Au–Ag and Pt–Ag bimetallic nanoparticles@halloysite nanotubes: morphological modulation,improvement of thermal stability and catalytic performance

In this study, Au–Ag and Pt–Ag bimetallic nanocages were loaded on natural halloysite nanotubes (HNTs) via galvanic exchange based on Ag@HNT. By changing the ratio of Au to Ag or Pt to Ag in exchange processes, Au–Ag@HNT and Pt–Ag@HNT with different nanostructures were generated. Both Au–Ag@HNT and Pt–Ag@HNT systems showed significantly improved efficiency as peroxidase-like catalysts in the oxidation of o-phenylenediamine compared with monometallic Au@HNT and Pt@HNT, although inert Ag is dominant in the composition of both Au–Ag and Pt–Ag nanocages. On the other hand, loading on HNTs enhanced the thermal stability for every system, whether monometallic Ag nanoparticles, bimetallic Au–Ag or Pt–Ag nanocages. Ag@HNT sustained thermal treatment at 400 °C in nitrogen with improved catalytic performance, while Au–Ag@HNT and Pt–Ag@HNT maintained or even had slightly enhanced catalytic efficiency after thermal treatment at 200 °C in nitrogen. This study demonstrated that natural halloysite nanotubes are a good support for various metallic nanoparticles, improving their catalytic efficiency and thermal stability.

Bimetallic Au–Ag@HNT and Pt–Ag@HNT nanocages showed significantly improved efficiency in the oxidation of o-phenylenediamine as peroxidase-like catalyst compared with corresponding monometallic nanoparticles.     

Ag–Au bimetallic nanocomposites stabilized with organic–inorganic hybrid microgels: synthesis and their regulated optical and catalytic properties

Herein, we present the synthesis of Ag–Au bimetallic nanocomposites stabilized with organic–inorganic hybrid microgels. The aim is to get both the surface plasmon resonance (SPR) and catalytic performance of the composite material can be changed in response to external stimuli. Ag@poly(N-isopropylacrylamide-co-3-methacryloxypro-pyltrimethoxysilane) (Ag@P(NIPAM-co-MAPTMS)) hybrid microgels were synthesized by seed-emulsion polymerization using Ag nanoparticles (NPs) as the core and NIPAM/MAPTMS as monomers. Ag–Au@P(NIPAM-co-MAPTMS) bimetallic hybrid microgels were prepared by a galvanic replacement (GR) reaction between Ag NPs and HAuCl₄, with the composition and structure of these bimetallic nanocomposites being determined by the amount of added HAuCl₄. The highly porous organic–inorganic microgel layer provided confined space for the GR reaction, effectively preventing the aggregation of Ag–Au NPs. The shell layer of P(NIPAM-co-MAPTMS) three-dimensional network chains not only enhanced nanocomposite dispersity and stability, but also provided highly porous gel microdomains that could increase the diffusion of the substrate and hence enhanced catalytic activity. Additionally, the SPR and catalytic properties of Ag–Au@P(NIPAM-co-MAPTMS) are reversibly sensitive to external temperature. With increase of temperature, the maximum absorption peak of bimetallic nanocomposites shifted to longer wavelengths, and the catalytic activity of these composites for the reduction of 4-nitrophenol by NaBH₄ remarkably increased. The features above mentioned are related to presence of the thermosensitive PNIPAM chains and the highly porous structure constructed by rigid MAPTMS segments intersected between NIPAM chains.

Ag–Au bimetallic nanocomposites stabilized with organic–inorganic hybrid microgels allowed the mass transfer of reactants to be controlled by temperature modulation.     

Au-based bimetallic catalysts: how the synergy between two metals affects their catalytic activity

Supported bimetallic nanoparticles are particularly attractive catalysts due to increased activity and stability compared to their monometallic counterparts. In this work, gold-based catalysts have been studied as catalysts for the selective base-free oxidation of glucose. TiO₂-supported Au–Pd and Au–Cu series prepared by the sol-immobilization and precipitation-reduction methods, respectively, showed a significant synergistic effect, particularly when the theoretical weight ratio of the two metals was close to 1 : 1 (with an actual experimental bulk Au/Pd molar ratio of ca. 0.8 and ca. 0.4 for Au/Cu) in both cases. XPS analysis showed that the presence of Au^δ+, Pd²⁺ and CuOH species played an important role in the base-free glucose oxidation.

Supported bimetallic nanoparticles are particularly attractive catalysts due to increased activity and stability compared to their monometallic counterparts.     

The promoted catalytic hydrogenation performance of bimetallic Ni–Co–B noncrystalline alloy nanotubes

A noncrystalline Ni–B alloy in the shape of nanotubes has demonstrated its superior catalytic performance for some hydrogenation reactions. Remarkable synergistic effects have been observed in many reactions when bimetallic catalysts were used; however, bimetallic noncrystalline alloy nanotubes are far less investigated. Here, we report a simple acetone-assisted lamellar liquid crystal approach for synthesizing a series of bimetallic Ni–Co–B nanotubes and investigate their catalytic performances. The dilution effect of acetone on liquid crystals was characterized by small-angle X-ray diffraction (SAXRD) and scanning electron microscopy (SEM). The Ni/Co molar ratio of the catalyst was varied to study the composition, porous structure, electronic interaction, and catalytic efficiency. In the liquid-phase hydrogenation of p-chloronitrobenzene, the as-prepared noncrystalline alloy Ni–Co–B nanotubes exhibited higher catalytic activity and increased stability as compared to Ni–B and Co–B alloy nanotubes due to electronic interactions between the nickel and cobalt. The excellent hydrogenation performance of the Ni–Co–B nanotubes was attributed to their high specific surface area and the characteristic confinement effects, compared with Ni–Co–B nanoparticles.

Ni–Co–B noncrystalline alloy nanotubes exhibited higher catalytic activity and better stability due to the synergistic interactions between nickel and cobalt.     

Ru–Ni bimetallic catalysts for steam reforming of xylene: effects of active metals and calcination temperature of the support

A series of Ru and Ni supported catalysts were prepared and their catalytic performance was evaluated in the steam reforming of xylenes. The effects of active metals, active metal loading sequence, and the calcination temperature of the support on the catalyst activity and stability were investigated. The bimetallic 2Ru → 15Ni catalyst shows much higher activity and stability than the monometallic 2Ru and 15Ni catalyst owing to the synergic effect of Ni and Ru. The 2Ru → 15Ni catalyst has the least coke deposition owing to its high conversion performance and much less coke precursor being formed on the catalyst surface. After decoking, most of the small-sized pores cannot be recovered because of the pore collapse under severe hydrothermal conditions. o-Xylene has the lowest reactivity due to electronic and steric effects. Besides the steam reforming reaction, demethylation and C–C cracking are also observed, forming benzene and toluene. The catalyst with a loading sequence of 15Ni → 2Ru shows high activity at low temperatures (550–600 °C), but undergoes an activity drop at high temperatures (625–650 °C) because the Ni sintering at high temperatures greatly affects the state of Ru on the catalyst. The catalyst with a loading sequence of 2Ru → 15Ni has an advantage at high temperatures owing to its better sintering resistance. The simultaneously loaded 2Ru ↔ 15Ni catalyst shows the lowest activity. The high calcination temperature of the support enhances the catalyst stability by eliminating the small-sized pores before reaction; on the other hand, the elimination of pores decreases the dispersion of the active metals. The 2Ru → 15Ni catalyst calcined at 1000 °C balances the active metal dispersion and resistance to sintering under severe hydrothermal conditions, showing the best activity and stability. The catalyst calcined at 1000 °C has the best coke resistance with only 0.166 g g_cat⁻¹ of coke formation after the 24 h durability test. The DTG results indicate that the carbon formed on the catalysts is mainly graphitic carbon.

The performance of the bimetallic 2Ru15Ni/La₂O₃–MgO–Al₂O₃ catalyst in the steam reforming of xylene greatly depends on the metal loading sequence and support calcination temperature.     

A simple hydrothermal route for the preparation of novel Na–Y–W nano-oxides and their application in dye degradation

The fabricated NaY(WO₄)₂ was identified through diverse analysis methods. Therefore, to optimize NaY(WO₄)₂ morphology, saccharide carbohydrates were manipulated as a capping agent. In this study, glucose, fructose, lactose, cellulose, and starch were utilized as the capping agents. SEM images show that fructose was the optimal capping agent for achieving uniform and well-shaped nanoparticles. The photodegradation of organic dyes such as M.O and Rd.B by NaY(WO₄)₂ was evaluated under UV and Vis light. The bandgap energy of the as-prepared sample was measured by the Tauc plot, and was found to be nearly 3.85 eV. To study the photocatalytic characteristics, the influence of dye dosage and reusability on photodegradation behavior were investigated.

NaY(WO₄)₂ nanoparticles were fabricated via a simple hydrothermal method using saccharide carbohydrates as capping agents. The photocatalytic behavior of the as-prepared NaY(WO₄)₂ nanostructures was studied.     

Improved performance of self-reactivated Pt–ThO2/C catalysts in a direct ethanol fuel cell

A novel self-reactivated catalyst Pt–ThO₂/C was prepared for the first time by selecting radioactive material ThO₂ as the catalytic additive to address the low activity and toxicity of the anode Pt/C catalyst in a direct ethanol fuel cell. The catalytic activity and resistance to CO poisoning of Pt-6.67 wt%ThO₂/C were found to be superior to those of Pt/C–NaBH₄ in electrochemical workstation and single-cell tests. It is speculated that the exist of ThO₂ not only improves the catalytic activity via the synergistic effect of Pt and Th, but also produces a large amount of radiolysis products, OH radicals, due to ²³²Th which oxidatively desorbs CO from Pt–CO_ads and solves the CO poisoning problem.

Self-reactivation of Pt–ThO₂/C achieved by introducing radioactive material ThO₂ improves the performance of the original Pt/C catalyst.     

Pt–Ni/ZnO-rod catalysts for hydrogen production by steam reforming of methanol with oxygen

Ni, Pt and a mixture of Ni and Pt supported on ZnO-rods were evaluated in autothermal steam reforming of methanol (ASRM) for hydrogen production as a function of the reaction temperature. The catalytic materials were characterized by SEM-EDS, XRD, TEM, HRTEM, TPR and BET. Analysis by SEM and TEM showed structural modifications on the surface of the ZnO rods after Ni impregnation. The reactivity of the catalytic materials in the range of 200–500 °C showed that the bimetallic sample had better catalytic activity among all the catalysts studied. This finding could be associated to PtZn and NiZn alloys present in this catalyst, which were identified by XRD and HRTEM analyses. Catalyst characterization by XRD after the catalytic testing showed that the intermetallic PtZn phase was stable during the reaction in the Pt/ZnO-rod sample. The cubic Ni_0.75–Zn_0.25 structure identified in the Ni/ZnO-rod sample was transformed to Zn_0.1–Ni_0.9–O and metallic Ni phases, respectively. On the bimetallic PtNi/ZnO-rod sample, the cubic Ni_0.75–Zn_0.25 structure remained, although the tetragonal NiZn structure is unstable and was destroyed during the ASRM reaction and then a new phase of Ni_0.7Pt_0.3 emerged. The promotion effect of Pt and/or Ni on the ZnO-rod was clearly shown.

PtZn and NiZn alloys on ZnO-1D samples were evaluated in the ASRM. Bifunctional behavior between PtZn, NiZn alloys and the ZnO were reported. The ZnO provides the adsorption sites for the reagents and the alloy particles facilitate the H₂ transfer.     

Molten salt synthesis of carbon-supported Pt–rare earth metal nanoalloy catalysts for oxygen reduction reaction

The synthesis of nano-sized alloys of Pt and rare earth (RE) metal catalysts has been a huge challenge due to a significantly large standard reduction potential difference of Pt and RE metals and the high synthesis temperature. Pt_xY/C catalysts with an average particle size of around 21 nm, were synthesized by mixing K₂PtCl₄ with Y₂O₃ (a molar ratio of Pt : Y = 1 : 1) with a carbon support in a molten LiCl–CaH₂ system by a one-step molten salt synthesis method at 600 °C. The synthesis processes of the Pt_xY/C alloys are proposed as follows: Pt nanoparticles were first obtained by the reaction of K₂PtCl₄ and CaH₂ at 210 °C, then Y ions were preferentially reduced on the Pt nanoparticle surface by the reduction of CaH₂, followed by Pt_xY alloy formation in the molten LiCl–CaH₂ system at 600 °C. Molten LiCl provides a strong reducing environment and lowers the formation temperature of alloys. Pt₂Gd/C and Pt₂La/C were also obtained with Gd₂O₃ and La₂O₃ as the starting raw materials, respectively by using the same process. When investigated as an electrocatalyst for the oxygen reduction reaction (ORR), the half-wave potentials of Pt_xRE/Cs are all more positive than that of commercial Pt/C catalyst (e.g., 0.905 V for Pt_xY/C while 0.880 V for JM Pt/C), and the nano-sized Pt_xY/C alloy shows higher electrocatalytic activity toward the ORR and preferable catalytic durability with respect to JM Pt/C catalysts. This facile synthesis method provides an effective strategy for the preparation of Pt–RE based multicomponent nanoalloys, especially in large-scale production.

The synthesis mechanism of Pt–RE nanoalloy particles prepared by one-step molten salt synthesis as an advanced ORR catalyst is proposed.     

Modified graphene supported Ag–Cu NPs with enhanced bimetallic synergistic effect in oxidation and Chan–Lam coupling reactions

Herein, well dispersed Ag–Cu NPs supported on modified graphene have been synthesized via a facile and rapid approach using sodium borohydride as a reducing agent under ambient conditions. Dicyandiamide is selected as an effective nitrogen source with TiO₂ as an inorganic material to form two kinds of supports, labelled as TiO₂–NGO and NTiO₂–GO. Initially, the surface area analysis of these two support materials was carried out which indicated that N-doping of GO followed by anchoring with TiO₂ has produced support material of larger surface area. Using both types of supports, ten nano-metal catalysts based on Ag and Cu were synthesized. Benefiting from the bimetallic synergistic effect and larger specific surface area of TiO₂–NGO, Cu@Ag–TiO₂–NGO is found to be a highly active and reusable catalyst out of other synthesized catalysts. It exhibits excellent catalytic activity for oxidation of alcohols and hydrocarbons as well as Chan–Lam coupling reactions. The nanocatalyst is intensively characterized by BET, SEM, HR-TEM, ICP-AES, EDX, CHN, FT-IR, TGA, XRD and XPS.

Cu@Ag–TiO₂–NGO prepared from modified graphene by simple methodology exhibits enhanced catalytic activity towards oxidation and Chan–Lam coupling due to the synergistic effect between Ag and Cu NPs.     

Efficient synthesis of Pt–Co nanowires as cathode catalysts for proton exchange membrane fuel cells

A simple and efficient method was used to prepare highly active and durable carbon-supported ultrathin Pt–Co nanowires (NWs) as oxygen reduction reaction (ORR) catalysts for the cathode in a proton exchange membrane fuel cell (PEMFC). Chromium hexacarbonyl plays a significant role in making Pt and Co form an alloyed NW, which acts as both a reducing agent and a structure directing agent. The nanocrystal exhibits a uniform nanowire morphology with a diameter of 2 nm and a length of 30 nm. In half cell tests, the Pt–Co NWs/C catalyst has a mass activity of 291.4 mA mg_Pt⁻¹, which is significantly better than commercial Pt/C catalysts with 85.5 mA mg_Pt⁻¹. And after the accelerated durability test (ADT), Pt–Co NWs/C shows an electrochemically active surface area (ECSA) loss of 19.1% while the loss in the commercial catalyst is 41.8%. Also, the membrane electrode assembly (MEA) was prepared using Pt–Co NWs/C as the cathode catalyst, resulting in a maximum power density of 952 mW cm⁻², which is higher than that of Pt/C. These results indicate that the one-dimensional structure of the catalyst prepared herein is favorable to improve the activity and durability, and the application of the catalyst in the MEA is also realized.

A simple and efficient method was used to prepare highly active and durable carbon-supported ultrathin Pt–Co nanowires (NWs) as oxygen reduction reaction (ORR) catalysts for the cathode in a proton exchange membrane fuel cell (PEMFC).     

Monometallic and bimetallic Cu–Ag MOF/MCM-41 composites: structural characterization and catalytic activity

Monometallic and bimetallic MOF/MCM-41 composites (Cu, Ag and Cu–Ag) were synthesized via a solvothermal method. The synthesized composites were characterized by XRD, FTIR, SEM, EDX and BET surface area measurements. The acidity was determined through two techniques; potentiometric titration with n-butyl amine for determining the strength and the total number of acid sites and FTIR spectra of chemisorbed pyridine on the surface of MOFs for determining the type of acid sites (Brønsted and/or Lewis). All the prepared MOFs showed Lewis-acid sites and the higher acidity was observed for the bimetallic Cu–Ag MOF/MCM-41 composite. The catalytic activity was examined on the synthesis of 1-amidoalkyl-2-naphthol via the reaction of benzaldehyde, 2-naphthol and benzamide. The best yield (92.86%) was obtained in the least time (10 min) with a molar ratio 1.2 : 1.2 : 1.7 of benzaldehyde : β-naphthol : benzamide and 0.1 g bimetallic Cu–Ag MOF/MCM-41 composite under solvent-free conditions at 130 °C. Reuse of the catalysts showed that they could be used at least four times without any reduction in the catalytic activity.

Monometallic and bimetallic MOF/MCM-41 composites (Cu, Ag and Cu–Ag) were synthesized via a solvothermal method.     

Exposure of mass-selected bimetallic Pt–Ti nanoalloys to oxygen explored using scanning transmission electron microscopy and density functional theory

The response of nanoparticles to exposure to ambient conditions and especially oxidation is fundamental to the application of nanotechnology. Bimetallic platinum–titanium nanoparticles of selected mass, 30 kDa and 90 kDa, were produced using a magnetron sputtering gas condensation cluster source and deposited onto amorphous carbon TEM grids. The nanoparticles were analysed with a C_s-corrected Scanning Transmission Electron Microscope (STEM) in High Angle Annular Dark Field (HAADF) mode. It was observed that prior to full Ti oxidation, Pt atoms were dispersed within a Ti shell. However, after full oxidation by prolonged exposure to ambient conditions prior to STEM, the smaller size 30 kDa particles form a single Pt core and the larger size 90 kDa particles exhibit a multi-core structure. Electron beam annealing induced a single core morphology in the larger particles. First principles density functional theory (DFT) calculations were employed to calculate the lowest energy structure of the Pt–Ti nanoparticles with and without the presence of oxygen. It was demonstrated that, as the concentration of oxygen increases, the lowest energy structure changes from dispersed Pt to multiple Pt cores and finally a single Pt core, which is in good agreement with the experimental observations.

Theoretical and experimental morphology induced by oxidation of the Ti element.     

Nonstoichiometric oxygen in Mn–Ga–O spinels: reduction features of the oxides and their catalytic activity

The subject of this study was the content of oxygen in mixed oxides with the spinel structure Mn_1.7Ga_1.3O₄ that were synthesized by coprecipitation and thermal treatment in argon at 600–1200 °C. The study revealed the presence of excess oxygen in “low-temperature” oxides synthesized at 600–800 °C. The occurrence of superstoichiometric oxygen in the structure of Mn_1.7Ga_1.3O_4+δ oxide indicates the formation of cationic vacancies, which shows up as a decreased lattice parameter in comparison with “high-temperature” oxides synthesized at 1000–1200 °C; the additional negative charge is compensated by an increased content of Mn³⁺ cations according to XPS. The low-temperature oxides containing excess oxygen show a higher catalytic activity in CO oxidation as compared to the high-temperature oxides, the reaction temperature was 275 °C. For oxides prepared at 600 and 800 °C, catalytic activity was 0.0278 and 0.0048 cm³ (CO) per g per s, and further increase in synthesis temperature leads to a drop in activity to zero. The process of oxygen loss by Mn_1.7Ga_1.3O_4+δ was studied in detail by TPR, in situ XRD and XPS. It was found that the hydrogen reduction of Mn_1.7Ga_1.3O_4+δ proceeds in two steps. In the first step, excess oxygen is removed, Mn_1.7Ga_1.3O_4+δ → Mn_1.7Ga_1.3O₄. In the second step, Mn³⁺ cations are reduced to Mn²⁺ in the spinel structure with a release of manganese oxide as a single crystal phase, Mn_1.7Ga_1.3O₄ → Mn₂Ga₁O₄ + MnO.

The hydrogen reduction of Mn_1.7Ga_1.3O_4+δ proceeds in two steps. In the first step, excess oxygen is removed, Mn_1.7Ga_1.3O_4+δ → Mn_1.7Ga_1.3O₄. In the second step, Mn³⁺ cations are reduced to Mn²⁺ in the spinel structure and formation of MnO, Mn_1.7Ga_1.3O₄ → Mn₂Ga₁O₄ + MnO.     

Fast photocatalytic degradation of dyes using low-power laser-fabricated Cu2O–Cu nanocomposites

In this study, we report a simple method to controllably synthesize Cu₂O–Cu nanocomposites by using a low-power CO₂ laser, and application of these nanomaterials for photocatalytic degradation of methylene blue (MB). Our experiments demonstrate that efficient tailoring of the Cu₂O–Cu nanocomposites can be realized by accurate control and optimization of the ambient parameters, such as laser energy and NaOH concentration. Compared to hydrothermally fabricated Cu₂O–Cu catalysts, the laser-reduced composites exhibit better visible-light photocatalytic activity for MB degradation, which could be attributed to the formation of special catalytically active structures on the nanocomposite surface. Under the conditions of 10 mA laser irradiation and 5 M NaOH addition, the fabricated Cu₂O–Cu composites had the highest catalytic activity. The degradation rate of MB is 90.10% after visible-light irradiation for 50 min under the optimum conditions. The as-synthesized Cu₂O–Cu composites showed selective dye degradation, and exhibit relatively higher photocatalytic efficiency for positively charged dyes. This work could lead to facile synthesis of high-performance photocatalysts for fast removal of environmentally hazardous dyes from aqueous solution.

Facile synthesis of Cu₂O–Cu nanocomposites by using a low-power CO₂ laser was realized, and the fabricated nanomaterials showed excellent photocatalytic activity for the degradation of various dyes.     

Experimental and theoretical investigation of oxidative methane activation on Pd–Pt catalysts

Density functional theory (DFT) and measurements of rate are used to provide evidence for the rate determining step (RDS) and requirements of the active site for CH₄ combustion on Pd–Pt bimetallic catalysts in five different distinct kinetic regimes. These five regimes exhibit different rate equations for methane combustion due to the reaction rate constants and diverse dominant adsorbed species for these different kinetically relevant steps. Oxygen chemical potential at the Pd–Pt surface was replaced by oxygen pressure, reflecting the kinetic coupling between C–H and O O bond cleavage steps. C–H bond cleavage occurs on different active sites in five of these kinetic regimes, evolving from vacancy–vacancy (*–*) to oxygen–vacancy (O*–*), oxygen–oxygen (O*–O*) site pairs, monolayer Pd–O, and ultimately to oxide bulk with Pd–O site pairs as the oxygen chemical potential increases. It is easier to form a metallic surface at low oxygen pressure, implying minimal O* coverage. The sole kinetically relevant step on uncovered Pd–Pt surfaces for methane combustion is O O bond cleavage. The supply of oxygen is obviously more important than the supply of methane in regime (I). As vacancies become less available on metallic surfaces, C–H bond cleavage occurs via O*–* paired sites, the energy barrier of which is much higher than that on uncovered Pd–Pt surfaces. In this regime (II), O O bond cleavage is still an irreversible process because O* will be consumed by the rapidly formed products of methane dissociation. For the oxygen saturated surfaces in regime (III), C–H bond cleavage occurs on two adjacent adsorbed oxygens that form OH and weak CH₃–O bond interactions, resulting in a low activity for methane combustion. On the oxidation surfaces (IV and V), exposed metal atoms and their adjacent exposed lattice oxygen were the active sites, leading to a large decrease in C–H bond cleavage energy barrier, deduced from both experiment and theory. The increase of the metallic oxide thickness (increase of oxygen potential) increases the methane combustion turnover rates on Pd–Pt catalysts.

Density functional theory and measurements of rate are used to provide evidence for the rate determining step and requirements of the active site for CH₄ combustion on Pd–Pt bimetallic catalysts in five different distinct kinetic regimes.     

Construction of Cu–Ce/graphene catalysts via a one-step hydrothermal method and their excellent CO catalytic oxidation performance

Cu–Ce/graphene catalysts show high dispersion of metal particles and excellent activity and stability for catalytic oxidation. In this study, a hydrothermal method was used to synthesize a series of bimetallic Cu–Ce/graphene catalysts, and the effects of the proportions of Cu and Ce on CO oxidation were investigated in detail. Indispensable characterizations such as XPS, XRD, TEM, BET, and H₂-TPR were conducted to explore the effect of the Cu/Ce molar ratio and the metal valence on the activity and determine the structure–performance relationship. The results showed that bimetallic supported catalysts, such as 3Cu5Ce/graphene, 1Cu1Ce/graphene, and 5Cu3Ce/graphene, possessed significant catalytic activity. Especially, the 5Cu3Ce/graphene catalyst showed highest catalytic activity for CO oxidation, the T₁₀₀ value was 132 °C, and the apparent activation energy was 68.03 kJ mol⁻¹. Furthermore, the stability of the 5Cu3Ce/graphene catalyst was outstanding, which could be maintained for at least 12 h. Moreover, the CeO₂ particles were well crystalline with the size 5–9 nm in these catalysts, and the CuO nanoparticles were well dispersed on CeO₂ and graphene. Notably, the ratio of Cu/Ce in the catalyst was higher, the interaction between the Ce species and the graphene was stronger, and the Cu species were more easily reduced; this was beneficial for the oxidation of CO.

Cu–Ce/graphene catalysts show high dispersion of metal particles and excellent activity and stability for catalytic oxidation.     

Synergetic effects of graphene–CoPc/silk fibroin three-dimensional porous composites as catalysts for acid red G degradation

The disposal of dye wastewater is one of the hotspots of scientific research. Upon combining the ability of graphene to accelerate the hydroxyl radical generation with the Fenton system, it has shown a faster degradation rate and can be recycled, showing greater degradation efficiency than the traditional dye treatment method. Herein, a catalytic system based on the regenerated silk fibroin (SF) gel integrated with cobalt tetraaminophthalocyanine (CoTAPc)-grafted-reduced graphene oxide (RGO) sheets were fabricated, and its catalytic activity was assessed via the degradation of acid red G (ARG) at varying catalyst and H₂O₂ dosages, pH values, and temperatures. The results revealed that the three-dimensional (3D) porous RGO-CoTAPc/SF gel exhibited a much stronger catalytic behavior than the other arbitrary components due to its high surface area and synergetic hydroxyl radical generation efficiency, with the dye removal ratio by RGO-CoTAPc/SF being higher in an acidic medium than in an alkaline medium. It also increases with the increase in temperature and RGO-CoTAPc/SF and H₂O₂ dosages. Further, the catalytic oxidation process of ARG was determined, and the possible degradation mechanism of ARG has been discussed. Our results suggest that the composite materials with high catalytic activity can provide a reference for future Fenton-like catalytic systems.

The disposal of dye wastewater is one of the hotspots of scientific research, and graphene–CoTAPc–SF composites exhibit more effective catalytic abilities.     

Solar driven reduction of CO2 using Pt–Cu/C as a catalyst in a photoelectrochemical cell: experiment and mechanism study

Carbon supported nano-metal catalysts are expected to improve CO₂ reduction selectivity and efficiency due to the addition of more active sites and enhancement of electron transport ability. In this study, HKUST-1 was pyrolyzed and decorated with Pt to prepare Pt–Cu/C catalysts. The catalytic effect of the catalysts with different Pt contents in the CO₂ photoeletrochemical reduction reaction (CO₂PRR) were compared. The total carbon atom conversion rate in CO₂PRR experiments using Pt–Cu/C catalysts first increased to a peak when using 1.6 wt% Pt–Cu/C catalyst and then decreased with the increase of Pt content. The 1.6 wt% Pt–Cu/C catalyst showed good hydrogen evolution reaction (HER) inhibiting ability compared with other Pt–Cu/C catalysts. Density functional theory (DFT) calculations were conducted to give an insight into the CO₂PRR mechanism on some possible active sites in Pt–Cu/C catalysts. The result demonstrated that HER was more likely to be inhibited on the Cu/Pt active surface and at the same time CO₂PRR was promoted.

Carbon supported nano-metal catalysts are expected to improve CO₂ reduction selectivity and efficiency due to the addition of more active sites and enhancement of electron transport ability.     

Role of composition and texture on bifunctional catalytic performance of extruded Au–Cu alloys

The catalytic activity of Au₂Cu and AuCu samples for the electro-oxidation of CH₃OH and HCOOH, together with their structure and micro-hardness were investigated using various techniques. The addition of Cu can improve the micro-hardness of samples, which is ascribed to the solid solution strengthening effect. The Schmid factor and low angle grain boundary fraction confirm the difference of plastic deformation ability for samples, being consistent with hardness results. The Au–Cu samples exhibit good bifunctional catalytic performance due to the synergistic effect between Au and Cu. In addition, the Au₂Cu sample exhibits a higher catalytic activity than the AuCu sample, suggesting that appropriate preferred orientation plays a key role in the improvement of catalytic activities of Au based catalysts.

Extruded Au–Cu alloys can be used as bifunctional catalysts for the electro-oxidation of CH₃OH and HCOOH, and their catalytic activities can be improved based on alloying and appropriate texture.