Catalysts, Volume 14, Issue 5 (May 2024) – 40 articles

To solve the shuttling effect and transformations of LiPSs in lithium–sulfur batteries, heterostructures have been designed to immobilize LiPSs and boost their reversible conversions. In this paper, we have constructed AlN/InN heterojunctions with AlN with a wide band gap and InN with a narrow band gap. The heterojunctions show metallic properties, which are primarily composed of 2s, 2p N atoms and 5s, 5p In atoms. InN has relatively higher adsorptivity for LiPSs than AlN. Reaction profiles show that on the surface of AlN, there is a lower rate-limiting step than on that of InN, from S₈ to Li₂S₆, and a higher rate-limiting step from Li₂S₄ to Li₂S₂, which is more favorable for InN during the reduction from Li₂S₄ to Li₂S₂. The heterojunction can realize the synergistic reaction of trapping–diffusion–conversion for LiPSs, in which AlN traps large Li₂S₈ and Li₂S₆, the heterojunction causes the diffusion of Li₂S₄, and InN completes the conversion of Li₂S₄ to Li₂S. Full article

This study examines the catalytic activity of NiFeCoO_x catalysts for anion exchange membrane (AEM) water electrolysis. The catalysts were synthesized with a Ni to Co ratio of 2:1 and Fe content ranges from 2.5 to 12.5 wt%. The catalysts were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The catalytic activity of the NiFeCoO_x catalysts was evaluated through linear sweep voltammetry (LSV) and chronoamperometry (CA) experiments for the oxygen evolution reaction (OER). The catalyst with 5% Fe content exhibited the highest catalytic activity, achieving an overpotential of 228 mV at a current density of 10 mA cm⁻². Long-term catalyst testing for the OER at 50 mA cm⁻² showed stable electrolysis operation for 100 h. The catalyst was further analyzed in an AEM water electrolyzer in a single-cell test, and the NiFeCoO_x catalyst with 5% Fe at the anode demonstrated the highest current densities of 1516 mA cm⁻² and 1620 mA cm⁻² at 55 °C and 70 °C at 2.1 V. The maximum current density of 1880 mA cm⁻² was achieved at 2.2 V and 70 °C. The Nyquist plot analysis of electrolysis at 55 °C showed that the NiFeCoO_x catalyst with 5% Fe had lower activation resistance compared with the other Fe loadings, indicating enhanced performance. The durability test was performed for 8 h, showing stable AEM water electrolysis with minimum degradation. An overall cell efficiency of 70.5% was achieved for the operation carried out at a higher current density of 0.8 A cm⁻². Full article

A self-sufficient bifunctional enzyme integrating reductive amination and coenzyme regeneration activities was developed and successfully employed to synthesize (S)-cyclopropylglycine with an improved reaction rate 2.1-fold over the native enzymes and a short bioconversion period of 6 h at a high substrate concentration of 120 g·L⁻¹ and space–time yield of (S)-cyclopropylglycine up to 377.3 g·L⁻¹·d⁻¹, higher than that of any previously reported data. Additionally, (S)-cyclopropylglycine could be continuously synthesized for 90 h with the enzymes packed in a dialysis tube, providing 634.6 g of (S)-cyclopropylglycine with >99.5% ee and over 95% conversion yield up to 12 changes. These results confirmed that the newly developed NADH-driven biocatalytic system could be utilized as a self-sufficient biocatalyst for industrial application in the synthesis of (S)-cyclopropylglycine, which provides a chiral center and cyclopropyl fragment for the frequent synthesis of preclinical/clinical drug molecules. Full article

Having a comprehensive knowledge of phase equilibrium is advantageous for industrial simulation and design of chemical processes. For further acquisition of primary data to facilitate the separation and purification of waste oil biodiesel systems, a liquid–liquid equilibrium (LLE) tank is deployed for the ternary system of waste oil biodiesel + methanol + glycerin, thereby enhancing the precision and efficiency of the process. The phase equilibrium system was constructed under the influence of atmospheric pressure at precise temperatures of 303.15 K, 313.15 K, and 323.15 K. The equilibrium components of each substance were analyzed by employing high-temperature gas chromatography, a sophisticated analytical method that enables the identification and quantification of individual components of a sample. Moreover, the ternary liquid–liquid equilibrium data were correlated by implementing the NRTL and UNIQUAC activity coefficient models. Subsequently, the binary interaction parameters of the ternary system were derived by conducting regression analysis. The experimental data demonstrated that the presence of lower methanol content in the system resulted in nearly immiscible biodiesel and glycerol phases, which ultimately facilitated the separation of biodiesel and glycerol. Conversely, with the increase in methanol content, the mutual solubility of biodiesel and glycerol was observed to increase gradually. The results showed that the calculated values of the NRTL and UNIQUAC models aligned well with the experimental values. The root-mean-square deviations of the NRTL and UNIQUAC models at 313.15 K were 2.76% and 3.56%, respectively. Full article

Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes. Full article

Bimetallic AuCu/SiO₂ nanosized catalysts were prepared using the wet chemical reduction technique. From among Au_0.1–1.5Cu₁₀/SiO₂ catalysts, the Au_0.5Cu₁₀/SiO₂ catalyst gave the highest yield of calcium lactate of 87% at a glycerol conversion of 96% when the reaction of glycerol with calcium hydroxide at a mole ratio of calcium hydroxide to glycerol of 0.8:1 was conducted under an anaerobic atmosphere at 200 °C for 2 h. The interactions between metallic Au⁰ and Cu⁰ nanoparticles facilitate calcium lactate formation. The simulation of glycerol consumption rate with an empirical power-function reaction kinetics equation yielded a reaction activation energy of 44.3 kJ∙mol⁻¹, revealing that the catalytic reaction of glycerol with calcium hydroxide to calcium lactate can be conducted by overcoming a mild energy barrier. The synthesis of calcium lactate through the catalytic reaction of glycerol with calcium hydroxide on a bimetallic AuCu/SiO₂ nanosized catalyst under a safe anaerobic atmosphere is an alternative to the conventional calcium lactate production technique through the reaction of expensive lactic acid with calcium hydroxide. Full article

Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually >USD 10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances, and pharmaceuticals, the need for them will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established and newer experimental methods. A wide range of methods, utilising microporous and mesoporous catalysts, has been explored, including their preparation and modification before use in industry. Their potential drawbacks and benefits have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in the field of fine chemical production using micro- and mesoporous heterogeneous catalysts. Full article

Compared to steam reforming techniques, partial oxidation of methane (POM) is a promising technology to improve the efficiency of synthesizing syngas, which is a mixture of CO and H₂. In this study, partial oxidation of methane (POM) was used to create syngas, a combination of CO and H₂, using the SAPO-5-supported Ni catalysts. Using the wetness impregnation process, laboratory-synthesized Ni promoted with Sr, Ce, and Cu was used to modify the SAPO-5 support. The characterization results demonstrated that Ni is appropriate for the POM due to its crystalline structure, improved metal support contact, and increased thermal stability with Sr, Ce, and Cu promoters. During POM at 600 °C, the synthesized 5Ni+1Sr/SAPO-5 catalyst sustained stability for 240 min on stream. While keeping the reactants stoichiometric ratio of (CH₄:O₂ = 2:1), the addition of Sr promoter and active metal Ni to the SAPO-5 increased the CH₄ conversion from 41.13% to 49.11% and improved the H₂/CO ratio of 3.33. SAPO-5-supported 5Ni+1Sr catalysts have great potential for industrial catalysis owing to their unique combination of several oxides. This composition not only boosts the catalyst’s activity but also promotes favorable physiochemical properties, resulting in improved production of syngas. Syngas is a valuable intermediate in various industrial processes. Full article

Semi-hydrogenation of acetylene to ethylene over metal oxide-supported Au nanoparticles is an interesting topic. Here, a hydrotalcite-based MMgAlO_x (M=Cu, Ni, and Co) composite oxide was exploited by introducing different Cu, Ni, and Co dopants with unique properties, and then used as support to obtain Au/MMgAlO_x catalysts via a modified deposition–precipitation method. XRD, BET, ICP-OES, TEM, Raman, XPS, and TPD were employed to investigate their physic-chemical properties and catalytic performances for the semi-hydrogenation of acetylene to ethylene. Generally, the catalytic activity of the Cu-modified Au/CuMgAlO_x catalyst was higher than that of the other modified catalysts. The TOR for Au/CuMgAlO_x was 0.0598 h⁻¹, which was 30 times higher than that of Au/MgAl₂O₄. The SEM and XRD results showed no significant difference in structure or morphology after introducing the dopants. These dopants had an unfavorable effect on the Au particle size, as confirmed by the TEM studies. Accordingly, the effects on catalytic performance of the M dopant of the obtained Au/MMgAlO_x catalyst were improved. Results of Raman, NH₃-TPD, and CO₂-TPD confirmed that the Au/CuMgAlO_x catalyst had more basic sites, which is beneficial for less coking on the catalyst surface after the reaction. XPS analysis showed that gold nanoparticles exhibited a partially oxidized state at the edges and surfaces of CuMgAlO_x. Besides an increased proportion of basic sites on Au/CuMgAlO_x catalysts, the charge transfer from nanogold to the Cu-doped matrix support probably played a positive role in the selective hydrogenation of acetylene. The stability and deactivation of Au/CuMgAlO_x catalysts were also discussed and a possible reaction mechanism was proposed. Full article

This study explores the use of the iron-containing metal–organic framework (MOF), Basolite^®F300, as a heterogeneous catalyst for electrochemically-driven Fenton processes. Electrochemical advanced oxidation processes (EAOPs) have shown promise on the abatement of recalcitrant organic pollutants such as pharmaceuticals. Tetracyclines (TC) are a frequently used class of antibiotics that are now polluting surface water and groundwater sources worldwide. Acknowledging the fast capability of EAOPs to treat persistent pharmaceutical pollutants, we propose an electrochemical Fenton treatment process that is catalyzed by the use of a commercially available MOF material to degrade TC. The efficiency of H₂O₂ generation in the IrO₂/carbon felt setup is highlighted. However, electrochemical oxidation with H₂O₂ production (ECO-H₂O₂) alone is not enough to achieve complete TC removal, attributed to the formation of weak oxidant species. Incorporating Basolite^®F300 in the heterogeneous electro-Fenton (HEF) process results in complete TC removal within 40 min, showcasing its efficacy. Additionally, this study explores the effect of varying MOF concentrations, indicating optimal removal rates at 100 mg L⁻¹ due to a balance of kinetics and limitation of active sites of the catalysts. Furthermore, the impact of the applied current on TC removal is investigated, revealing a proportional relationship between current and removal rates. The analysis of energy efficiency emphasizes 50 mA as the optimal current, however, balancing removal efficiency with electrical energy consumption. This work highlights the potential of Basolite^®F300 as an effective catalyst in the HEF process for pollutant abatement, providing valuable insights into optimizing electrified water treatment applications with MOF nanomaterials to treat organic pollutants. Full article

The imperative reduction of carbon dioxide into valuable fuels stands as a crucial step in the transition towards a more sustainable energy system. Perovskite oxides, with their high compositional and property adjustability, emerge as promising catalysts for this purpose, whether employed independently or as a supporting matrix for other active metals. In this study, an A-site-deficient La_0.9FeO₃ perovskite underwent surface decoration with Ni, Cu or Ni + Cu via a citric acid-templated wet impregnation method. Following extensive characterization through XRD, N₂ physisorption, H₂-TPR, SEM-EDX, HAADF STEM-EDX mapping, CO₂-TPD and XPS, the prepared powders underwent reduction under diluted H₂ to yield metallic nanoparticles (NPs). The prepared catalysts were then evaluated for CO₂ reduction in a CO₂/H₂ = 1/4 mixture. The deposition of Ni or Cu NPs on the perovskite support significantly enhanced the conversion of CO₂, achieving a 50% conversion rate at 500 °C, albeit resulting in only CO as the final product. Notably, the catalyst featuring Ni-Cu co-deposition outperformed in the intermediate temperature range, exhibiting high selectivity for CH₄ production around 350 °C. For this latter catalyst, a synergistic effect of the metal–support interaction was evidenced by H₂-TPR and CO₂-TPD experiments as well as a better nanoparticle dispersion. A remarkable stability in a 20 h time-span was also demonstrated for all catalysts, especially the one with Ni-Cu co-deposition. Full article

Increased demand for ethylene has motivated direct ethane dehydrogenation over Pt-based catalysts. PtSn/γ-Al₂O₃ and PtSnZnCa/γ-Al₂O₃ catalysts were investigated with the aim of understanding the effect of the pretreatment environment on the state of dispersed Pt for ethane dehydrogenation. The catalysts were prepared by the impregnation method and pretreated in different environments like static air (SA), flowing air (FA), and nitrogen (N₂) atmospheres. A comprehensive characterization of the catalysts was performed using Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR), NH₃ Temperature-Programmed Desorption (NH₃-TPD), X-ray photoelectron spectroscopy (XPS), and Transmission Electron Microscopy (TEM) techniques. The results reveal that the PtSn on Al₂O₃ catalyst pretreated in the static air environment (PtSn-SA) exhibits 21% ethylene yield with 95% selectivity at 625 °C. XPS analysis found more platinum and tin on the catalyst surface after static air treatment. The overall acidity of the catalysts decreased after thermal treatment in static air. Elemental mapping demonstrated that Pt agglomeration was pronounced in catalysts calcined under flowing air and nitrogen. These factors are responsible for the enhanced activity of the PtSn-SA catalyst compared to the other catalysts. The addition of Zn and Ca to the PtSn catalysts increases the yield of the catalyst calcined in static air (PtSnZnCa-SA). The PtSnZnCa-SA catalyst showed the highest ethylene yield of 27% with 99% selectivity and highly stable activity at 625 °C for 10 h. Full article

Soil contamination by polycyclic aromatic hydrocarbons (PAHs) has been an environmental issue worldwide, which aggravates the ecological risks faced by animals, plants, and humans. In this work, the composites of nanoscale zero-valent iron supported on carbonylated activated carbon (nZVI-CAC) were prepared and applied to activate persulfate (PS) for the degradation of PAHs in contaminated soil. The prepared nZVI-CAC catalyst was characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It was found that the PS/nZVI-CAC system was superior for phenanthrene (PHE) oxidation than other processes using different oxidants (PS/nZVI-CAC > PMS/nZVI-CAC > H₂O₂/nZVI-CAC) and it was also efficient for the degradation of other six PAHs with different structures and molar weights. Under optimal conditions, the lowest and highest degradation efficiencies for the selected PAHs were 60.8% and 90.7%, respectively. Active SO₄^−• and HO^• were found to be generated on the surface of the catalysts, and SO₄^−• was dominant for PHE oxidation through quenching experiments. The results demonstrated that the heterogeneous process using activated PS with nZVI-CAC was effective for PAH degradation, which could provide a theoretical basis for the remediation of PAH-polluted soil. Full article

The lack of efficient and non-precious metal catalysts poses a challenge for electrochemical water splitting in hydrogen and oxygen evolution reactions. Here, we report on the preparation of growing Ni(OH)₂ nanosheets in situ on a Ni and graphene hybrid using supergravity electrodeposition and the hydrothermal method. The obtained catalyst displays outstanding performance with small overpotentials of 161.7 and 41 mV to acquire current densities of 100 and 10 mA cm⁻² on hydrogen evolution reaction, overpotentials of 407 and 331 mV to afford 100 and 50 mA cm⁻² on oxygen evolution reaction, and 10 mA·cm⁻² at a cell voltage of 1.43 V for water splitting in 1 M KOH. The electrochemical activity of the catalyst is higher than most of the earth-abundant materials reported to date, which is mainly due to its special hierarchical structure, large surface area, and good electrical conductivity. This study provides new tactics for enhancing the catalytic performance of water electrolysis. Full article

The main groups of catalytic materials used in the conversion of methanol to dimethyl ether (the MTD process) were presented with respect to their advantages, disadvantages, and the methods of their modifications, resulting in catalysts with improved activity, selectivity, and stability. In particular, the effects of strength, surface concentration, and the type of acid sites, the porous structure and morphology of the catalytic materials, the role of catalyst activators, and others, were considered. The prosed mechanisms of the MTD process over various types of catalysts are presented. Moreover, the advantages of membrane reactors for the MTD process are presented and analysed. The perspectives in the development of effective catalysts for the dehydration of methanol to dimethyl ether are presented and discussed. Full article

The combination of water electrolysis and renewable energy to produce hydrogen is a promising way to solve the climate and energy crisis. However, the fluctuating characteristics of renewable energy not only present a significant challenge to the use of water electrolysis electrodes, but also limit the development of the hydrogen production industry. In this study, the effects of three different types of waveforms (square, step, and triangle, which were used to simulate the power input of renewable energy) on the electrochemical catalysis behavior of Ni plate cathodes for HER was investigated. During the test, the HER performance of the Ni cathode increased at first and then slightly decreased. The fluctuating power led to the degradation of the Ni cathode surface, which enhanced the catalysis effect by increasing the catalytic area and the active sites. However, prolonged operation under power fluctuations could have damaged the morphology of the electrode surface and the substances comprising this surface, potentially resulting in a decline in catalytic efficiency. In addition, the electrochemical catalysis behavior of the prepared FeNiMo-LDH@NiMo/SS cathode when subjected to square-wave potential with different fluctuation amplitudes was also extensively studied. A larger amplitude of fluctuating power led to a change in the overpotential and stability of the LDH electrode, which accelerated the degradation of the cathode. This research provides a technological basis for the coupling of water electrolysis and fluctuating renewable energy and thus offers assistance to the development of the “green hydrogen” industry. Full article

Manganese oxide-cerium oxide supported on titanate nanotubes (i.e., MnCe/TiNTs) were prepared and their catalytic activities towards NH₃-SCR of NO were tested. The results indicated that the MnCe/TiNT catalyst can achieve a high NO removal efficiency above 95% within the temperature range of 150–350 °C. Even after exposure to a HCl-containing atmosphere for 2 h, the NO removal efficiency of the MnCe/TiNT catalyst maintains at approximately 90% at 150 °C. This is attributed to the large specific surface area as well as the unique hollow tubular structure of TiNTs that exposes more Ce atoms, which preferentially react with HCl and thus protect the active Mn atoms. Moreover, the abundant OH groups on TiNTs serve as Brønsted acid sites and provide H protons to expel Cl atom from the catalyst surface. The irreversible deactivation caused by HCl can be alleviated by H₂O. That is because the dissociated adsorption of H₂O on TiNTs forms additional OH groups and relieves HCl poisoning. Full article

A binuclear dioxomolybdenum catalyst [(MoO₂Cl₂)₂(L)] (1) (with L (1S,2S)-N,N′-bis(2-pyridinecarboxamide)-1,2-cyclohexane) was prepared and used as catalyst for the desulfurization of a multicomponent model fuel containing the most refractory sulfur compounds in real fuels. This complex was shown to have a high efficiency to oxidize the aromatic benzothiophene derivative compounds present in fuels, mainly using a biphasic 1:1 model fuel/MeOH system. This process conciliates catalytic oxidative and extractive desulfurization, resulting in the oxidation of the sulfur compounds in the polar organic solvent. The oxidative catalytic performance of (1) was shown to be influenced by the presence of water in the system. Using 50% aq. H₂O₂, it was possible to reuse the catalyst and the extraction solvent, MeOH, during ten consecutive cycles without loss of desulfurization efficiency. Full article

The immobilization of enzymes is an important strategy to improve their stability and reusability. Enzyme immobilization technology has broad application prospects in biotechnology, biochemistry, environmental remediation, and other fields. In this study, composites of chitosan (CS) and sodium alginate (SA) with Cu²⁺ forming a double-network crosslinked structure of hydrogels were prepared and used for the immobilization of laccase. Fourier infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy tests revealed that laccase molecules were immobilized on the composite hydrogel surface by a covalent bonding method. Compared to free laccase, the pH, temperature, and storage stability of the immobilized laccase were markedly improved. In addition, the immobilized laccase could be easily separated from the reaction system and reused, and it maintained 81.6% of its initial viability after six cycles of use. Bisphenol A (BPA) in polluted water was efficiently degraded using immobilized laccase, and the factors affecting the degradation efficiency were analyzed. Under the optimal conditions, the BPA removal was greater than 82%, and the addition of a small amount of ABTS had a significant effect on BPA degradation, with a removal rate of up to 99.1%. Experimental results indicated that immobilized laccases had enormous potential in actual industrial applications. Full article

The global issue for proton exchange membrane fuel cell market development is a reduction in the device cost through an increase in efficiency of the oxygen reduction reaction occurring at the cathode and an extension of the service life of the electrochemical device. Losses in the fuel cell performance are due to various degradation mechanisms in the catalytic layers taking place under conditions of high electric potential, temperature, and humidity. This review is devoted to recent advances in the field of increasing the efficiency and durability of electrocatalysts and other electrode materials by introducing structured carbon components into their composition. The main synthesis methods, physicochemical and electrochemical properties of materials, and performance of devices on their basis are presented. The main correlations between the composition and properties of structured carbon electrode materials, which can provide successful solutions to the highlighted issues, are revealed. Full article

It is common to use efficient catalysts in the anodes and cathodes of methanol and ethanol fuel cells, such as platinum and ruthenium. However, due to their expansivity and rarity, finding a suitable alternative is important. In this work, multi-component catalysts consisting of tungsten oxide, nickel cobaltite, and activated carbon were synthesized through the hydrothermal method. The performance of catalysts in the processes of methanol and ethanol oxidation reactions (MOR and EOR) were investigated. The addition of activated carbon obtained from wheat husk, with an excellent active surface and acceptable electrical conductivity, to the matrix of the catalyst significantly facilitated the oxidation process of alcohols and enhanced the efficiency of the catalyst. The physical and electrochemical characterization of the NiCo₂O₄/WO₃ hybridized with the wheat husk-derived activated carbon (ACWH) catalyst indicated its successful synthesis and good performance in the alcohol oxidation process. NiCo₂O₄/WO₃/ACWH with an oxidation current density of 63.39 mA/cm² at the peak potential of 0.58 V (1.59 vs. RHE), a cyclic stability of 98.6% in the methanol oxidation reaction (MOR) and 27.98 mA/cm² at the peak potential of 0.67 V (1.68 vs. RHE), and a cyclic stability of 95.7% in the ethanol oxidation reaction (EOR) process can be an interesting option for application in the anodes of alcohol fuel cells. Full article

A proton exchange membrane fuel cell (PEMFC) is an efficient and environmentally friendly power production technology that uses hydrogen energy. The cathodic oxygen reduction electrode is a critical component in the development of PEMFC. Most techniques deposit catalyst nanoparticles in areas that are inaccessible for catalytic processes, reducing platinum utilization. The substrate used in this study was carbon paper (CP) with a self-supporting structure. First, electrochemical acidification technology was employed to modify the CP’s surface, followed by nanoparticle manufacturing and fixation on the CP in a single step by electrodeposition. The Pt/C_0.5V_2.24CP catalyst electrode demonstrated high-quality activity in the oxygen reduction reaction (ORR), with a homogeneous particle dispersion and particle size of around 50 nm. The mass activity and electrochemical active surface area (ECSA) of the Pt/C_0.5V_2.24CP catalyst electrode were 1.74 and 3.98 times higher than those of the Pt/C/CP-1 electrodes made with commercial catalysts, respectively. After 5000 cycles of accelerated durability testing (ADT), the mass activity and ECSA were 1.28 times and 6.16 times more than Pt/C/CP-1. This paper successfully proved the viability of electrodepositing Pt nanoparticles on CP following acidification, and that the electrochemical acidification methods have a positive influence on improving electrode ORR activity. Full article

CeO₂-ZrO₂-La₂O₃ supported Pt-Pd bimetallic three-way catalysts (0.6Pt-0.4Pd/CZL) were synthesized through the conventional impregnation method and then subjected to severe thermal aging. Reactivating treatments under different temperatures were then applied to the aged catalysts above. Three-way catalytic performance evaluations and dynamic operation window tests along with detailed physio-chemical characterizations were carried out to explore possible structure–activity evolutions during the reactivating process. Results show that the reactivating process conducted at proper temperatures (500~550 °C) could effectively restore the TWC catalytic performance and widen the operation window width. The suitable reactivating temperature ranges are mainly determined by the decomposing temperature of PMO_x species, the thermal stability of PM-O-Ce species, and the encapsulation temperature of precious metals by CZL support. Reactivating under appropriate temperature helps to restore the interaction between Pt and CZL support to a certain extent and to re-expose part of the encapsulated precious metals. Therefore, the dynamic oxygen storage/release capacity, redox ability, as well as thermal stability of PtOx species, can be improved, thus benefiting the TWC catalytic performances. However, the excessively high reactivating temperature would cause further embedment of Pd by CZL support, thus leading to a further decrease in both dynamic oxygen storage/release capacity and the TWC catalytic performance after reactivating treatment. Full article

The manipulation of trap states plays a crucial role in the development of efficient photocatalysts. An ultrathin-shelled Zn-AgIn₅S₈/ZnS quantum dots (QDs) photocatalyst was synthesized via in situ growth using a low-temperature hydrothermal method. The optical properties of the samples coated with ZnS shell were studied vis UV-vis absorption and fluorescence spectra. The ultrathin ZnS shell plays an important role in the Zn-AgIn₅S₈/ZnS core–shell heterostructure photocatalytic water splitting system, which could reduce surface defects, prolong the carrier lifetime and improve the photo-generated electron–hole pair separation effectively, resulting in the improved photocatalytic efficiency and enhanced stability of the catalyst. The results provide an effective guideline for shell thickness design in future constructions of the core–shell heterostructure photocatalyst. Full article

High-performance Cu catalysts were developed for the selective hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO). Among the various catalysts prepared by ammonia evaporation (AE) and impregnation (IM) methods with silica or MFI zeolite supports, the 5% Cu-SiO₂-AE catalyst was the best one. It exhibited 95% selectivity for BDO and 71% conversion of GBL after 2–8 h reaction at 200 °C and 4 MPa H_2, with high stability in five-cycle runs. Comprehensive characterizations showed that the AE method favored generating nano Cu particles with an average size of 2.9 nm on the 5% Cu-SiO₂-AE catalyst. The silica support derived from a sol demonstrated an advantage over the MFI zeolite in the preparation of a highly dispersed and stable Cu catalyst, in view of its anti-sintering and robust composition of Cu⁰, Cu⁺, and Cu²⁺ in the cycling operation. The reaction pathways for GBL to BDO over the Cu catalysts were found to commonly involve reversible reactions of hydrogenation and dehydrogenation, along with subsequent dehydration to form THF. The high performance of the Cu catalysts in the conversion of GBL to BDO was attributed to the high dispersion of Cu, the presence of stable active sites, and fewer strong acid sites in the catalyst. Full article

Water electrolysis is a crucial technology in the production of hydrogen energy. Due to the escalating industrial demand for green hydrogen, the required electrode size for a traditional alkaline water electrolyzer has been increasing. Numerous studies have focused on developing highly active oxygen evolution reaction (OER) catalysts for water electrolysis. However, there remains a significant gap between the microscale synthesis of catalysts in laboratory settings and the macroscale preparation required for industrial scenarios. This challenge is particularly pronounced in the synthesis of sizable self-supported electrodes. In this work, we employed a commercially available Raney Ni-coated Ni mesh as a precursor material to fabricate a self-supported NiFe(OH)_x@Raney Ni anode with a substantial dimension exceeding 300 mm through a straightforward immersion technique. The as-prepared electrode exhibited remarkable electrocatalytic OER activity, as an overpotential of only 240 mV is required to achieve 10 mA cm⁻². This performance is comparable to that of NiFe-LDHs synthesized via a hydrothermal method, which is difficult to scale up for industrial applications. Furthermore, the electrode demonstrated exceptional durability, maintaining stable operation for over 100 h at a current density of 500 mA cm⁻². The large-scale electrode displayed consistent overpotentials across various areas, indicating uniform catalytic activity. When integrated into an alkaline water electrolysis device, it delivered an average cell voltage of 1.80 V at 200 mA cm⁻² and achieved a direct current hydrogen production energy consumption as low as 4.3 kWh/Nm³. These findings underline the suitability of electrodes for industrial scale applications, offering a promising alternative for energy-efficient hydrogen production. Full article

Three-way catalysts (TWCs) are widely used in vehicles to convert the exhaust emissions from internal combustion engines into less toxic pollutants. After around 8–10 years of use, the declining catalytic activity of TWCs causes them to need replacing, leading to the generation of substantial amounts of spent TWC material containing precious metals, including palladium. It has previously been reported that [NⁿBu₄]₂[Pd₂I₆] is obtained in high yield and purity from model TWC material using a simple, inexpensive and mild reaction based on tetrabutylammonium iodide in the presence of iodine. In this contribution, it is shown that, through a simple ligand exchange reaction, this dimeric recovery complex can be converted into PdI₂(dppf) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), which is a direct analogue of a commonly used catalyst, PdCl₂(dppf). [NⁿBu₄]₂[Pd₂I₆] displayed high catalytic activity in the oxidative functionalisation of benzo[h]quinoline to 10-alkoxybenzo[h]quinoline and 8-methylquinoline to 8-(methoxymethyl)quinoline in the presence of an oxidant, PhI(OAc)₂. Near-quantitative conversions to the desired product were obtained using a catalyst recovered from waste under milder conditions (50 °C, 1–2 mol% Pd loading) and shorter reaction times (2 h) than those typically used in the literature. The [NⁿBu₄]₂[Pd₂I₆] catalyst could also be recovered and re-used multiple times after the reaction, providing additional sustainability benefits. Both [NⁿBu₄]₂[Pd₂I₆] and PdI₂(dppf) were also found to be active in Buchwald–Hartwig amination reactions, and their performance was optimised through a Design of Experiments (DoE) study. The optimised conditions for this waste-derived palladium catalyst (1–2 mol% Pd loading, 3–6 mol% of dppf) in a bioderived solvent, cyclopentyl methyl ether (CPME), offer a more sustainable approach to C-N bond formation than comparable amination protocols. Full article

The hydrogenation of carbon monoxide (CO) offers a promising avenue for reducing air pollution and promoting a cleaner environment. Moreover, by using suitable catalysts, CO can be transformed into valuable hydrocarbons. In this study, we elucidate the mechanistic aspects of the catalytic conversion of CO to hydrocarbons on the surface of manganese-doped graphene oxide (Mn-doped GO), where the GO surface includes one OH group next to one Mn adatom. To gain insight into this process, we have employed calculations based on the density functional theory (DFT) to explore both the thermodynamic properties and reaction energy barriers. The Mn adatoms were found to significantly activate the catalyst surface by providing stronger adsorption geometries. Our study concentrated on two mechanisms for CO hydrogenation, resulting in either CH₄ production via the reaction sequence CO → HCO → CH₂O → CH₂OH → CH₂ → CH₃ → CH₄ or CH₃OH formation through the CO → HCO → CH₂O → CH₂OH → CH₃OH pathway. The results reveal that both products are likely to be formed on the Mn-doped GO surface on both thermodynamic grounds and considering the reaction energy barriers. Furthermore, the activation energies associated with each stage of the synthesis show that the conversion reactions of CH₂ + OH → CH₃ + O and CH₂O + OH → CH₂OH + O with energy barriers of 0.36 and 3.86 eV are the fastest and slowest reactions, respectively. The results also indicate that the reactions: CH₂OH + OH → CH₂ + O + H₂O and CH₂OH + OH → CH₃OH + O are the most exothermic and endothermic reactions with reaction energies of −0.18 and 1.21 eV, respectively, in the catalytic pathways. Full article