ZnO–ZnCr2O4 composite prepared by a glycine nitrate process method and applied for hydrogen production by steam reforming of methanol

To address climate change, the energy crisis, and global warming, hydrogen (H₂) can be used as a potential energy carrier because it is clean, non-toxic and efficient. Today, the mainstream industrial method of H₂ generation is steam reforming of methanol (SRM). In this process, a zinc-based commercial catalyst is usually used. In this work, a ZnO–ZnCr₂O₄ catalyst was successfully synthesised by the glycine nitrate process (GNP) and developed for use in H₂ production by SRM. The specific surface area, porous structure and reaction sites of the zinc-based catalyst were effectively increased by the preparation method. The as-combusted ZnO–ZnCr₂O₄ composite catalyst had a highly porous structure due to the gas released during the GNP reaction process. Moreover, according to the ZnO distribution and different G/N ratios, the specific surface area (S_BET) of the as-combusted ZnO–ZnCr₂O₄ catalyst varied from 29 m² g⁻¹ to 46 m² g⁻¹. The ZnO–ZnCr₂O₄ composite catalyst (G/N 1.7) exhibited the highest hydrogen production, 4814 ml STP min⁻¹ g-cat⁻¹, at a reaction temperature of 450 °C without activation treatment. After activation, the ZnO–ZnCr₂O₄ composite catalyst achieved hydrogen production of 6299 ml STP min⁻¹ g-cat⁻¹ at a reaction temperature of 500 °C. The hydrogen production performance of the ZnO–ZnCr₂O₄ composite powder was improved by the uniform addition of ZnO to ZnCr₂O₄. Based on the performance, this ZnO–ZnCr₂O₄ composite catalyst has great potential to have industrial and economic impact due to its high efficiency in hydrogen production.

ZnO–ZnCr₂O₄ composite for hydrogen production by steam reforming of methanol.     

The influence of composition on the functionality of hybrid CuO–ZnO–Al2O3/HZSM-5 for the synthesis of DME from CO2 hydrogenation

A series of CuO–ZnO–Al₂O₃/HZSM-5 hybrid catalysts with different Cu/Zn ratios and disparate Al₂O₃ doping were prepared and characterized by XRD, BET, H₂-TPR, NH₃-TPD and XPS techniques. The optimal Cu/Zn ratio is 7 : 3, and the introduction of a suitable amount of Al₂O₃ to form hybrid catalysts increased the BET specific area and micropore volume, facilitated the CuO dispersion, decreased the CuO crystallite size, increased the interaction between CuO and ZnO, enhanced the number of weak acid sites, altered the copper chemical state and improved the catalytic performance consequently. The highest CO₂ conversion, DME selectivity and DME yield of 27.3%, 67.1% and 18.3%, respectively, were observed over the CZA₇H catalyst. The suitable temperature of 260 °C and the appropriate space velocity of 1500 h⁻¹ for one-step synthesis of dimethyl ether (DME) from carbon dioxide (CO₂) hydrogenation were also investigated. The 50 h stability of the CZA₇H catalyst was also tested.

The introduction of Al₂O₃ increased the number of weak acid sites, altered the copper chemical state and improved the catalytic performance and stability consequently.     

Microstructure–mechanical properties of Ag0/Au0 doped K–Mg–Al–Si–O–F glass-ceramics

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied. The thermal parameters viz., glass transition temperature (T_g) and crystallization temperature (T_c) were extensively changed by varying NPs (in situ or ex situ). Tc was found to be increased (T_c = 870–875 °C) by 90–110 °C when ex situ NPs were present in the glass system. Under controlled heat-treatment at 950 ± 10 °C, the glasses were converted into glass-ceramics with the predominant presence of crystalline phase (XRD) fluorophlogopite mica, [KMg₃(AlSi₃O₁₀)F₂]. Along with the secondary phase enstatite (MgSiO₃), the presence of Ag and Au particles (FCC system) were identified by XRD. A microstructure containing spherical crystallite precipitates (∼50–400 nm) has been observed through FESEM in in situ doped GCs. An ex situ Ag doped GC matrix composed of rock-like and plate-like crystallites mostly of size 1–3 μm ensured its superior machinability. Vicker''s and Knoop microhardness of in situ doped GCs were estimated within the range 4.45–4.61 GPa which is reduced to 4.21–4.34 GPa in the ex situ Ag system. Machinability of GCs was found to be in the order, ex situ Ag > ex situ Au ∼ in situ Ag > in situ Au. Thus, the ex situ Ag/Au doped SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ GC has potential for use as a machinable glass-ceramic.

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied.     

Improvement of low-temperature NH3-SCR catalytic performance over nitrogen-doped MOx–Cr2O3–La2O3/TiO2–N (M = Cu,Fe, Ce) catalysts

A series of MO_x–Cr₂O₃–La₂O₃/TiO₂–N (M = Cu, Fe, Ce) catalysts with nitrogen doping were prepared via the impregnation method. Comparing the low-temperature NH₃-SCR activity of the catalysts, CeCrLa/Ti–N (xCeO₂–yCr₂O₃–zLa₂O₃/TiO₂–N) exhibited the best catalytic performance (NO conversion approaching 100% at 220–460 °C). The physico-chemical properties of the catalysts were characterized by XRD, BET, SEM, XPS, H₂-TPR, NH₃-TPD and in situ DRIFTS. From the XRD and SEM results, N doping affects the crystalline growth of anatase TiO₂ and MO_x (M = Cu, Fe, Ce, Cr, La) which were well dispersed over the support. Moreover, the doping of N promotes the increase of the Cr⁶⁺/Cr ratio and Ce³⁺/Ce ratio, and the surface chemical adsorption oxygen content, which suggested the improvement of the redox properties of the catalyst. And the surface acid content of the catalyst increased with the doping of N, which is related to CeCrLa/TiO₂–N having the best catalytic activity at high temperature. Therefore, the CeCrLa/TiO₂–N catalyst exhibited the best NH₃-SCR performance and the redox performance of the catalysts is the main factor affecting their activity. Furthermore, in situ DRIFTS analysis indicates that Lewis-acid sites are the main adsorption sites for ammonia onto CeCrLa/TiO₂–N and the catalyst mainly follows the L–H mechanism.

A series of MO_x–Cr₂O₃–La₂O₃/TiO₂–N (M = Cu, Fe, Ce) catalysts with nitrogen doping were prepared via the impregnation method.     

Investigation on the promotional role of Ga2O3 on the CuO–ZnO/HZSM-5 catalyst for CO2 hydrogenation

Dimethyl ether (DME) can be directly synthesized from carbon dioxide and hydrogen by mixing methanol synthesis catalysts and methanol dehydration catalysts. The activity and selectivity of the catalyst can be greatly affected by the promoter; herein, we presented a series of CuO–ZnO–Ga₂O₃/HZSM-5 hybrid catalysts, which were prepared by the coprecipitation method. The effect of the Ga₂O₃ content on the structure and performance of the Ga-promoted Cu–ZnO/HZSM-5 based catalysts was thoroughly investigated. The results showed that the addition of Ga₂O₃ significantly increased specific surface areas and Cu areas, decreased the size of Cu particles, maintained the proportion of Cu⁺/Cu⁰ on the surface of the catalyst, and strengthened the metal–support interaction, resulting in high catalytic performance.

The additive Ga₂O₃ improved the catalytic performance of CuO–ZnO/HZSM-5 catalysts for hydrogenation of CO₂ to DME.     

Photocatalytic activity of Ag/Al2O3–Gd2O3 photocatalysts prepared by the sol–gel method in the degradation of 4-chlorophenol

The photocatalytic activity in the degradation of 4-chlorophenol (4-ClPh) in aqueous medium (80 ppm) using 2.0 wt% Ag/Al₂O₃–Gd₂O₃ (Ag/Al–Gd-x; where x = 2.0, 5.0, 15.0, 25.0 and 50.0 wt% of Gd₂O₃) photocatalysts prepared by the sol–gel method was studied under UV light irradiation. The photocatalysts were characterized by N₂ physisorption, X-ray diffraction, SEM, HRTEM, UV-Vis, XPS, FTIR and fluorescence spectroscopy. About 67.0% of 4-ClPh was photoconverted after 4 h of UV light irradiation using Ag/γ-–Al₂O₃. When Ag/Al–Gd-x photocatalysts were tested, the 4-ClPh photoconversion was improved and more than 90.0% of 4-ClPh was photoconverted after 3 h of UV light irradiation in the materials containing 15.0 and 25.0 wt% of Gd₂O₃. Ag/Al–Gd-25 was the material with the highest efficacy to mineralize dissolved organic carbon, mineralizing more than 85.0% after 4 h of UV light irradiation. Silver nanoparticles and micro-particles of irregular pentagonal shape intersected by plane nanobelts of Al₂O₃–Gd₂O₃ composite oxide were detected in the Ag/Al–Gd-25 photocatalyst. This material is characterized by a lowest recombination rate of electron–hole pairs. The low recombination rate of photo-induced electron–hole pairs in the Ag/Al–Gd-x photocatalysts with high Gd₂O₃ contents (≥15.0 wt%) confirmes that the presence of silver nanoparticles and microparticles interacting with Al₂O₃–Gd₂O₃ composite oxide entities favors the separation of photo-induced charges (e⁻ and h⁺). These materials could be appropriate to be used as highly efficient photocatalysts to eliminate high concentrations of 4-ClPh in aqueous medium.

Ag/Al₂O₃–Gd₂O₃ showed high efficacy to photodegradate 4-chlorophenol, the strong interaction between silver nano-particles and micro-particles and Al₂O₃–Gd₂O₃ entities favors the decrease in the recombination rate.     

Boosting the singlet oxygen production from H2O2 activation with highly dispersed Co–N-graphene for pollutant removal

Singlet oxygen (¹O₂) is a promising reactive species for the selective degradation of organic pollutants. However, it is difficult to generate ¹O₂ from H₂O₂ activation with high efficiency and selectivity. In this work, a graphene-supported highly dispersed cobalt catalyst with abundant Co–N_x active sites (Co–N-graphene) was synthesized for activating H₂O₂. The Co–N-graphene catalyzed H₂O₂ reaction system selectively catalyzed ¹O₂ production associated with the superoxide radical (O₂˙⁻) as the critical intermediate, as proven by scavenger experiments, electron spin resonance (ESR) spin trapping and a kinetic solvent isotope effect study. This resulted in excellent degradation efficiency towards the model organic pollutant methylene blue (MB), with an outstanding pseudo-first-order kinetic rate constant of 0.432 min⁻¹ (g L_catalyst⁻¹)⁻¹ under optimal reaction conditions (C_H2O2 = 400 mM, initial pH = 9). Furthermore, this Co–N-graphene catalyst enabled strong synergy with HCO₃⁻ in accelerating MB degradation, whereas the scavenger experiment implied that the synergy herein differed significantly from the current Co²⁺–HCO₃⁻ reaction system, in which contribution of O₂˙⁻ was only validated with a Co–N-graphene catalyst. Therefore, this work developed a novel catalyst for boosting ¹O₂ production from H₂O₂ activation and will extend the inventory of catalysts for advanced oxidation processes.

A graphene-supported highly dispersed cobalt catalyst with abundant Co–N_x active sites was synthesized to boost ¹O₂ production from H₂O₂ activation, exhibiting excellent degradation efficiency towards the model organic pollutant methylene blue.     

VOX supported on TiO2–Ce0.9Zr0.1O2 core–shell structure catalyst for NH3-SCR of NO

In this experiment, a TiO₂–Ce_0.9Zr_0.1O₂ support with core–shell structure was successfully prepared by a precipitation method and VO_X/TiO₂–Ce_0.9Zr_0.1O₂ catalyst was prepared by an impregnation method, and the catalyst was used to catalyze the NH₃-SCR of NO. Based on the results of HRTEM, XRD, BET, H₂-TPR, NH₃-TPD, XPS, Py-IR, it was speculated that due to the interaction between TiO₂ and Ce_0.9Zr_0.1O₂, more oxygen vacancies and Ce³⁺ are generated, which are beneficial to the existence of low-valence V by electron transfer between high valence state V and Ce³⁺and increase the acidic sites on the catalyst surface. The catalytic activity (>97%) of the VO_X/TiO₂–Ce_0.9Zr_0.1O₂ catalyst is superior to the current commercial catalyst (V₂O₅–WO₃/TiO₂) and has a higher N₂ selectivity (>97.5%) at 40 000 h⁻¹ GHSV and 250–400 °C.

VO_X/TiO₂–Ce_0.9Zr_0.1O₂ catalyst exhibits high activity and selectivity in a wide temperature window.     

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.     

Conversion of levulinic acid to γ-valerolactone over Ru/Al2O3–TiO2 catalyst under mild conditions

Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water. In this study, mixed oxides Al₂O₃–TiO₂, Al₂O₃–MoO₃ and Al₂O₃–Co₃O₄ were synthesized by co-precipitation using aqueous solution of NaOH as precipitant. Ru catalysts supported on mixed oxides were prepared by impregnation method and their catalytic performances were tested in the hydrogenation of LA to GVL on a fixed bed reactor. The physicochemical properties of the catalysts were characterized by XRD, H₂-TPR, NH₃-TPD, and BET techniques. The TiO₂ component significantly affected the acidity of the catalyst, and thus its catalytic activity for the GVL yield was affected. The desired product GVL with a yield of about 97% was obtained over the Ru/Al₂O₃–TiO₂ catalyst under mild conditions (WHSV = 1.8 h⁻¹, T = 80 °C). Moreover, the catalyst Ru/Al₂O₃–TiO₂ exhibited excellent thermal stability in the test period of time.

Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water.     

Study of resistance performance of Al2O3–ZnO–Y2O3 thermal control coating exposed to vacuum-ultraviolet irradiation

As deep space exploration moves farther and farther away, thermal control coating of the in-orbit spacecraft will suffer a serious vacuum-ultraviolet radiation environment, which seriously threatens the reliability of the spacecraft in orbit. Therefore, it is important to improve the vacuum-ultraviolet resistance performance of the thermal control coating. In this work, the inorganic Al₂O₃–ZnO–Y₂O₃ thermal control coating was in situ fabricated on a 6061 aluminum alloy surface by PEO technology, and its vacuum-ultraviolet resistance performance was investigated. The results show that the Al₂O₃–ZnO–Y₂O₃ thermal control coating has a good resistance performance to vacuum-ultraviolet radiation, which is mainly because the large extinction coefficients of the ZnO and Y₂O₃ materials in the ultraviolet band are conducive to improving the ultraviolet resistance performance. Furthermore, the life prediction model of the Al₂O₃–ZnO–Y₂O₃ thermal control coating shows that its Δα_s value first slightly increases and then tends to be stable with the increase of ultraviolet irradiation time from 0 ESH to 25 000 ESH, and the maximum variation of Δα_s is about 0.0536. This work provides a material basis and technical support for the thermal control system of spacecraft with long life and high reliability.

The Al₂O₃–ZnO–Y₂O₃ thermal control coating in situ fabricated by PEO technology, shows a good resistance performance to vacuum-ultraviolet radiation. Further, its life prediction model at vacuum-ultraviolet irradiation is preliminarily established.     

Effect of unmelted lime on the element distribution behavior on a CaO–SiO2–MgO–Al2O3–FeO–CaF2(–Cr2O3) slag

In this study, a CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂(–Cr₂O₃) slag was chosen according to the compositions of the stainless steel slag for industrial production, and a CaO block was added to the molten slag after the synthetic slag was fully melted. The influences of unmelted lime on the distribution of elements and the structure of product layers at the lime/slag boundary, particularly the existing state of chromium oxide in the chromium-bearing stainless steel slag, were deeply discussed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and FactSage 7.1. The experiment results indicated that when the unmelted lime existed in the CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂ slag system, two product layers of periclase (MgO) and dicalcium silicate (Ca₂SiO₄) at the boundary of the CaO block were formed. However, when the CaO block was added in the CaO–SiO₂–Al₂O₃–MgO–FeO–CaF₂–Cr₂O₃ stainless steel slag, besides MgO and Ca₂SiO₄ product layers, needle-shaped calcium chromite (CaCr₂O₄) was also precipitated around the CaO block. Moreover, a small amount of Cr dissolved in the periclase phase. Eh–pH diagrams showed that the CaCr₂O₄ and MgO phase unstably existed in a weak acid aqueous solution. Therefore, the existence of unmelted lime in the stainless steel slag could enhance the leachability of chromium.

The effect of unmelted lime on the distribution of elements and structure of product layers in CaO–SiO₂–MgO–Al₂O₃–FeO–CaF₂(–Cr₂O₂) stainless steel slag and the action of unmelted lime phase mechanism in experimental slags was conducted.     

Recyclable MFe2O4 (M = Mn,Zn, Cu,Ni, Co) coupled micro–nano bubbles for simultaneous catalytic oxidation to remove NOx and SO2 in flue gas

NO_x can be efficiently removed by micro–nano bubbles coupling with Fe³⁺ and Mn²⁺, but the catalyst cannot be reused and the adsorption wastewater should be treated. This work developed a new technology that uses micro–nano bubbles and recyclable MFe₂O₄ to simultaneously remove NO_x and SO₂ from flue gas, and clarified the effectiveness and reaction mechanism. MFe₂O₄ (M = Mn, Zn, Cu, Ni and Co) prepared by a hydrothermal method was characterized. The results show that MFe₂O₄ can be activated to produce ˙OH which can accelerate the oxidation absorption of NO_x. Compared with no catalyst, the NO_x conversion rate increased from 32.85% to 83.88% in the NO_x–SO₂–MFe₂O₄-micro–nano bubble system, while the removal rate of SO₂ can reach 100% at room temperature. The catalytic activities of MFe₂O₄ showed the following trend: CuFe₂O₄ > ZnFe₂O₄ > MnFe₂O₄ > CoFe₂O₄ > NiFe₂O₄. The results provide a new idea for the application of advanced oxidation processes in flue gas treatment.

NO_x-SO₂-MFe₂O₄-micro–nano bubbles system for NO_x removal.     

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.     

Effect of Ni/Co mass ratio and NiO–Co3O4 loading on catalytic performance of NiO–Co3O4/Nb2O5–TiO2 for direct synthesis of 2-propylheptanol from n-valeraldehyde

In the direct synthesis of 2-propylheptanol (2-PH) from n-valeraldehyde, a second-metal oxide component Co₃O₄ was introduced into NiO/Nb₂O₅–TiO₂ catalyst to assist in the reduction of NiO. In order to optimize the catalytic performance of NiO–Co₃O₄/Nb₂O₅–TiO₂ catalyst, the effects of the Ni/Co mass ratio and NiO–Co₃O₄ loading were investigated. A series of NiO–Co₃O₄/Nb₂O₅–TiO₂ catalysts with different Ni/Co mass ratios were prepared by the co-precipitation method and their catalytic performances were evaluated. The result showed that NiO–Co₃O₄/Nb₂O₅–TiO₂ with a Ni/Co mass ratio of 8/3 demonstrated the best catalytic performance because the number of d-band holes in this catalyst was nearly equal to the number of electrons transferred in hydrogenation reaction. Subsequently, the NiO–Co₃O₄/Nb₂O₅–TiO₂ catalysts with different Ni/Co mass ratios were characterized by XRD and XPS and the results indicated that both an interaction of Ni with Co and formation of a Ni–Co alloy were the main reasons for the reduction of NiO–Co₃O₄/Nb₂O₅–TiO₂ catalyst in the reaction process. A higher NiO–Co₃O₄ loading could increase the catalytic activity but too high a loading resulted in incomplete reduction of NiO–Co₃O₄ in the reaction process. Thus the NiO–Co₃O₄/Nb₂O₅–TiO₂ catalyst with a Ni/Co mass ratio of 8/3 and a NiO–Co₃O₄ loading of 14 wt% showed the best catalytic performance; a 2-PH selectivity of 80.4% was achieved with complete conversion of n-valeraldehyde. Furthermore, the NiO–Co₃O₄/Nb₂O₅–TiO₂ catalyst showed good stability. This was ascribed to the interaction of Ni with Co, the formation of the Ni–Co alloy and further reservation of both in the process of reuse.

NiO–Co₃O₄/Nb₂O₅–TiO₂ catalyst with a Ni/Co mass ratio of 8/3 and NiO–Co₃O₄ loading of 14% shows the best catalytic performance.     

Acid–base sites synergistic catalysis over Mg–Zr–Al mixed metal oxide toward synthesis of diethyl carbonate

In heterogeneous catalysis processes, development of high-performance acid–base sites synergistic catalysis has drawn increasing attention. In this work, we prepared Mg/Zr/Al mixed metal oxides (denoted as Mg₂Zr_xAl_1−x–MMO) derived from Mg–Zr–Al layered double hydroxides (LDHs) precursors. Their catalytic performance toward the synthesis of diethyl carbonate (DEC) from urea and ethanol was studied in detail, and the highest catalytic activity was obtained over the Mg₂Zr_0.53Al_0.47MMO catalyst (DEC yield: 37.6%). By establishing correlation between the catalytic performance and Lewis acid–base sites measured by NH₃-TPD and CO₂-TPD, it is found that both weak acid site and medium strength base site contribute to the overall yield of DEC, which demonstrates an acid–base synergistic catalysis in this reaction. In addition, in situ Fourier transform infrared spectroscopy (in situ FTIR) measurements reveal that the Lewis base site activates ethanol to give ethoxide species; while Lewis acid site facilitates the activated adsorption of urea and the intermediate ethyl carbamate (EC). Therefore, this work provides an effective method for the preparation of tunable acid–base catalysts based on LDHs precursor approach, which can be potentially used in cooperative acid–base catalysis reaction.

Mg/Zr/Al mixed metal oxides were prepared via a facile phase transformation process of hydrotalcite precursors, which showed acid–base sites synergistic catalytic performance toward the synthesis of diethyl carbonate from ethanol and urea.     

Greener and facile synthesis of Cu/ZnO catalysts for CO2 hydrogenation to methanol by urea hydrolysis of acetates

Cu/ZnO-based catalysts for methanol synthesis by CO_x hydrogenation are widely prepared via co-precipitation of sodium carbonates and nitrate salts, which eventually produces a large amount of wastewater from the washing step to remove sodium (Na⁺) and/or nitrate (NO₃⁻) residues. The step is inevitable since the remaining Na⁺ acts as a catalyst poison whereas leftover NO₃⁻ induces metal agglomeration during the calcination. In this study, sodium- and nitrate-free hydroxy-carbonate precursors were prepared via urea hydrolysis co-precipitation of acetate salt and compared with the case using nitrate salts. The Cu/ZnO catalysts derived from calcination of the washed and unwashed precursors show catalytic performance comparable to the commercial Cu/ZnO/Al₂O₃ catalyst in CO₂ hydrogenation at 240–280 °C and 331 bar. By the combination of urea hydrolysis and the nitrate-free precipitants, the catalyst preparation is simpler with fewer steps, even without the need for a washing step and pH control, rendering the synthesis more sustainable.

Sodium- and nitrate-free hydroxy-carbonate precursors were prepared via urea hydrolysis co-precipitation of acetate salt, which is simpler with fewer steps, even without the need for a washing and pH control, rendering the synthesis more sustainable.     

One step synthesis of high-efficiency AgBr–Br–g-C3N4 composite catalysts for photocatalytic H2O2 production via two channel pathway

In this work, a two-component modified AgBr–Br–g-C₃N₄ composite catalyst with outstanding photocatalytic H₂O₂ production ability is synthesized. XRD, UV-Vis, N₂ adsorption, TEM, XPS, EPR and PL were used to characterize the obtained catalysts. The as-prepared AgBr–Br–g-C₃N₄ composite catalyst shows the highest H₂O₂ equilibrium concentration of 3.9 mmol L⁻¹, which is 7.8 and 19.5 times higher than that of GCN and AgBr. A “two channel pathway” is proposed for this reaction system which causes the remarkably promoted H₂O₂ production ability. In addition, compared with another two-component modified catalyst, Ag–AgBr–g-C₃N₄, AgBr–Br–g-C₃N₄ composite catalyst displays the higher photocatalytic H₂O₂ production ability and stability.

In this work, a two-component modified AgBr–Br–g-C₃N₄ composite catalyst with outstanding photocatalytic H₂O₂ production ability is synthesized.     

Correlation among the structural,electric and magnetic properties of Al3+ substituted Ni–Zn–Co ferrites

This study explored the structural, electrical, and magnetic properties of diamagnetic aluminium (Al³⁺) substituted nickel-zinc-cobalt (Ni–Zn–Co) mixed spinel ferrites, though the research on this area is in the infancy stage. Single-phase cubic spinel structures with the Fd$\bar{3}$m space group of the synthesized Ni_0.4Zn_0.35Co_0.25Fe_(2−x)Al_xO₄ (0 ≤ x ≤ 0.12) ferrite samples were confirmed by X-ray diffraction (XRD) analysis. The average particle size ranged from 0.67 to 0.39 μm. Selected area electron diffraction (SAED) patterns were indexed according to the space group Fd3m, representing the particle''s crystallinity. The optical band gaps ranged from 4.784 eV to 4.766 eV. Frequency-dependent dielectric constants and ac conductivity measurement suggested that the prepared ferrites were highly resistive. Relaxation times were reduced to a low value from 45.45 μs to 1.54 μs with the composition x. The Curie temperatures (T_c) were 615–623 K for all samples. Real part permeabilities (μ^/) were relatively stable up to an extended frequency range of 10⁶ Hz with relative quality factors (RQF) of around 10³. Tuning of the properties indicates that the fabricated ferrites may be promising for high-frequency electronic devices.

This study explored the structural, electrical, and magnetic properties of diamagnetic aluminium (Al³⁺) substituted nickel–zinc–cobalt (Ni–Zn–Co) mixed spinel ferrites, though the research on this area is in the infancy stage.     

Reactive adsorption desulfurization of NiO and Ni0 over NiO/ZnO–Al2O3–SiO2 adsorbents: role of hydrogen pretreatment

Reactive adsorption desulfurization (RADS) of Fluidized Catalytically Cracked (FCC) gasoline on reduced and unreduced NiO/ZnO–Al₂O₃–SiO₂ adsorbents was studied. Various characterizations such as powder X-ray diffraction (XRD), H₂-temperature-programmed reduction (H₂-TPR), the H₂/O₂ pulse titration (HOPT), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are used to evaluate the effects of hydrogen pretreatment of the adsorbents. XRD and HOPT results indicate that NiO is hard to be reduced to Ni⁰ under the conditions of RADS. H₂-TPR shows that NiO might be reduced to Ni⁰ at the temperature of 598 °C, much higher than the temperature of RADS. The Ni 2p_3/2 spectrum of Ni⁰ is not observed for the reduced adsorbent, but the main peak of Ni 2p_3/2 of NiS is found for the spent adsorbent. The unreduced NiO/ZnO–Al₂O₃–SiO₂ adsorbent performs a better desulfurization than the reduced adsorbent at the beginning of desulfurization process. NiO and Ni⁰ are assumed as the main active components and present a good desulfurization ability in RADS. Finally, a change in the RADS mechanism is presented and discussed.

A possible reaction mechanism of desulfurization on NiO/ZnO–Al₂O₃–SiO₂ is discussed.