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.     

Microstructure,friction and corrosion resistance properties of a Ni–Co–Al2O3 composite coating

Ni–Co–Al₂O₃ composite coatings were prepared by pulsed electrodeposition and electrophoresis–electrodeposition on aluminum alloy. The content of Al₂O₃ particles of the Ni–Co–Al₂O₃ composite coating prepared by electrophoresis–electrodeposition was significantly higher than the composite coating prepared by pulsed electrodeposition. The composite coating prepared by electrophoresis–electrodeposition exhibited a better anti-wear performance than that prepared by pulsed electrodeposition. The morphology, composition and microstructure of the composite coatings were determined by means of X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The hardness and friction properties of the samples were tested on the microhardness tester and the friction and wear loss tester respectively.

Ni–Co–Al₂O₃ composite coatings were prepared by pulsed electrodeposition and electrophoresis–electrodeposition on aluminum alloy.     

Palladium supported on mixed-metal–organic framework (Co–Mn-MOF-74) for efficient catalytic oxidation of CO

Successful monometallic and bimetallic metal–organic frameworks with different Co/Mn ratios have been synthesized under solvothermal conditions. The as-synthesized MOFs followed by deposition of Pd nanoparticles with 0.5 to 7 wt%. The XRD, BET, SEM, TEM, EDAX and FT-IR characterization results reveal that bimetallic MOFs and Pd nanoparticles were finely dispersed on the prepared MOFs surfaces. XRD results confirm the formation of the desire MOFs and show the high degree of dispersion of Pd nanoparticles. TEM images show that Pd nanoparticles are nano-sized with almost uniform shape. EDAX shows that Pd nanoparticles successfully loaded on Co_0.5–Mn_0.5-MOF-74 catalyst. CO oxidation as a model reaction was then used to assess the catalytic performance of the prepared catalysts. The catalytic activity results show enhancement in the catalytic activities of monometallic MOFs after introducing another metal in the same framework and show an excellent improvement in CO conversion after loading with Pd nanoparticles. Furthermore, the samples that contain Pd nanoparticles exhibits higher catalytic activities which raised with increasing the content of Pd nanoparticles.

Pd nanoparticles were loaded on Co_x–Mn_(1−x)-MOF-74. 5 wt% Pd@Co_0.5–Mn_0.5-MOF-74 was the most effective catalyst for CO oxidation. The prepared catalysts displayed excellent stability during CO oxidation without significant decrease in catalytic performance.     

Facile preparation of porous sheet–sheet hierarchical nanostructure NiO/Ni–Co–Mn–Ox with enhanced specific capacity and cycling stability for high performance supercapacitors

NiO, Ni–Co–Mn–O_x and NiO/Ni–Co–Mn–O_x on nickel foam substrates were prepared via a chemical bath deposition–calcination. The thermodynamic behavior was observed by TG/DTA. The chemical structure and composition, phase structure and microstructures were tested by XPS, XRD, FE-SEM and TEM. The electrochemical performance was measured by CV, GCD and EIS. The mechanism for formation and enhancing electrochemical performance is also discussed. Firstly, the precursors such as NiOOH, CoOOH and MnOOH grow on nickel foam substrates from a homogeneous mixed solution via chemical bath deposition. Thereafter, these precursors are calcined and decomposed into NiO, Co₃O₄ and MnO₂ respectively under different temperatures in a muffle furnace. Notably, NiO/Ni–Co–Mn–O_x on nickel foam substrates reveals a high specific capacity with 1023.50 C g⁻¹ at 1 A g⁻¹ and an excellent capacitance retention with 103.94% at 5 A g⁻¹ after 3000 cycles in 2 M KOH, its outstanding electrochemical performance and cycling stability are mainly attributed to a porous sheet–sheet hierarchical nanostructure and synergistic effects of pseudo-capacitive materials and excellent redox reversibility. Therefore, this research offers a facile synthesis route to transition metal oxides for high performance supercapacitors.

NiO, Ni–Co–Mn–O_x and NiO/Ni–Co–Mn–O_x on nickel foam substrates were prepared via a chemical bath deposition–calcination.     

Integral structured Co–Mn composite oxides grown on interconnected Ni foam for catalytic toluene oxidation

Considering the three-dimensional ordered network of Ni foam-supported catalysts and the toxicity effects of volatile organic compounds (VOCs), the design of proper active materials for the highly efficient elimination of VOCs is of vital importance in the environmental field. In this study, a series of Co–Mn composite oxides with different Co/Mn molar ratios grown on interconnected Ni foam are prepared as monolithic catalysts for total toluene oxidation, in which Co_1.5Mn_1.5O₄ with a molar ratio of 1 : 1 achieves the highest catalytic activity with complete toluene oxidation at 270 °C. The Co–Mn monolithic catalysts are characterized by XRD, SEM, TEM, H₂-TPR and XPS. It is observed that a moderate ratio of Mn/Co plays significant effects on the textural properties and catalytic activities. From the XPS and H₂-TPR characterization results, the obtained Co_1.5Mn_1.5O₄ (Co/Mn = 1/1) favors the excellent low-temperature reducibility, high concentration of surface Mn³⁺ and Co³⁺ species, and rich surface oxygen vacancies, resulting in superior oxidation performance due to the formation of a solid solution between the Co and Mn species. It is deduced that the existence of the synergistic effect between Co and Mn species results in a redox reaction: Co³⁺–Mn³⁺ ↔ Co²⁺–Mn⁴⁺, and enhances the catalytic activity for total toluene oxidation.

A series of Co–Mn oxides with different Co/Mn molar ratios grown on interconnected Ni foam were prepared as monolithic catalysts for total toluene oxidation.     

Production of green biofuel by using a goat manure supported Ni–Al hydrotalcite catalysed deoxygenation process

The high oxygen content in natural biomass resources, such as vegetable oil or biomass-pyrolysed bio oil, is the main constraint in their implementation as a full-scale biofuel for the automotive industry. In the present study, renewable fuel with petrodiesel-like properties was produced via catalytic deoxygenation of oleic acid in the absence of hydrogen (H₂). The deoxygenation pathway of oleic acid to bio-hydrocarbon involves decarboxylation/decarbonylation of the oxygen content from the fatty acid structure in the form of carbon dioxide (CO₂)/carbon monoxide (CO), with the presence of a goat manure supported Ni–Al hydrotalcite (Gm/Ni–Al) catalyst. Goat manure is an abundant bio-waste, containing a high mineral content, urea as well as cellulosic fiber of plants, which is potentially converted into activated carbon. Synthesis of Gm/Ni–Al was carried out by incorporation of pre-activated goat manure (GmA) during co-precipitation of Ni–Al catalyst with 1 : 3, 1 : 1 and 3 : 1 ratios. The physico-chemical properties of the catalysts were characterized by X-ray diffractometry (XRD), Brunauer–Emmet–Teller (BET) surface area, field emission surface electron microscopy (FESEM) and temperature program desorption ammonia (TPD-NH₃) analysers. The catalytic deoxygenation reaction was performed in a batch reactor and the product obtained was characterized by using gas chromatography-mass spectroscopy (GCMS) for compound composition identification as well as gas chromatography-flame ionisation detector (GC-FID) for yield and selectivity determination. The optimization and evaluation were executed using response surface methodology (RSM) in conjunction with central composite design (CCD) with 5-level-3-factors. From the RSM reaction model, it was found that the Gm/Ni–Al 1 : 1 catalysed deoxygenation reaction gives the optimum product yield of 97.9% of hydrocarbon in the range of C₈–C₂₀, with diesel selectivity (C₁₇: heptadecane and heptadecene compounds) of 63.7% at the optimal reaction conditions of: (1) reaction temperature: 327.14 °C, (2) reaction time: 1 h, and (3) catalyst amount: 5 wt%.

Deoxygenation pathway of oleic acid to bio-hydrocarbon involves decarboxylation/decarbonylation of oxygen content from fatty acid structure in the form of carbon dioxide (CO₂)/carbon monoxide (CO), respectively, with the presence of goat manure supported Ni–Al hydrotalcite (Gm/Ni–Al) catalyst.     

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.     

Tensile mechanical performance of Ni–Co alloy nanowires by molecular dynamics simulation

In this present contribution, tensile mechanical properties of Ni–Co alloy nanowires with Co content from 0 to 20% were studied by molecular dynamics. The simulation results show the alloy nanowire with the Co content of 5% has the highest yield value of 9.72 GPa. In addition, more Frank dislocations were generated during the loading process to improve the performance of the alloy nanowire. The Young''s modulus increases little by little from 105.68 to 179.78 GPa with the increase of Co content. Secondly, with the increase of temperature, the yield strength gradually decreases to 2.13 GPa. Young''s modulus tends to decrease linearly from 170.7 GPa to 48.21 GPa. At the temperatures of 500 K and 700 K, it is easier to form Frank dislocation and Hirth dislocation, respectively, in the loading process. The peak value of the radial distribution function decreases and the number of peaks decreases, indicating the disappearance of the ordered structure. Finally, after the introduction of the surface and inner void, the yield strength of the nanowire drops about to 8.97 and 6.6 GPa, respectively, and the yield strains drop to 0.056 and 0.043. In the case of the existence of internal void, perfect dislocation and Hirth dislocation can be observed in the structure.

The addition of a little Co can promote the formation of Frank and other fixed dislocations, making the alloy system have high yield strength. The defects in nanowires accelerated the occurrence of yield behavior.     

Hydrodesulfurization of dibenzothiophene using Pd-promoted Co–Mo/Al2O3 and Ni–Mo/Al2O3 catalysts coupled with ionic liquids at ambient operating conditions

Sulfur compounds in fuel oils are a major source of atmospheric pollution. This study is focused on the hydrodesulfurization (HDS) of dibenzothiophene (DBT) via the coupled application of 0.5 wt% Pd-loaded Co–Mo/Al₂O₃ and Ni–Mo/Al₂O₃ catalysts with ionic liquids (ILs) at ambient temperature (120 °C) and pressure (1 MPa H₂). The enhanced HDS activity of the solid catalysts coupled with [BMIM]BF₄, [(CH₃)₄N]Cl, [EMIM]AlCl₄, and [(n-C₈H₁₇)(C₄H₉)₃P]Br was credited to the synergism between hydrogenation by the former and extractive desulfurization and better H₂ transport by the latter, which was confirmed by DFT simulation. The Pd-loaded catalysts ranked highest by activity i.e. Pd–Ni–Mo/Al₂O₃ > Pd–Co–Mo/Al₂O₃ > Ni–Mo/Al₂O₃ > Co–Mo/Al₂O₃. With mild experimental conditions of 1 MPa H₂ pressure and 120 °C temperature and an oil : IL ratio of 10 : 3.3, DBT conversion was enhanced from 21% (by blank Ni–Mo/Al₂O₃) to 70% by Pd–Ni–Mo/Al₂O₃ coupled with [(n-C₈H₁₇)(C₄H₉)₃P]Br. The interaction of polarizable delocalized bonds (in DBT) and van der Waals forces influenced the higher solubility in ILs and hence led to higher DBT conversion. The IL was recycled four times with minimal loss of activity. Fresh and spent catalysts were characterized by FESEM, ICP-MS, EDX, XRD, XPS and BET surface area techniques. GC-MS analysis revealed biphenyl as the major HDS product. This study presents a considerable advance to the classical HDS processes in terms of mild operating conditions, cost-effectiveness, and simplified mechanization, and hence can be envisaged as an alternative approach for fuel oil processing.

Synergistic application of ionic liquids with Pd loaded Co–Mo@Al₂O₃ and Ni–Mo@Al₂O₃ catalysts for efficient hydrodesulfurization of dibenzothiophene at ambient conditions.     

A new highly active La2O3–CuO–MgO catalyst for the synthesis of cumyl peroxide by catalytic oxidation

In this study, different magnesium, copper, lanthanide single metal, and composite multimetal oxide catalysts were prepared via the coprecipitation route for the aerobic oxidation of cumene into cumene hydroperoxide. All catalysts were characterized using several analytical techniques, including XRD, SEM, EDS, FT-IR, BET, CO₂-TPD, XPS, and TG-DTG. La₂O₃–CuO–MgO shows higher oxidation activity and yield than other catalysts. The results of XRD and SEM studies show that the copper and magnesium particles in the catalyst are smaller in size and have a distribution over a larger area due to the introduction of the lanthanum element. The CO₂-TPD results confirmed that the catalyst has more alkali density and alkali strength, which can excite active sites and prevent the decomposition of cumene hydroperoxide. XPS results show that due to the promotional effect of La₂O₃, there are more lattice and active oxygen species in the catalyst, which can effectively utilize the lattice defects under the strong interaction between metal oxides for rapid adsorption and activation, thus improving the oxidation performance. Besides, La₂O₃–CuO–MgO exhibits good stability and crystalline structure due to its high oxygen mobility inhibiting coking during the cycle stability test. Finally, the possible reaction pathway and promotional mechanism on La₂O₃–CuO–MgO in cumene oxidation are proposed. We expect this study to shed more light on the nature of the surface-active site(s) of La₂O₃–CuO–MgO catalyst for cumene oxidation and the development of heterogeneous catalysts with high activity in a wide range of applications.

The La₂O₃–CuO–MgO catalyst acts on the oxidation of cumene and shows excellent catalytic activity through the coordination of surface and interior.     

Magnetic and spectroscopic properties of Ni–Zn–Al ferrite spinel: from the nanoscale to microscale

This article presents the annealing effect on the structural, elastic, thermodynamic, optical, magnetic, and electric properties of Ni_0.6Zn_0.4Fe_1.5Al_0.5O₄ (NZFAO) nanoparticles (NPs). The samples were successfully synthesized by the sol–gel method followed by annealing of the as-synthesized at 600, 800, 900, 1050, and 1200 °C. This approach yielded the formation of a highly crystalline structure with crystallite size ranging from 17 nm to 40 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM) techniques, as well as energy disperse spectroscopy (EDS), Fourier transform infrared (FTIR) and Raman spectroscopy, were used in order to determine the structural and morphological properties of the prepared samples. Rietveld XRD refinement reveals that Ni–Zn–Al ferrite nanoparticles crystallize in inverse cubic (Fd$\bar{3}$m) spinel structure. Using FTIR spectra, the elastic and thermodynamic properties were estimated. It was observed that the particle size had a pronounced effect on elastic and thermodynamic properties. Magnetic measurements were performed up to 700 K. The prepared ferrite samples present the highest Curie temperature, which decreases with increasing particle size and which is consistent with finite-size scaling. The thickness of the surface shell of about 1 nm was estimated from size-dependent magnetization measurements using the core–shell model. Besides, spin resonance, magnetostriction, temperature coefficient of resistance (TCR), and electrical resistivity properties have been scientifically studied and appear to be different according to their size. The optical properties of synthesized NZFAO nanoparticles were investigated, and the differences caused by the particle sizes are discussed on the basis of the phonon confinement effect. This effect was also inspected by the Raman analysis. Tuning of the physical properties suggests that the Ni–Zn–Al ferrite samples may be promising for multifunctional diverse applications.

This article presents the annealing effect on the structural, elastic, thermodynamic, optical, magnetic, and electric properties of Ni_0.6Zn_0.4Fe_1.5Al_0.5O₄ (NZFAO) nanoparticles (NPs).     

Effect of Re promoter on the structure and catalytic performance of Ni–Re/Al2O3 catalysts for the reductive amination of monoethanolamine

In this paper, Ni/Al₂O₃ catalysts (15 wt% Ni) with different Re loadings were prepared to investigate the effect of Re on the structure and catalytic performance of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine. Reaction results reveal that the conversion and ethylenediamine selectivity increase significantly with increasing Re loading up to 2 wt%. Ni–Re/Al₂O₃ catalysts show excellent stability during the reductive amination reaction. The characterization of XRD, DR UV-Vis spectroscopy, H₂-TPR, and acidity–basicity measurements indicates that addition of Re improves the Ni dispersion, proportion of octahedral Ni²⁺ species, reducibility, and acid strength for Ni–Re/Al₂O₃ catalysts. The Ni15 and Ni15–Re2 catalysts were chosen for in-depth study. The results from SEM-BSE, TEM, and CO-TPD indicate that smaller Ni⁰ particle size and higher Ni⁰ surface area are obtained in the reduced Ni–Re/Al₂O₃ catalysts. Results from in situ XPS and STEM-EDX line scan suggest that Re species show a mixture of various valances and have a tendency to aggregate on the surface of Ni⁰ particles. During reaction, the Ni⁰ particles on the Al₂O₃ support are stabilized and the sintering process is effectively suppressed by the incorporation of Re. It could be concluded that sufficient Ni⁰ sites, the collaborative effect of Ni–Re, and brilliant stability contribute to the excellent catalytic performance of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine.

Re promoters improve the catalyst performance and stability of Ni–Re/Al₂O₃ catalysts for the reductive amination of monoethanolamine.     

Synergetic effect over flame-made manganese doped CuO–CeO2 nanocatalyst for enhanced CO oxidation performance

CuO–CeO₂ nanocatalysts with different amounts of Mn dopping (Mn/Cu molar ratios of 0.5 : 5, 1 : 5 and 1.5 : 5) were synthesized by flame spray pyrolysis (FSP) method and tested in the catalytic oxidation of CO. The physicochemical properties of the synthesised samples were characterized systematically, including using X-ray diffraction (XRD), Raman spectroscopy, field-emission scanning electron microscopy (FESEM), Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), oxygen-temperature programmed desorption (O₂-TPD), hydrogen-temperature programmed reduction (H₂-TPR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). The results showed that the 1Mn–Cu–Ce sample (Mn/Cu molar ratio of 1 : 5) exhibited superior catalytic activity for CO oxidation, with the temperature of 90% CO oxidation at 131 °C at a high space velocity (SV = 60 000 mL g⁻¹ h⁻¹), which was 56 °C lower than that of the Cu–Ce sample. In addition, the 1Mn–Cu–Ce sample displays excellent stability with prolonged time on CO stream and the resistance to water vapor. The significantly enhanced activity was correlated with strong synergetic effect, leading to fine textual properties, abundant chemically adsorbed oxygen and high lattice oxygen mobility, which further induced more Cu⁺ species and less formation of carbon intermediates during the CO oxidation process detected by in situ DRIFTS analysis. This work will provide in-depth understanding of the synergetic effect on CO oxidation performances over Mn doped CuO–CeO₂ composite catalysts through FSP method.

The synergetic effect is promoted on Mn doped CuO–Ce O₂ catalyst to induce less carbon intermediates to enhance CO oxidation performance.     

Facile solvothermal preparation of Fe3O4–Ag nanocomposite with excellent catalytic performance

Functional nanocomposites demonstrate excellent comprehensive properties and outstanding characteristics for numerous applications. Magnetic nanocomposites are an important type of composite materials, due to their applications in optics, medicine and catalysis. In this report, a new Fe₃O₄-loaded silver (Fe₃O₄–Ag) nanocomposite has been successfully synthesized via a simple solvothermal method and in situ growth of silver nanowires. The silver nanowires were prepared via the reduction of silver vanadate with the addition of uniformly dispersed Fe₃O₄ nanoparticles. Structural and morphological characterizations of the obtained Fe₃O₄–Ag nanocomposite were carried out using many characterization methods. As a new composite catalyst, the synthesized magnetic Fe₃O₄–Ag nanocomposite displayed a high utilization rate of catalytically active sites in catalytic reaction medium and showed good separation and recovery using an external magnetic field. The facile preparation and good catalytic performance of this Fe₃O₄–Ag nanocomposite material demonstrate its potential applications in catalytic treatment and composite materials.

A new Fe₃O₄–Ag nanocomposite was prepared via solvothermal method, demonstrating potential application in catalytic degradation of wastewater treatment and composite materials.     

Efficient Ce–Co composite oxide decorated Au nanoparticles for catalytic oxidation of CO in the simulated atmosphere of a CO2 laser

Gold nanoparticles have a high activity for CO oxidation, making them suitable to be used in a CO₂ laser which maintains its efficiency and stability via the recombination of CO and O₂ produced by the CO₂ decomposition. However, the high concentration of CO₂ in the working environment greatly reduces the activity of the catalyst and makes the already unstable gold nanoparticles even more so. A novel Au/Ce-Co-O_x/Al₂O₃ gold catalyst, prepared by a deposition precipitation method in this study, displays high activity and good stability for CO oxidation in a simulated atmosphere of a CO₂ laser with the feed gases containing a high concentration of CO₂ up to 60 vol% but a low concentration of O₂ for the stoichiometric reaction with CO. An excellent performance for CO oxidation under CO₂-rich conditions could be achieved by decorating the surface of the Al₂O₃ support with Ce–Co composite oxides. The strong interaction between gold and the composite support, accompanied by the increase of labile lattice oxygen species and the decrease of surface basicity, led to a high CO oxidation rate and resistance towards CO₂ poisoning.

Novel Au/Ce-Co-O_x/Al₂O₃ showed a very excellent performance for CO oxidation in the simulated atmosphere of CO₂-laser mainly due to SMSI and labile lattice oxygen.     

Unravelling the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol catalysed by supported RANEY® Ni–Sn alloy catalysts

Bimetallic Ni–Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY® nickel–tin alloy supported on aluminium hydroxide (RNi–Sn(x)/AlOH; x is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi–Sn(1.4)/AlOH catalyst exhibited the highest yield of 1,4-PeD (78%). The reduction of RNi–Sn(x)/AlOH with H₂ at 673–873 K for 1.5 h resulted in the formation of Ni–Sn alloy phases (e.g., Ni₃Sn and Ni₃Sn₂) and caused the transformation of aluminium hydroxide (AlOH) to amorphous alumina (AA). The RNi–Sn(1.4)/AA 673 K/H₂ catalyst contained a Ni₃Sn₂ alloy as the major phase, which exhibited the best yield of 1,4-PeD from furfural (87%) at 433 K, H₂ 3.0 MPa for 12 h and from levulinic acid (up to 90%) at 503 K, H₂ 4.0 MPa, for 12 h. Supported RANEY® Ni–Sn(1.5)/AC and three types of supported Ni–Sn(1.5) alloy (e.g., Ni–Sn(1.5)/AC, Ni–Sn(1.5)/c-AlOH, and Ni–Sn(1.5)/γ-Al₂O₃) catalysts afforded high yields of 1,4-PeD (65–87%) both from furfural and levulinic acid under the optimised reaction conditions.

The RANEY® Ni–Sn(x) alloy catalysed the one-pot conversion of biomass-derived furfural and levulinic acid to allow remarkable yield of 1,4-pentanediol (up to 90%) under the mild reaction conditions.     

Effect of cobalt addition on the structure and properties of Ni–MCM-41 for the partial oxidation of methane to syngas

A one-step hydrothermal crystallization method was used to synthesize Co–Ni–MCM-41 catalysts for the partial oxidation of methane to syngas reaction. Co was added as an assistant in the synthesis process. The formation of a Ni–Co alloy decreased the damage of Ni ions to the framework of MCM-41. The Ni–Co alloy introduced more Ni into the channel exposing more active sites. The properties of the synthesized catalysts were characterized by XRD, N₂ adsorption–desorption, TEM, ICP, FT-IR, H₂-TPR, XPS and TGA techniques. Co–Ni–MCM-41 catalysts showed superior catalytic performance and sintering resistance than Ni–MCM-41 catalyst without Co. The Ni–Co alloy inhibited the formation of the NiO, thus reducing the sintering of the catalyst. The result was attributed to higher metal dispersion and more regular pore structure of the Co–Ni–MCM-41 catalysts. When the Co content was 1%, a conversion of 88% and selectivity of 87% was achieved.

The Ni–Co alloy confined within MCM-41 improved dispersibility and the stability of Ni.     

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.     

Retraction: Honeycomb-like Co–B amorphous alloy catalysts assembled by a solution plasma process show enhanced catalytic hydrolysis activity for hydrogen generation

Retraction of ‘Honeycomb-like Co–B amorphous alloy catalysts assembled by a solution plasma process show enhanced catalytic hydrolysis activity for hydrogen generation’ by Dong Ge Tong et al., RSC Adv., 2012, 2, 2369–2376.

We, the authors, hereby wholly retract this article due to inaccuracies in the scale bars of Fig. 1b, 4h and 5h and the wrong images being presented in Fig. 5d and e.We, the authors, repeated the experiments and believe that the scientific content and conclusions of the related studies presented in the published paper can be reproduced. However, due to the large number of images, it is not possible to replace the published images with the new figures. Therefore, to protect the rigor of the scientific record, we decided to retract this article on our own initiative.Signed: Dong Ge Tong (on behalf of the authors).Date: 6^th March 2020.Retraction endorsed by Laura Fisher, Executive Editor, RSC Advances.     

Sword-like CuO/CeO2 composites derived from a Ce-BTC metal–organic framework with superior CO oxidation performance

Porous shape-controllable metal oxide composites derived from a metal–organic framework have gained more and more attention due to their extensive applications. In this paper, sword-like CuO/CeO₂ composites were successfully synthesized by calcination of a strawsheave-like Ce-based metal–organic framework (Ce-BTC) containing suitable Cu loading as self-sacrificial templates at 500 °C. Moreover, sword-like CuO/CeO₂ composites displayed superior catalytic performance for CO oxidation, which was ascribed to a good interfacial contact, easily reducible surface copper species at low temperature and abundant surface lattice oxygen species, more Cu⁺ and oxygen vacancies.

Porous shape-controllable metal oxide composites derived from a metal–organic framework have gained more and more attention due to their extensive applications.