounts of the expensive noble metals, we attempted to prepare zinc-rich intermetallic compounds via a CaH₂-assisted molten salt synthesis method with a stronger reduction capacity than the common hydrogen reduction method. X-ray diffraction results indicated the formation of RhZn₁₃ and Pt₃Zn₁₀ in the samples prepared by the reduction of ZnO-supported metal precursors. In a hydrogenation reaction of p-nitrophenol to p-aminophenol, the ZnO-supported RhZn₁₃ and Pt₃Zn₁₀ catalysts showed a higher selectivity than the RhZn/ZnO and PtZn/ZnO catalysts with the almost similar conversions. Thus, it was demonstrated that the zinc-rich intermetallic compounds of RhZn₁₃ and Pt₃Zn₁₀ could be superior selective hydrogenation catalysts compared to the conventional intermetallic compound catalysts of RhZn and PtZn. Full article

Three-way catalyst (TWC) is the mainstream technology for stoichiometric natural gas vehicle gas emission purification to meet the China VI emission standard for heavy-duty vehicles. Due to the high price of Pd-Rh TWC widely used at present, it is of great significance to develop cheaper Pt-only catalysts as substitutes. However, there are few studies on Pt-only TWC, especially for natural gas vehicles. It remains a formidable challenge to develop Pt-only TWC with excellent activity and stability. In this study, we significantly improved the catalytic performance of Pt/CeO₂ TWC through thermal treatment, especially steam treatment at 800 °C, and used XRD, TEM, H₂-TPR, and XPS techniques to investigate how Pt/CeO₂ can be activated via these treatments. Our results suggested that after these treatments, CeO₂ crystallites sintered slightly, while platinum particles remained highly dispersed. Moreover, these treatments also weakened the Pt-CeO₂ interaction, promoted the formation of oxygen vacancies in CeO₂ support, and generated a new type of active surface oxygen in the vicinity of Pt^δ+, thus improving the activity of the catalyst. After 800 °C steam treatment, the T₅₀ of CH₄ and NO decreased by 31 and 36 °C, respectively. The results obtained in this study provide implications for the synthesis of efficient Pt-based catalysts. Full article