Catalysis for Sustainable Chemistry and Energy

Selective catalytic reduction (SCR) is an effective system for treating nitrogen oxides (NO_x; mainly NO), and fast SCR requires the equimolar reactants of NO and NO₂. This study focused on catalysts for oxidizing 50% of NO to NO₂. A series of catalysts composed of a variety of components, such as mesoporous mMnO₂-nCeO₂ as carrier catalysts (m:n = 9:1 and 7:3) and transition metals (e.g., Fe, Co, Ni, Cu, and Cr), were synthesized and characterized using N₂ adsorption, in situ XRD, TEM, and XPS. All samples had a mesoporous structure with pore size around 8 nm. XPS results demonstrated that addition of cerium ion increased the surface area and provided oxygen vacancy due to the formation of Ce³⁺ within the structure. NO oxidation activity was tested using a feed (205~300 ppm NO and 6% O₂) that simulated typical flue gas conditions. Doped mesoporous mMnO₂–nCeO₂ has higher NO oxidation activity than pristine mMnO₂–nCeO₂. The doped mMnO₂-nCeO₂ catalyzed 50% of NO to NO₂ at between 140 and 200 °C resulting in an equivalent amount of NO and NO₂. Among the transition metals, Cu, Ni, Co, Fe, and Cr have the highest to lowest oxidation activity, respectively. The precatalytic oxidation of NO can potentially be combined with the current SCR system without changes to existing equipment and can be applied to the exhaust gas treatment for de-NO_x. Full article

Nanostructured materials have gained much attention in recent engineering and material- science research due to their unique structural makeup, which stands them out from their bulk counterparts. Their novel properties of tiny-size structural elements (molecules or crystallites, clusters) of nanoscale dimensions (1 to 100 nm) make them a perfect material for energy applications. The recent keen interest in nanostructured materials research by academia and industrial experts arises from the unique variable characteristics of increased electrical and thermal conductivity. This occurs as nanostructured materials undergo a transient process from infinite-extended solid to a particle of ascertainable numbers of atoms. The commercial and energy sectors are very interested in developing and expanding simple synthetic pathways for nanostructured-electrocatalysts materials to aid in optimizing the number of active regions. Over the decades, various techniques have been put forward to design and synthesize nanostructured-electrocatalysts materials for electrochemical generation of energy and storage applications. As a result, the design of fuel cells, supercapacitors, and energy-storage devices has advanced significantly. This review provides a comprehensive outlook of various synthesis techniques and highlight the challenges of nanostructured- electrocatalysts materials application in fuel cells. Several synthesis methods are discussed and summarized for enhanced nanomaterial preparation and high product attainment with the sol-gel synthesis method being emphasized. The design methodology for an effective nanostructured electrocatalysts with high efficiency for fuel cells was also discussed. Full article

Water gas shift reactions (WGS) were evaluated over Ni/CeO₂ and Ni/CeSmO catalysts for hydrogen production. The effects of catalyst preparation method and Sm loading were investigated. The Ni/ceria and Ni/CeSmO catalysts were synthesized by combustion, sol gel and sol gel-combustion method. After WGS tests, the catalysts were determined the carbon deposition by thermogravimetric analysis. The thermogravimetric analysis and temperature programmed NH₃ desorption showed that addition of Sm promoter made higher the weak acid sites and lower the amount of carbon deposition than the unpromoted catalyst due to it being easily removed. CO chemisorption result indicated that Ni/Ce5%SmO catalyst prepared by combustion method has the highest Ni metal dispersion and metallic surface area compared to the other catalysts. The enhancement of WGS activity of this catalyst is due to more surface active sites being exposed to reactants. Furthermore, H₂-temperature programmed reduction analysis confirmed an easiest reduction of this catalyst. This behavior accelerates the redox process at the ceria surface and enhances the oxygen vacancy concentration. The catalytic activity measurements exhibited that the optimum Sm loading was 5% wt. and the best catalyst preparation was the combustion method. The high surface area and small crystallite size of the 5%Ni/Ce5%SmO (combustion) catalyst resulted in sufficient dispersion, which closely related to the WGS activity of the catalyst. Full article

This study aims to examine the hydrodeoxygenation (HDO) of vanillin, an oxygenated phenolic compound present in bio-oil, into creosol. Biochar residue generated when wood is slowly pyrolyzed is utilized as a catalyst support. To improve biochar’s physicochemical properties, H₂SO₄ (sulfuric acid) and KOH (potassium hydroxide) are used as chemical activators. By means of a wet impregnation method with nickel salt, an Ni/biochar catalyst was prepared and utilized in the HDO of vanillin using a 100 mL Parr reactor, catalyst loading 0.4–0.8 g, temperature 100 °C to 150 °C, hydrogen (H₂) pressures of 30 to 50 bar, and a stirring rate of 1000 rpm. The prepared catalysts were characterized with the nitrogen-sorption isotherm technique, carbon dioxide temperature-programmed desorption (CO₂-TPD), scanning electron microscopy (SEM) coupled with energy dispersed X-ray analysis (EDX), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). Based on chemical treatment, Ni/biochar (KOH) pore sizes were found to be dominated by mesopores, with a surface area increase of 64.7% and a volume increase of 65.3%, while Ni/biochar (H₂SO₄) was mostly microporous and mesoporous, with an area increase of 372.3% and a volume increase of 256.8% in comparison to Ni/biochar (74.84 m²g⁻¹ and 0.095 cm³g⁻¹). Vanillin conversion of up to 97% with 91.17% selectivity to p-creosol was obtained over Ni/biochar catalyst; in addition to being highly selective and active for p-creosol, a plausible fuel, the catalyst was stable after four cycles. Chemical treatments of the biochar support resulted in improved physicochemical properties, leading to improved catalytic performance in terms of vanillin conversion and p-creosol yield in the order Ni/biochar (H₂SO₄) > Ni/biochar (KOH) > Ni/biochar. Full article

Ultrasound (US)-assisted synthesis of a N-doped TiO₂ catalyst supported on magnetically separable Fe₃O₄@ZnO particles and its subsequent application for catalytic desulfurization were performed in the present work. The catalyst was also synthesized conventionally to compare the role of acoustic cavitation (US horn working at 20 kHz frequency) in improving the catalyst characteristics. The effects of different ultrasonic (US) power (80 W to 120 W) and duration (15 min to 75 min) were studied to elucidate the best operating conditions for obtaining the minimum particle size of the catalyst. Under optimal conditions of 80 W power and 30 min of time, a minimum particle size of 31.22 μm was obtained. The particle size for the conventionally synthesized catalyst was 806.4 µm, confirming that the particles were agglomerated in the absence of ultrasound. The synthesized catalyst was used for the desulfurization of thiophene to assess the performance of the catalyst, along with a comparative study between the conventionally synthesized catalyst and that obtained using the US-assisted approach. It was evident that the performance of the catalyst synthesized sonochemically was superior, as US enhanced the activity of the catalyst by reducing the particle size and achieving homogeneity. The desulfurization achieved using the sonochemically synthesized catalyst was 47% in 100 min at a 2 g/L catalyst dose and a 3 mL/L H₂O₂ dose. The desulfurization was only 25% using the conventionally synthesized catalysts under the same operating conditions. Overall, the present work demonstrates the advantages of US in improving the catalyst characteristics, as well as the successful application of catalyst in desulfurization. Full article

The susceptibility of the carbonyl group towards nucleophilic attack affords the construction of various organic compounds. Thus, investigations of carbonyl activation applying greener methodologies are highly important. In the present work, among the investigated N-halo compounds, N-fluorobenzenesulfonimide (NFSi) has been found as an efficient and selective catalyst in the reaction of direct esterification of aryl and alkyl carboxylic acids supported by microwave (MW) irradiation. The comprehensive esterification of different benzoic acids and mono-, di- and tri-carboxy alkyl derivatives was performed, whereby significant reaction time reductions were achieved. The presented method used NFSi as an easily manipulatable, non-metal, water- and air-tolerant catalyst, allowing simple synthetic and isolation procedures and energy saving, compared to conventional methodologies. Importantly, in contrast to esterification under thermal conditions, where N-halo compounds behave as pre-catalysts, in the MW-supported protocol, a distinct reaction mechanism has been proposed that assumes NFSi as a sustainable catalyst. Moreover, a scale-up of the industrially important derivative was performed. Full article

In this study, an efficient hierarchical Co–Pi cluster/Fe₂O₃ nanorod/fluorine-doped tin oxide (FTO) micropillar three-dimensional (3D) branched photoanode was designed for enhanced photoelectrochemical performance. A periodic array of FTO micropillars, which acts as a highly conductive “host” framework for uniform light scattering and provides an extremely enlarged active area, was fabricated by direct printing and mist-chemical vapor deposition (CVD). Fe₂O₃ nanorods that act as light absorber “guest” materials and Co–Pi clusters that give rise to random light scattering were synthesized via a hydrothermal reaction and photoassisted electrodeposition, respectively. The hierarchical 3D branched photoanode exhibited enhanced light absorption efficiency because of multiple light scattering, which was a combination of uniform light scattering from the periodic FTO micropillars and random light scattering from the Fe₂O₃ nanorods. Additionally, the large surface area of the 3D FTO micropillar, together with the surface area provided by the one-dimensional Fe₂O₃ nanorods, contributed to a remarkable increase in the specific area of the photoanode. Because of these enhancements and further improvements facilitated by decoration with a Co–Pi catalyst that enhanced water oxidation, the 3D branched Fe₂O₃ photoanode achieved a photocurrent density of 1.51 mA cm⁻² at 1.23 V_RHE, which was 5.2 times higher than that generated by the non-decorated flat Fe₂O₃ photoanode. Full article

For over 2000 years, ginseng (roots of Panax ginseng C.A. Meyer) has been used as a traditional herbal medicine. Ginsenosides are bioactive compounds present in ginseng responsible for the pharmacological effects and curing various acute diseases as well as chronic diseases including cardiovascular disease, cancer and diabetes. Structurally, ginsenosides consist of a hydrophobic aglycone moiety fused with one to four hydrophilic glycoside moieties. Based on the position of sugar units and their abundance, ginsenosides are classified into major and minor ginsenosides. Despite the great potential of ginsenosides, major ginsenosides are poorly absorbed in the blood circulation, resulting in poor bioavailability. Interestingly, owing to their small molecular weight, minor ginsenosides exhibit good permeability across cell membranes and bioavailability. However, extremely small quantities of minor ginsenosides extracted from ginseng plants cannot fulfill the requirement of scientific and clinical studies. Therefore, the production of minor ginsenosides in mass production is a topic of interest. In addition, their poor solubility and lack of targetability to tumor tissues limits their application in cancer therapy. In this review, various methods used for the transformation of major ginsenosides to minor ginsenoside compound K (CK) are summarized. For the production of CK, various transformation methods apply to major ginsenosides. The challenges present in these transformations and future research directions for producing bulk quantities of minor ginsenosides are discussed. Furthermore, attention is also paid to the utilization of nanoformulation technology to improve the bioavailability of minor ginsenoside CK. Full article

Elucidation of the intrinsic catalytic principle of iron carbides remains a substantial challenge in iron-catalyzed Fischer-Tropsch synthesis (FTS), due to possible interference from other Fe-containing species. Here, we propose a facile approach to synthesize single-phase θ-Fe₃C via the pyrolysis of a molecularly defined Fe-C complex (Fe₄[Fe(CN)₆]₃), thus affording close examination of its catalytic behavior during FTS. The crystal structure of prepared θ-Fe₃C is unambiguously verified by combined XRD and MES measurement, demonstrating its single-phase nature. Strikingly, single-phase θ-Fe₃C exhibited excellent selectivity to light olefins (77.8%) in the C₂-C₄ hydrocarbons with less than 10% CO₂ formation in typical FTS conditions. This strategy further succeeds with promotion of Mn, evident for its wide-ranging compatibility for the promising industrial development of catalysts. This work offers a facile approach for oriented preparation of single-phase θ-Fe₃C and provides an in-depth understanding of its intrinsic catalytic performance in FTS. Full article

The dry reforming of methane (DRM) reaction is among the most popular catalytic reactions for the production of syngas (H₂/CO) with a H₂:CO ratio favorable for the Fischer–Tropsch reaction; this makes the DRM reaction important from an industrial perspective, as unlimited possibilities for production of valuable products are presented by the FT process. At the same time, simultaneously tackling two major contributors to the greenhouse effect (CH₄ and CO₂) is an additional contribution of the DRM reaction. The main players in the DRM arena—Ni-supported catalysts—suffer from both coking and sintering, while the activation of the two reactants (CO₂ and CH₄) through different approaches merits further exploration, opening new pathways for innovation. In this review, different families of materials are explored and discussed, ranging from metal-supported catalysts, to layered materials, to organic frameworks. DRM catalyst design criteria—such as support basicity and surface area, bimetallic active sites and promoters, and metal–support interaction—are all discussed. To evaluate the reactivity of the surface and understand the energetics of the process, density-functional theory calculations are used as a unique tool. Full article

The oxygen reduction reaction (ORR) is one of the crucial energy conversion reactions in proton exchange membrane fuel cells (PEMFCs). Low price and remarkable catalyst performance are very important for the cathode ORR of PEMFCs. Among the various explored ORR catalysts, non-noble metals (transition metal: Fe, Co, Mn, etc.) and N co-doped C (M–N–C) ORR catalysts have drawn increasing attention due to the abundance of these resources and their low price. In this paper, the recent advances of single-atom catalysts (SACs) and double-atom catalysts (DACs) in the cathode ORR of PEMFCs is reviewed systematically, with emphasis on the synthesis methods and ORR performance of the catalysts. Finally, challenges and prospects are provided for further advancing non-noble metal catalysts in PEMFCs. Full article

Increasing energy consumption and environmental pollution problems have forced people to turn their attention to the development and utilization of hydrogen energy, which requires that hydrogen energy can be efficiently prepared. However, the sluggish kinetics of hydrogen evolution reaction (HER) requires higher overpotential. It is urgent to design and fabricate catalysts to drive the procedure and decrease the overpotential of HER. It is well known that platinum catalysts are the best for HER, but their high cost limits their wide application. Transition metals such as Fe, Co, Mo and Ni are abundant, and transition metal phosphides are considered as promising HER catalysts. Nevertheless, catalysts in powder form are very easily soluble in the electrolyte, which leads to inferior cycling stability. In this work, Ni₅P₄ anchored on Ni foam was doped with Se powder. After SEM characterization, the Ni₅P₄-Se was anchored on Ni foam, which circumvents the use of the conductive additives and binder. The Ni₅P₄-Se formed a porous nanosheet structure with enhanced electron transfer capability. The prepared Ni₅P₄-Se exhibited high electrochemical performances. At 10 mA cm⁻², the overpotential was only 128 mV and the Tafel slope is 163.14 mV dec⁻¹. Additionally, the overpotential was stabilized at 128 mV for 30 h, suggesting its excellent cycling stability. The results show that Se doping can make the two phases achieve a good synergistic effect, which makes the Ni₅P₄-Se catalyst display excellent HER catalytic activity and stability. Full article

Photocatalysis is a promising process for decomposing harmful organic pollutants in water. In this study, solar/photocatalytic degradation of two model azo dyes, i.e., methylene blue (MB) and methyl red (MR), in water usinga nanostructured chitosan-modified nickel magnetite (CS-NM) bio-composite was investigated. The CS-NM bio-composite was synthesized through a co-precipitation method and characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermogravimetry (TGA), and UV-Vis spectroscopy. FTIR analysis showed the uniform incorporation and conjugation of nickel magnetite (NM) into the chitosan (CS) polymer matrix. SEM showed that the average particle size was 0.5 μm. The TGA results revealed the good thermal stability of the prepared bio-composite at 300 °C. The point of zero charge was calculated as 7.5. The effect of water quality and process parameters, such as concentration of dyes, catalyst dose, solution pH, and temperatures, was investigated, for application purposes. The solar/CS-NM photocatalysis resulted in 99 and 96% degradation of individual MB and MR (C₀ = 50 ppm), respectively, in 90 min. The degradation of MB and MR by solar/CS-NM photocatalysis followed pseudo-first-order kinetics, with observed rate constants (k) of 0.077 and 0.072 min⁻¹, respectively. The CS-NM photocatalyst showed high recyclability, represented by only a 4–6% loss in the photocatalytic efficiency, after four cycles. The results showed that solar/CS-NM photocatalysis is an efficient technique for degrading recalcitrant organic pollutants, such as azo dyes, in water environments. Full article

Inorganic perovskite ferroelectric-based nanomaterials as sustainable new energy materials, due to their intrinsic ferroelectricity and environmental compatibility, are intended to play a crucial role in photoelectrochemical field as major functional materials. Because of versatile physical properties and excellent optoelectronic properties, ferroelectric-based nanomaterials attract much attention in the field of photocatalysis, photoelectrochemical water splitting and photovoltaic. The aim of this review is to cover the recent advances by stating the different kinds of ferroelectrics separately in the photoelectrochemical field as well as discussing how ferroelectric polarization will impact functioning of photo-induced carrier separation and transportation in the interface of the compounded semiconductors. In addition, the future prospects of ferroelectric-based nanomaterials are also discussed. Full article

Hydrogen is the mainstream future energy source because of its high energy density and environmentally-friendly properties. In this study, Fe-Co₂P/NPC materials were prepared by the wet chemical synthesis method, in which Fe-Co₂P nanowires were wrapped by the N, P co-doped carbon layers (NPC) under aging and phosphorylation strategies. When Fe-Co₂P/NPC/NF was subjected to hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), the overpotential was only 73 mV and 217 mV to reach the current density of 10 mA cm⁻², respectively. When the cathode and anode were both Fe-Co₂P/NPC/NF, a current density of 10 mA cm⁻² was achieved with only 1.56 V. This work provides a new idea for the design and preparation of non-precious metal-based transition metal phosphide catalysts. Full article

A series of rutile TiO₂-supported Ni catalysts with varying Ni sizes were prepared and reduced at 650 °C to explore the effect of Ni size on the strong metal–support interactions (SMSI) and its consequences on the hydrodeoxygenation (HDO) of m-cresol at 350 °C and atmospheric pressure. When the Ni size increases from 4 to 29.1 nm, the SMSI becomes stronger, e.g., the thickness of the TiO_x overlayer and the coverage extent of TiO_x on the Ni particle surface increase. Direct deoxygenation to toluene is the dominant pathway on Ni/TiO₂ catalysts with varying Ni loadings, with almost no CH₄ being formed. These results indicate that the TiO_x overlayer significantly alters the property of Ni. That is, the C-C hydrogenolysis activity on bare Ni is completely inhibited due to SMSI, while the deoxygenation activity is improved at the Ni-TiO_x interfacial perimeter sites. Meanwhile, the turnover frequency of HDO on small Ni particles of 4 nm is > 2 times higher than that on large Ni particles of 29.1 nm, indicating that the small Ni particle with moderate SMSI appears to be optimal for the direct deoxygenation of m-cresol to toluene. The results suggest HDO activity may be enhanced by tuning the metal particle size and SMSI degree. Full article

Catalytic conversions of bioethanol to propylene were investigated over different zeolite catalysts. H-ZSM-5 (SiO₂/Al₂O₃ = 80) was found to be the most effective for propylene production. Furthermore, H-ZSM-5 (SiO₂/Al₂O₃ = 80) was investigated under different variables of catalytic reaction (calcination temperature, feed composition, reaction temperature, and time on stream) for the conversion of ethanol to propylene. The H-ZSM-5(80) catalysts calcined at 600 °C showed the highest propylene yield. The moderate acidic site on ZSM-5 is required for the production of propylene. The activity on ZSM-5 is independent of the ethanol feed composition. H-ZSM-5 catalyst deactivation was observed, owing to dealumination. The highest propylene yield was 23.4% obtained over HZSM-5(80). Propylene, butene, and ≥C5 olefins were formed by parallel reaction from ethylene. Olefins were converted to each paraffin by sequential hydrogenation reaction. HZSM-5(80) catalyst is a promising catalyst not only for ethanol but also for the conversion of bioethanol to light olefins. Full article

Although they are of significant importance for environmental applications, the industrialization of photocatalytic techniques still faces many difficulties, and the most urgent concern is cost control. Natural minerals possess abundant chemical inertia and cost-efficiency, which is suitable for hybridizing with various effective photocatalysts. The use of natural minerals in photocatalytic systems can not only significantly decrease the pure photocatalyst dosage but can also produce a favorable synergistic effect between photocatalyst and mineral substrate. This review article discusses the current progress regarding the use of various mineral classes in photocatalytic applications. Owing to their unique structures, large surface area, and negatively charged surface, silicate minerals could enhance the adsorption capacity, reduce particle aggregation, and promote photogenerated electron-hole pair separation for hybrid photocatalysts. Moreover, controlling the morphology and structure properties of these materials could have a great influence on their light-harvesting ability and photocatalytic activity. Composed of silica and alumina or magnesia, some silicate minerals possess unique orderly organized porous or layered structures, which are proper templates to modify the photocatalyst framework. The non-silicate minerals (referred to carbonate and carbon-based minerals, sulfate, and sulfide minerals and other special minerals) can function not only as catalyst supports but also as photocatalysts after special modification due to their unique chemical formula and impurities. The dye-sensitized minerals, as another natural mineral application in photocatalysis, are proved to be superior photocatalysts for hydrogen evolution and wastewater treatment. This work aims to provide a complete research overview of the mineral-supported photocatalysts and summarizes the common synergistic effects between different mineral substrates and photocatalysts as well as to inspire more possibilities for natural mineral application in photocatalysis. Full article

Electrochemical water splitting has wide applicability in preparing high-density green energy. The Proton exchange membrane (PEM) water electrolysis system is a promising technique for the generation of hydrogen due to its high electrolytic efficiency, safety and reliability, compactness, and quick response to renewable energy sources. However, the instability of catalysts for electrochemical water splitting under operating conditions limits their practical applications. Until now, only precious metal-based materials have met the requirements for rigorous long-term stability and high catalytic activity under acid conditions. In this review, the recent progress made in this regard is presented and analyzed to clarify the role of precious metals in the promotion of the electrolytic decomposition of water. Reducing precious metal loading, enhancing catalytic activity, and improving catalytic lifetime are crucial directions for developing a new generation of PEM water electrolysis catalysts. A summary of the synthesis of high-performance catalysts based on precious metals and an analysis of the factors affecting catalytic performance were derived from a recent investigation. Finally, we present the remaining challenges and future perspectives as guidelines for practical use. Full article

The deactivation of catalysts and their regeneration are two very important challenges that need to be addressed for many industrial processes. The most quoted reasons for the deterioration of dimethyl ether synthesis (DME) concern the sintering and the hydrothermal leaching of copper particles, their migration to acid sites, the partial formation of copper and zinc hydroxycarbonates, the formation of carbon deposits, and surface contamination with undesirable compounds present in syngas. This review summarises recent findings in the field of DME catalyst deactivation and regeneration. The most-used catalysts, their modifications, along with a comparison of the basic parameters, deactivation approaches, and regeneration methods are presented. Full article

The need for energy resources is growing all the time, which means that more fossil fuels are needed to provide them. People prefer to consume chicken as a source of protein, and this creates an abundance of waste. Thus, microbial fuel cells represent a new technological approach with the potential to generate electricity through the action of electrogenic bacteria toward chicken manure, while reducing the abundance of chicken manure. This study investigated the effect of different pretreatment (thermal, alkaline, and sonication pretreatment) of chicken manure to improve the performance of a membrane-less microbial fuel cell (ML-MFC). Statistical response surface methodology (RSM) through a central composite design (CCD) under a quadratic model was conducted for optimization of the ML-MFC performance focusing on the COD removal efficiency (R² = 0.8917), biomass (R² = 0.9101), and power density response (R² = 0.8794). The study demonstrated that the highest COD removal (80.68%), biomass (7.8539 mg/L), and power density (220 mW/m²) were obtained when the pretreatment conditions were 140 °C, 20 kHz, and pH 10. The polarization curve of the best condition of ML-MFC was plotted to classify the behavior of the ML-MFC. The kinetic growth of Bacillus subtillis (BS) showed that, in treated chicken manure, the specific growth rate µ = 0.20 h⁻¹ and doubling time Td = 3.43 h, whereas, in untreated chicken manure, µ = 0.11 h⁻¹ and Td = 6.08. Full article

In this work, photocatalytic performance is divulged in the ternary CuO-Ag-ZnO nanowire synthesized via a two-step approach. The decoration of Ag and CuO nanostructures onto the surface of ZnO nanowires was simply carried out by using the plasma electrolytic oxidation method in a short time. The structure, size, morphology, and optical properties of as-prepared samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, and spectrophotometry measurements. The diameters of Ag nanoparticles and ZnO nanoflowers are in the range of 5–20 nm and 20–60 nm, respectively. Within the first 15 min, methyl orange was decolorized 96.3 and 82.8% in the CuO-Ag-ZnO and Ag-ZnO, respectively, and there is only about 46.7% of that decomposed in pure ZnO. The CuO-Ag-ZnO shows a higher rate constant k = 0.2007 min⁻¹ and a lower half-life time t = 6.1 min compared to Ag-ZnO and bare ZnO nanowires. The photo-reusability of the ternary nanostructures was estimated to be much outweighed compared to ZnO nanowires. Interestingly, the synergic incorporation between noble metal–semiconductor or semiconductor–semiconductor in the interfaces of Ag-CuO, Ag-ZnO, and CuO-ZnO expands the visible light absorption range and eliminates the photogenerated electron–hole recombination, resulting in a superior visible-light-driven photocatalyst. Full article

Silica, titania, and mixed silica–titania powders have been used as supports for loading 5 wt% Cu, 5 wt% Ag, and 2.5 wt% Cu-2.5 wt% Ag with the aim of providing a series of nanomaterials with antifouling properties. All the solids were easily prepared by the wetness-impregnation method from commercially available chemical precursors. The resulting materials were characterized by several techniques such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, N₂ physisorption, and temperature-programmed reduction measurements. Four selected Cu and Ag SiO₂- and TiO₂-supported powders were tested as fillers for the preparation of marine antifouling coatings and complex viscosity measurements. Titania-based coatings showed better adhesion than silica-based coatings and the commercial topcoat. The addition of fillers enhances the resin viscosity, suggesting better workability of titania-based coatings than silica-based ones. The ecotoxicological performance of the powders was evaluated by Microtox luminescence tests, using the marine luminescent bacterium Vibrio fisheri. Further investigations of the microbiological activity of such materials were carried out focusing on the bacterial growth of Pseudoalteromonas sp., Alteromonas sp., and Pseudomonas sp. through measurements of optical density at 600 nm (OD_600nm). Full article

The replacement of noble metal catalysts by abundant iron as an active compound in CO oxidation is of ecologic and economic interest. However, improvement of their catalytic performance to the same level as state-of-the-art noble metal catalysts requires an in depth understanding of their working principle on an atomic level. As a contribution to this aim, a series of iron oxide catalysts with varying Fe loadings from 1 to 20 wt% immobilized on a γ-Al₂O₃ support is presented here, and a multidimensional structure–activity correlation is established. The CO oxidation activity is correlated to structural details obtained by various spectroscopic, diffraction, and microscopic methods, such as PXRD, PDF analysis, DRUVS, Mössbauer spectroscopy, STEM-EDX, and XAS. Low Fe loadings lead to less agglomerated but high percentual amounts of isolated, tetrahedrally coordinated iron oxide species, while the absolute amount of isolated species reaches its maximum at high Fe loadings. Consequently, the highest CO oxidation activity in terms of turnover frequencies can be correlated to small, finely dispersed iron oxide species with a large amount of tetrahedrally oxygen coordinated iron sites, while the overall amount of isolated iron oxide species correlates with a lower light-off temperature. Full article

The exploitation of highly efficient and stable hydrogen generation from chemical storage of formaldehyde (FA) is of great significance to the sustainable development of the future. Moreover, developing an accurate, rapid, reliable, and cost-effective catalyst for electrochemical detection of FA in solution is appealing. Herein, we report rational construction of Pd nanoparticles decorated reduced graphene oxides (Pd/rGO) nanohybrids not only as robust catalysts to produce hydrogen from alkaline FA solution and but also electrocatalysts for electrochemical detection of FA. By optimizing the reaction parameters including FA concentration, NaOH concentration and reaction temperature, Pd/rGO with Pd loading of 0.5 wt% could exhibit a high hydrogen production rate of 272 mL g⁻¹min⁻¹ at room temperature of 25 °C, which is 3.2 times that of conventional Pd NPs. In addition, as-prepared Pd/rGO nanohybrids modified glassy carbon (GC) electrodes are used as FA-detected electrochemical sensors. A sensitive oxidation peak with a current density of 8.38 mA/cm² was observed at 0.12 V (vs. Ag/AgCl) in 0.5 M NaOH containing 10 mM FA over Pd/rGO catalysts with Pd loading of 0.5 wt%. The results showed the prepared Pd/rGO nanocatalyst not only exhibited efficient and stable hydrogen production from alkaline FA solution but also had good electrocatalytic properties with respect to formaldehyde electrooxidation as a result of the synergistic effect of Pd NPs and rGO nanosheets. Full article

Activated two-dimension (2D) materials are used in various applications as high-performance catalysts. Breaking the long-range order of the basal plane of 2D materials can highly promote catalytic activity by supplying more active sites. Here we developed a method to synthesize ultrathin MCoO_x (M = V, Mn, Fe, Ni, Cu, Zn) amorphous nanosheets (ANSs). These Co-based ANSs show high oxygen evolution reaction (OER) activity in alkaline solution due to the broken long-range order and the presence of abundant low bonded O on the basal plane. The stable Fe₁Co₁O_x ANSs also show an overpotential of ca. 240 mV of achieving 10 mA/cm² in OER, better than most reported transition metal-based electrocatalysts. Full article

The Ni/P ratio of nickel phosphide has an important effect on the catalytic performance toward the deoxygenation of fatty acids to biofuel. The Ni₁₂P₅ cluster is preferred to model Ni₁₂P₅ catalyst with butyric acid as the reactant model of palmitic acid. The catalytic deoxygenation mechanism of butyric acid over Ni₁₂P₅ cluster has been theoretically investigated at GGA-PBE/DSPP, DNP level in dodecane solution. From butyric acid, the hydrodehydration is predominated to form n-butanal. Then, from n-butanal, low temperature benefits the hydroreduction to form butanol and then hydrodehydration to produce n-butane, whereas high temperature favors the direct decarbonylation to yield propane. n-Butane originates from n-butanol through hydrodehydration and not from n-butylene. Propane comes from n-butanal through decarbonylation and not from propanol and/or propylene. Additionally, CO stems from n-butanal through decarbonylation, whereas CO₂ is ruled out from butyric acid through decarboxylation. Compared with Ni₁₂P₆ cluster, Ni₁₂P₅ cluster exhibits higher catalytic activity for the formation of butanal, n-butanol, and n-butane, while it displays lower catalytic activity toward the direct decarbonylation and dehydration to yield propylene. These results can be attributed to less negative charges of Ni-sites over Ni₁₂P₅ cluster, compared with Ni₁₂P₆ cluster. Full article

Photocatalytic production from water is considered an effective solution to fossil fuel-related environmental concerns, and photocatalyst surface science holds a significant interest in balancing photocatalysts’ stability and activity. We propose a plasma-wind method to tune the surface properties of a photocatalyst with an amorphous structure. Theoretical calculation shows that the amorphous surface structure can cause an unsaturated coordination environment to adjust the electron distribution, forming more adsorption sites. Thus, the photocatalyst with a crystal–amorphous (C–A) interface can strengthen light absorption, harvest photo-induced electrons, and enrich the active sites, which help improve hydrogen yield. As a proof of concept, with indium sulfide (In₂S₃) nanosheets used as the catalyst, an impressive hydrogen production rate up to 457.35 μmol cm⁻² h⁻¹ has been achieved. Moreover, after plasma-assisted treatment, In₂S₃ with a C–A interface can produce hydrogen from water under natural outdoor conditions. Following a six-hour test, the rate of photocatalytic hydrogen evolution is found to be 400.50 μmol cm⁻² g⁻¹, which demonstrates that a catalyst prepared through plasma treatment is both effective and highly practical. Full article

Dry reforming of methane was studied over high-ratio zirconia in ceria-zirconia-mixed oxide-supported Ni catalysts. The catalyst was synthesized using co-precipitation and impregnation methods. The effects of the catalyst support and Ni composition on the physicochemical characteristics and performance of the catalysts were investigated. Characterization of the physicochemical properties was conducted using X-ray diffraction (XRD), N₂-physisorption, H₂-TPR, and CO₂-TPD. The results of the activity and stability evaluations of the synthesized catalysts over a period of 240 min at a temperature of 700 °C, atmospheric pressure, and WHSV of 60,000 mL g⁻¹ h⁻¹ showed that the 10%Ni/CeZrO₂ catalyst exhibited the highest catalytic performance, with conversions of CH₄ and CO₂ up to 74% and 55%, respectively, being reached. The H₂/CO ratio in the product was 1.4, which is higher than the stoichiometric ratio of 1, indicating a higher formation of H₂. The spent catalysts showed minimal carbon deposition based on the thermo-gravimetry analysis, which was <0.01 gC/gcat, so carbon deposition could be neglected. Full article

A series of tetrabutyl ammonium (TBA) salts of V-included Keggin-type polyoxoanions with W (TBA₄PW₁₁V₁O₄₀ and TBA₅PW₁₀V₂O₄₀) and Mo (TBA₄PMo₁₁V₁O₄₀ and TBA₅PMo₁₀V₂O₄₀) as addenda atoms were prepared using a hydrothermal method. These synthesized materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance (DRS UV-Vis), thermogravimetric analysis (TGA), CHN elemental analysis (EA), inductively coupled plasma spectrometry (ICP-MS), and N₂ physisorption techniques to assess their physicochemical/textural properties and correlate them with their catalytic performances. According to FT-IR and DRS UV-Vis, (PV_XW(Mo)_12−XO₄₀)^(3+X)− anions are the main species present in the TBA salts. Additionally, CHN-EA and ICP-MS revealed that the desired stoichiometry was obtained. Their catalytic activities in the liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde were studied at 5 bar of O₂ at 170 °C. Independently of the addenda atom nature, the catalytic activity increased with the number of V in the Keggin anion structure. For both series of catalysts, TBA salts of polyoxometalates with the highest V-substitution degree (TBA₅PMo₁₀V₂O₄₀ and TBA₅PW₁₀V₂O₄₀) showed higher activity. The maximum benzyl alcohol conversions obtained were 93% and 97% using (TBA)₅PMo₁₀V₂O₄₀ and (TBA)₅PW₁₀V₂O₄₀ as catalysts, respectively. In all the cases, the selectivity toward benzaldehyde was higher than 99%. Full article

Pt/Al₂O₃ catalysts prepared via supercritical deposition (SCD), with supercritical CO₂, wet impregnation (WI) methods and a selected benchmark catalyst, were evaluated for the dehydrogenation of perhydro-dibenzyltoluene (H18-DBT) at 300 °C in a batch reactor. After ten dehydrogenation runs, the average performance of the catalyst prepared using SCD was the highest compared to the benchmark and WI-prepared catalysts. The pre-treatment of the catalysts with the product (dibenzyltoluene) indicated that the deactivation observed is mainly due to the adsorbed H0-DBT blocking the active sites for the reactant (H18-DBT). Furthermore, the SCD method afforded a catalyst with a higher dispersion of smaller sized Pt particles, thus improving catalytic performance towards the dehydrogenation of H18-DBT. The particle diameters of the SCD- and WI-prepared catalysts varied in the ranges of 0.6–2.2 nm and 0.8–3.4 nm and had average particle sizes of 1.1 nm and 1.7 nm, respectively. Energy dispersive X-ray spectroscopy analysis of the catalysts after ten dehydrogenation runs revealed the presence of carbon. In this study, improved catalyst performance led to the production of more liquid-based by-products and carbon material compared to catalysts with low catalytic performance. Full article

Oxidative dehydrogenation (ODH) reaction has emerged as a promising route for converting 1-butene to value-added 1,3-butadiene (BD). However, the low BD selectivity of the current catalysts (≤40%) and high steam input are now the challenge of this process. Here, we demonstrate the fabrication BiMo oxides immobilized on carbon nanotubes (BiMo/CNTs), employing the sol–gel method, as a novel catalyst for the ODH of 1-butene without steam in a fixed-bed reactor. The catalytic performances of BiMo/CNTs with different compositions in the absence of steam were investigated. When BiMo/CNTs at a molar ratio of 0.018 were employed in the ODH of 1-butene under reaction conditions of 440 °C, 1-butene/oxygen = 1/0.8, and no steam, the optimal BD yield was achieved as high as 52.2%. Under this reaction condition, the catalyst maintains good stability without steam after 10 h of reaction. This work not only promotes the application of carbon materials in oxidative dehydrogenation reaction, but also accelerates the production of 1,3-butadiene in a more economical way. Full article

Selective hydrogenation of 1,3-butadiene (BD) is regarded as the most promising route for removing BD from butene streams. Bimetallic Pd–Ni catalysts with changed Pd/Ni molar ratios and monometallic Pd catalysts were synthesized using two differently structured metal-organic framework supports: UiO-66 and UiO-66-NH₂. The effects of the structure of support and the molar ratio of Pd/Ni on the catalytic property of selective BD hydrogenation were studied. The Pd–Ni bimetallic supported catalysts, PdNi/UiO-66 (1:1) and PdNi/UiO-66-NH₂ (1:1), exhibited fine catalytic property at low temperature. Compared with UiO-66, UiO-66-NH₂ with a certain number of alkaline sites could reduce the catalytic activity for the BD hydrogenation reaction. However, the alkaline environment of UiO-66-NH₂ is helpful to improve the butene selectivity. PdNi/UiO-66-NH₂ (1:1) catalyst presented better stability than PdNi/UiO-66 (1:1) under the reaction conditions, caused by the strong interaction between the –NH₂ groups of UiO-66-NH₂ and PdNi NPs. Moreover, the PdNi/UiO-66-NH₂ (1:1) catalyst presented good reproducibility in the hydrogenation of BD. These findings afford a beneficial guidance for the design and preparation of efficient catalysts for selective BD hydrogenation. Full article

The effect of sulfiding agent and sulfidation temperature on nickel catalysts supported on MgAl₂O₄ were investigated for propane dehydrogenation. The catalysts were prepared by reduction of NiO/MgAl₂O₄, followed by sulfidation using (NH₄)₂SO₄ (S1), (NH₄)₂S (S2), and DMSO (S3) as sulfiding agents. The catalysts were sulfided at 200 °C, 400 °C, and 550 °C to form Ni/MgAl₂O₄-Sx-y, where x and y represent the sulfiding agent and sulfidation temperature, respectively. Physiochemical properties of the catalysts were characterized by XRD, BET, SEM, TEM, and TGA to investigate the type of nickel-sulfur species, surface area, morphology, particle size, and stability of the catalysts. Structural and textural properties revealed that the anion present on the sulfiding agent as well as the sulfidation temperature affect both the type and the strength of the Ni-S species. For the S1 catalysts, the SO₄²⁻ ion interacted with the support to form MgSO₄, while the S²⁻ ion on the S2 and S3 catalysts was responsible for the formation of the Ni₃S₂ phase. The sulfidation temperature contributed to the %S present on each catalyst. Although the catalysts sulfided by S3 contained the least %S, Ni/MgAl₂O₄-S3-550 displayed the best catalytic performance as a result of the higher particle dispersion and stronger Ni-S interaction compared to S1 and S2 catalysts. Full article

Methyl lactate (MLA), a versatile biomass platform, was typically produced from the catalytic conversion of high-priced fructose. High fructose corn syrup (HFCS) is a mixture of glucose, fructose, water, etc., which is viewed as an economical substitute for fructose to produce MLA due to the much lower cost of separation and drying processes. However, the transformation of HFCS to MLA is still a challenge due to its complex components and the presence of water. In this work, the catalytic conversion of HFCS to MLA over CoO@silicalite-1 catalyst synthesized via a straightforward post citric acid treatment approach was reported. The maximum MLA yield reached 43.8% at 180 °C for 18 h after optimizing the reaction conditions and Co loading. Interestingly, adding extra 3% water could further increase the MLA yield, implying that our CoO@silicalite-1 catalyst is also capable for upgrading wet HFCS. As a result, the costly drying process of wet HFCS can be avoided. Moreover, the activity of CoO@silicalite-1 catalyst can be regenerated for at least four cycles via facile calcination in air. This study, therefore, will provide a new opportunity to not only solve the HFCS-overproduction issues but also produce value-added MLA. Full article

The introduction of nitrogen to carbonyl groups is considered both challenging and highly desirable by those who work in the field of organic synthesis. In this study, a diphenylethylenediamine-derived catalyst demonstrating N-selectivity was designed using a quantum calculation for the nitroso aldol reaction. The reductive monoalkylation of (R,R)-(+)-1,2-diphenylethylenediamine afforded an organic chiral diamine catalyst in high yield. The expected reaction mechanism for the nitroso aldol reaction was determined, and the product and solvent conditions were optimized through quantum calculations. The calculation results revealed that the enantioselectivity is determined by the hydrogen bond between the alkyl substituent of the chiral diamine and the oxygen of the aromatic aldehyde on the ammonium moiety. The reaction was found to proceed optimally in the presence of 5 mol % catalyst at −10 °C in brine. Using these conditions, an eco-friendly nitroso aldol reaction was performed in which the organic catalyst and cyclohexanone formed enamine. Nitrosobenzene, activated by hydrogen bonding with an ammonium catalyst, was used to minimize the steric hindrance between the catalyst and the reactant, resulting in high enantioselectivity. A nitroso aldol product with high N-selectivity and enantioselectivity (98% ee) was obtained in 95% yield. The catalyst developed in this study provides a less expensive and more environmentally friendly alternative for the nitroso aldol reaction. Full article

The recycling of heavy metal contaminants from wastewater as a source of valuable products perfectly fits with the principles of a Circular Economy system in view of restoring pollutants back into the system endowed with new social and economic benefits. Heavy metals are often present in such a low concentration that it makes the removal efficiency difficult to realize through the conventional physicochemical methods with high selectivity. Biosorption, conversely, by EPSs (extracellular polymeric substances) produced by several bacterial cells’ strains, is gaining a great deal of attention as an economic, efficient and sustainable depolluting process of wastewater from metal cations such as copper. Metal coordination to EPS components was thus deeply investigated by ¹H NMR titration experiments. The 1,10–Phenanthroline–copper complex was exploited for quantifying the ability of different strains to sequester copper by a practical UV-Vis spectrophotometric method. The obtained data distinguished Serratia plymuthica strain SC5II as the bacterial strain displaying copper-adsorbing properties higher than any other, with Stenotrophomonas sp. strain 13a resulting in the worst one. Different analytical techniques, i.e., Dynamic Light Scattering (DLS), FT-IR analysis and SEM spectroscopy were thus employed to rationalize these results. Finally, the obtained copper chelates were successfully employed as hybrid catalysts in the asymmetric boron addition to α,β-unsaturated chalcones for the synthesis of valuable pharmaceutical intermediates, thus placing waste management in a new circular perspective. Full article

Zeolites have been successfully applied as catalysts in the pyrolysis of plastics to obtain valuable lower molecular weight hydrocarbon compounds. In the present work, mordenite was directly synthesized and chemically modified from commercial mordenite to increase pore volume. For the first time, the performance of these mordenites was compared with that of an alkali-treated ZSM-5 as catalysts for assisting the pyrolysis of simulated urban plastic waste. The investigated zeolites were: (i) as-supplied synthetic ZSM-5 (ZSM-5/AS); (ii) 0.2 M NaOH treated ZSM-5 (ZSM-5/02); (iii) as-supplied mordenite (MOR/AS); (iv) 0.2 M NaOH treated mordenite (MOR/02); and (v) synthetic lab-developed mordenite (MOR/SD). The modified and synthesized zeolites were individually applied as catalysts in the 700 °C pyrolyzes of combined polyethylene, polypropylene, and polystyrene wastes in a mixture simulating most plastics found in Rio de Janeiro (Brazil) city garbage composition. X-ray diffraction revealed crystallite sizes of all zeolites in a nanometric range from 17 to 43 nm. Textural analysis disclosed the alkali-treated ZSM-5/02 with a superior external surface area, 153 m²/g, and mesopore volume equal to 0.253 cm³/g. Lower values were obtained by MOR/02 (39 m²/g and 0.072 cm³/g). The pyrolysis of the plastic mixture with ZSM-5/02 presented a lower initial degradation temperature, 387 °C, followed by MOR/02, with 417 °C. The ZSM-5/02 catalyst obtained the highest conversion in the pyrolysis of the plastic mixture, totaling 49.2%. However, pyrolysis assisted by the MOR/02 catalyst showed the largest fraction (81.5%) of light hydrocarbons. Full article

The present paper presents one- and two-step approaches for electrochemical Pt and Ir deposition on a porous Ti-substrate to obtain a bifunctional oxygen electrode. Surface pre-treatment of the fiber-based Ti-substrate with oxalic acid provides an alternative to plasma treatment for partially stripping TiO₂ from the electrode surface and roughening the topography. Electrochemical catalyst deposition performed directly onto the pretreated Ti-substrates bypasses unnecessary preparation and processing of catalyst support structures. A single Pt constant potential deposition (CPD), directly followed by pulsed electrodeposition (PED), created nanosized noble agglomerates. Subsequently, Ir was deposited via PED onto the Pt sub-structure to obtain a successively deposited PtIr catalyst layer. For the co-deposition of PtIr, a binary PtIr-alloy electrolyte was used applying PED. Micrographically, areal micro- and nano-scaled Pt sub-structure were observed, supplemented by homogenously distributed, nanosized Ir agglomerates for the successive PtIr deposition. In contrast, the PtIr co-deposition led to spherical, nanosized PtIr agglomerates. The electrochemical ORR and OER activity showed increased hydrogen desorption peaks for the Pt-deposited substrate, as well as broadening and flattening of the hydrogen desorption peaks for PtIr deposited substrates. The anodic kinetic parameters for the prepared electrodes were found to be higher than those of a polished Ir-disc. Full article

The thermocatalytic hydrogenation of carbon dioxide (CO₂) to methanol is considered as a potential route for green hydrogen storage as well as a mean for utilizing captured CO₂, owing to the many established applications of methanol. Copper–zinc bimetallic catalysts supported on a zirconium-based UiO-66 metal–organic framework (MOF) were prepared via slurry phase impregnation and benchmarked against the promoted, co-precipitated, conventional ternary CuO/ZnO/Al₂O₃ (CZA) catalyst for the thermocatalytic hydrogenation of CO₂ to methanol. A decrease in crystallinity and specific surface area of the UiO-66 support was observed using X-ray diffraction and N₂-sorption isotherms, whereas hydrogen-temperature-programmed reduction and X-ray photoelectron spectroscopy revealed the presence of copper active sites after impregnation and thermal activation. Other characterisation techniques such as scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis were employed to assess the physicochemical properties of the resulting catalysts. The UiO-66 (Zr) MOF-supported catalyst exhibited a good CO₂ conversion of 27 and 16% selectivity towards methanol, whereas the magnesium-promoted CZA catalyst had a CO₂ conversion of 31% and methanol selectivity of 24%. The prepared catalysts performed similarly to a CZA commercial catalyst which exhibited a CO₂ conversion and methanol selectivity of 30 and 15%. The study demonstrates the prospective use of Cu-Zn bimetallic catalysts supported on MOFs for direct CO₂ hydrogenation to produce green methanol. Full article

The degradation of pollutants in wastewater using abundant resources and renewable energy sources, such as light, is attractive from an environmental perspective. ZnO is a well-known photocatalytic material. Therefore, in this study, a hierarchical ZnO microsphere precursor was prepared using a hydrothermal method. The precursor was subsequently annealed at different temperatures, which enabled the production of a ZnO catalyst having a controllable morphology. Specifically, as the annealing temperature increased, the precursor crystallized into hexagonal wurtzite and the crystallinity also increased. The catalysts were tested for their photocatalytic activity for the degradation of dye molecules (methylene blue and rhodamine B), and the catalyst sample annealed at 400 °C showed the best photocatalytic activity. The origin of this activity was studied using electron paramagnetic resonance spectroscopy and transient photocurrent measurements, and the structure of the optimal catalyst was invested using electron microscopy measurements, which revealed that it was formed of two-dimensional nanosheets having smooth surfaces, forming a 2D cellular network. Thus, we have presented a promising photocatalyst for the mineralization of organic contaminants in wastewater. Full article

In the present investigation, ZnO films co-doped with Mn and La were synthesized by the sol–gel technique. XRD analysis revealed that ZnO had a hexagonal structure. Mixed hexagonal and cubic phases appeared in ZnO containing Mn (1%) and La (1.5%). The grain size, d-spacing, unit cell, lattice parameters, atomic packing fraction, volume, strain, crystallinity, and bond length of co-doped ZnO films were determined as a function of doped ion contents. Through UV analysis, it was found that pristine ZnO had E_g = 3.5 eV, and it decreased when increasing the doping concentration, reaching the minimum value for the sample with 1% Mn and 1% La. The optical parameters of the films, such as absorption, transmittance, dielectric constants, and refractive index, were also analyzed. DSSCs were fabricated using the prepared ZnO films. For pure ZnO film, the values were: efficiency = 0.69%, current density = 2.5 mAcm⁻², and open-circuit voltage = 0.56 V. When ZnO was co-doped with Mn and La, the efficiency increased significantly. DSSCs with a ZnO photoanode co-doped with 1% Mn and 1% La exhibited maximum values of J_sc = 4.28 mAcm⁻², V_oc = 0.6 V, and efficiency = 1.89%, which is 174% better than pristine ZnO-based DSSCs. This material is good for the electrode of perovskite solar cells. Full article

Using a modulated pulse power magnetron sputtering (MPP-MSP) coupled with a quadrupole mass spectrometer (Q-MS), intensive size-selected gold nanoclusters (Au_n) ranging from n = 5 to 40 in size are synthesized and soft landed onto a strontium titanate (STO) crystal surface as a co-catalyst for photocatalytic water splitting. The photocatalytic reactivity of the Au_n/STO is investigated by measuring the photocurrent density of the sample under visible light radiation. It is found that the Au_n co-catalysts enable the visible light response of the Au_n/STO photocatalyst. The photocurrent density is sensitively dependent on the size of the Au_n on the STO, and Au₁₆ exhibits its maximum photocurrent under visible light. The underlying physics of the size-specific photocurrent are explained in terms of the size-dependent electron affinity of Au_n. Full article

Exploring bifunctional electrocatalysts to lower the activation energy barriers for sluggish electrochemical reactions for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are of great importance in achieving lower energy consumption and higher conversion efficiency for future energy conversion and storage system. Despite the excellent performance of precious metal-based electrocatalysts for OER and ORR, their high cost and scarcity hamper their large-scale industrial application. As alternatives to precious metal-based electrocatalysts, the development of earth-abundant and efficient catalysts with excellent electrocatalytic performance in both the OER and the ORR is urgently required. Herein, we report a core–shell CoFeS₂@CoS₂ heterostructure entangled with carbon nanotubes as an efficient bifunctional electrocatalyst for both the OER and the ORR. The CoFeS₂@CoS₂ nanocubes entangled with carbon nanotubes show superior electrochemical performance for both the OER and the ORR: a potential of 1.5 V (vs. RHE) at a current density of 10 mA cm⁻² for the OER in alkaline medium and an onset potential of 0.976 V for the ORR. This work suggests a processing methodology for the development of the core–shell heterostructures with enhanced bifunctional performance for both the OER and the ORR. Full article

The need for sustainable energy sources is now more urgent than ever, and hydrogen is significant in the future of energy. However, several obstacles remain in the way of widespread hydrogen use, most of which are related to transport and storage. Dilute formic acid (FA) is recognized asa a safe fuel for low-temperature fuel cells. This review examines FA as a potential hydrogen storage molecule that can be dehydrogenated to yield highly pure hydrogen (H₂) and carbon dioxide (CO₂) with very little carbon monoxide (CO) gas produced via nanoheterogeneous catalysts. It also present the use of Au and Pd as nanoheterogeneous catalysts for formic acid liquid phase decomposition, focusing on the influence of noble metals in monometallic, bimetallic, and trimetallic compositions on the catalytic dehydrogenation of FA under mild temperatures (20–50 °C). The review shows that FA production from CO₂ without a base by direct catalytic carbon dioxide hydrogenation is far more sustainable than existing techniques. Finally, using FA as an energy carrier to selectively release hydrogen for fuel cell power generation appears to be a potential technique. Full article

Novel magnetic carbon microtube-based solid acid was synthesized via the carbonization of FeCl₃-doped willow catkin and benzenediazoniumsulfonate acid-based sulfonation. The biomass willow catkin provided the special microtube structure and the high surface area of 215 m²/g for the novel solid acid. The microtube structure was well conserved during the mild carbonization (400 °C) and sulfonation process. The large number of acidic sites (2.3 mmol/g) on the microtube surface was quite accessible to reactants. Its magnetic properties offered a simple separation process. The novel solid acid showed very high activity for biodiesel synthesis, using cooking oils as raw material, which gave a total yield of 99% and free fatty acid conversion of 98.7% under mild conditions (70 °C). The facile synthetic process, high activity, high stability, and high recovery simplicity were the main properties of the novel magnetic solid acid, which is one of the best choices for biodiesel synthesis. Full article