Search Results (677)

2,5-bis(hydroxymethy)lfuran (BHMF), a renewable compound with extensive industrial applications, can be obtained by selective hydrogenation of the C=O group of 5-hydroxymethylfurfural (HMF), a platform molecule derived from lignocellulosic biomass. In this work, we perform kinetic modeling of the selective liquid-phase hydrogenation of HMF to BHMF over a Cu/SiO₂ catalyst prepared by precipitation–deposition (PD) at a constant pH. Physicochemical characterization, using different techniques, confirms that the Cu/SiO₂–PD catalyst is formed by copper metallic nanoparticles of 3–5 nm in size highly dispersed on the SiO₂ surface. Before the kinetic study, the Cu/SiO₂-PD catalyst was evaluated in three solvents: tetrahydrofuran (THF), 2-propanol (2-POH), and water. The pattern of catalytic activity and BHMF yield for the different solvents was THF > 2-POH > H₂O. In addition, selectivity to BHF was the highest in THF. Thus, THF was chosen for further kinetic study. Several experiments were carried out by varying the initial HMF concentration (C⁰_HMF) between 0.02 and 0.26 M and the hydrogen pressure (P_H2) between 200 and 1500 kPa. In all experiments, BHMF selectivity was 97–99%. By pseudo-homogeneous modeling, an apparent reaction order with respect to HFM close to 1 was estimated for a C⁰_HMF between 0.02 M and 0.065 M, while when higher than 0.065 M, the apparent reaction order changed to 0. The apparent reaction order with respect to H₂ was nearly 0 when C⁰_HMF = 0.13 M, while for C⁰_HMF = 0.04 M, it was close to 1. The reaction orders estimated suggest that HMF is strongly absorbed on the catalyst surface, and thus total active site coverage is reached when the C⁰_HMF is higher than 0.065 M. Several Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic models were proposed, tested against experimental data, and statistically compared. The best fitting of the experimental data was obtained with an LHHW model that considered non-competitive H₂ and HMF chemisorption and strong chemisorption of reactant and product molecules on copper metallic active sites. This model predicts both the catalytic performance of Cu/SiO₂-PD and its deactivation during liquid-phase HMF hydrogenation. Full article

Industrial catalysts are accelerating the global transition toward renewable energy, serving as enablers for innovative technologies that enhance efficiency, lower costs, and improve environmental sustainability. This review explores the pivotal roles of industrial catalysts in hydrogen production, biofuel generation, and biomass conversion, highlighting their transformative impact on renewable energy systems. Precious-metal-based electrocatalysts such as ruthenium (Ru), iridium (Ir), and platinum (Pt) demonstrate high efficiency but face challenges due to their cost and stability. Alternatives like nickel-cobalt oxide (NiCo₂O₄) and Ti₃C₂ MXene materials show promise in addressing these limitations, enabling cost-effective and scalable hydrogen production. Additionally, nickel-based catalysts supported on alumina optimize SMR, reducing coke formation and improving efficiency. In biofuel production, heterogeneous catalysts play a crucial role in converting biomass into valuable fuels. Co-based bimetallic catalysts enhance hydrodeoxygenation (HDO) processes, improving the yield of biofuels like dimethylfuran (DMF) and γ-valerolactone (GVL). Innovative materials such as biochar, red mud, and metal–organic frameworks (MOFs) facilitate sustainable waste-to-fuel conversion and biodiesel production, offering environmental and economic benefits. Power-to-X technologies, which convert renewable electricity into chemical energy carriers like hydrogen and synthetic fuels, rely on advanced catalysts to improve reaction rates, selectivity, and energy efficiency. Innovations in non-precious metal catalysts, nanostructured materials, and defect-engineered catalysts provide solutions for sustainable energy systems. These advancements promise to enhance efficiency, reduce environmental footprints, and ensure the viability of renewable energy technologies. Full article

The precise synthesis of non-precious metal single-atom electrocatalysts is crucial for enhancing the yield of highly active reactive oxygen species (ROSs). Conventional oxidation methods, such as Fenton or NaClO processes, suffer from poor efficiency, high energy demand, and secondary pollution. In contrast, heterogeneous electro-Fenton systems based on cascade oxygen reduction reactions (ORRs), which require low operational voltage and cause pollutant degradation through both direct electron transfer and ROS generation, have emerged as a promising alternative. Recent studies showed that carbon cathodes decorated with atomically dispersed transition metals can effectively integrate the excellent conductivity of carbon supports with the tunable surface chemistry of metal centers. However, the electronic structure of active sites intrinsically hinders the simultaneous achievement of high activity and selectivity in cascade ORRs. This review summarizes the advances, specifically from 2020 to 2025, in understanding the mechanism of cascade ORRs and the synthesis of transition metal-based single-atom catalysts in cathode electrocatalysis for efficient wastewater treatment, and discusses the key factors affecting treatment performance. While employing atomically engineered cathodes is a promising approach for energy-efficient wastewater treatment, future efforts should overcome the barriers in active site control and long-term stability of the catalysts to fully exploit their potential in addressing water pollution challenges. Full article

This review examines the research progress on non-noble-metal-based catalysts for formaldehyde (HCHO) oxidation at room temperature. It begins with an introduction to the hazards of HCHO as an indoor pollutant and the urgency of its removal, comparing several HCHO removal technologies and highlighting the advantages of room-temperature catalytic oxidation. It delves into the classification, preparation methods, and regulation strategies for non-precious metal catalysts, with a focus on manganese-based, cobalt-based, and other transition metal-based catalysts. The effects of catalyst preparation methods, morphological structure, and specific surface area on catalytic performance are discussed, and the catalytic oxidation mechanisms of HCHO, including the Eley–Rideal, Langmuir–Hinshelwood, and Mars–van Krevelen mechanisms, are analyzed. Finally, the challenges faced by non-precious metal catalysts are summarized, such as issues related to the powder form of catalysts in practical applications, lower catalytic activity at room temperature, and insufficient research in the presence of multiple VOC molecules. Suggestions for future research directions are also provided. Full article

Hydrogen, as a renewable and clean energy with a high energy density, is of great significance to the realization of carbon neutrality. In recent years, extensive research has been conducted on the electrocatalytic hydrogen evolution reaction (HER) by splitting water, with a focus on developing efficient electrocatalysts that can perform the HER at an overpotential with minimal power consumption. Tungsten oxide (WO₃), a non-noble-metal-based material, has great potential in hydrogen evolution due to its excellent redox capability, low cost, and high stability. However, it cannot meet practical needs because of its poor electrical conductivity and the limited number of active sites; thus, it is necessary to further improve HER performance. In this review, recent advances related to WO3-based electrocatalysts for the HER are introduced. Most importantly, several tactics for optimizing the electrocatalytic HER activity of WO₃ are summarized, such as controlling its morphology, phase transition, defect engineering (anion vacancies, cation doping, and interstitial atoms), constructing a heterostructure, and the microenvironment effect. This review can provide insight into the development of novel catalysts with high activity for the HER and other renewable energy applications. Full article

In our previous work, we fabricated Ni single-atoms within Beta zeolite (Ni₁@Beta-NO₃⁻) using NiNO₃·6H₂O as a metal precursor without any chelating agents, which exhibited exceptional performance in the selective hydrogenation of furfural. Owing to the confinement effect, the as-encapsulated nickel species appears in the form of Ni⁰ and Ni^δ+, which implies its feasibility in metal catalysis and coordination catalysis. In the study reported herein, we further explored the hydrogen production and olefin oligomerization performance of Ni₁@Beta-NO₃⁻. It was found that Ni₁@Beta-NO₃⁻ demonstrated a high H₂ generation turnover frequency (TOF) and low activation energy (E_a) in a sodium borohydride (NaBH₄) hydrolysis reaction, with values of 331 min⁻¹ and 30.1 kJ/mol, respectively. In ethylene dimerization, it exhibited a high butylene selectivity of 99.4% and a TOF as high as 5804 h⁻¹. In propylene oligomerization, Ni₁@Beta-NO₃⁻ demonstrated high selectivity (75.21%) of long-chain olefins (≥C₆⁺), overcoming the problem of cracking reactions that occur during oligomerization using H-Beta. Additionally, as a comparison, the influence of the metal precursor (NiCl₂) on the performance of the encapsulated Ni catalyst was also examined. This research expands the application scenarios of non-noble metal single-atom catalysts and provides significant assistance and potential for the production of H₂ from hydrogen storage materials and the production of valuable chemicals. Full article

In the field of green chemistry, the development of more sustainable and cost-efficient methods for synthesizing primary amines is of paramount importance, with catalyst research being central to this effort. This work presents a facile, aqueous-phase synthesis of highly active cobalt catalysts (Co-Ph@SiO₂(x)) via pyrolysis of silica-supported cobalt–phenanthroline complexes. The optimized Co-Ph@SiO₂(900) catalyst achieved exceptional performance (>99% conversion, >98% selectivity) in the reductive amination of acetophenone to 1-phenylethanamine using NH₃/H₂. Systematic studies revealed that its exceptional performance originates from the in situ pyrolysis of the cobalt–phyllosilicate complex. This process promotes the uniform distribution of metal cobalt nanoparticles, simultaneously enhancing porosity and imparting bifunctional (acidic and basic) properties to the catalyst, resulting in outstanding catalytic activity and selectivity. The catalyst demonstrated broad applicability, efficiently converting diverse ketones (aryl-alkyl, dialkyl, bioactive) and aldehydes (halogenated, heterocyclic, biomass-derived) into primary amines with high yields (up to 99%) and chemoselectivity (>40 examples). This sustainable, non-noble metal-based catalyst system offers significant potential for industrial primary amine synthesis and provides a versatile tool for developing highly selective and active heterogeneous catalysts. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

The development of non-noble metal catalysts for gas-phase propylene epoxidation with H₂/O₂ remains challenging due to their inadequate activity and stability. Herein, we report a Cs⁺-modified Ni/TS-1 catalyst (9%Ni-Cs/TS-1), which exhibits unprecedented catalytic performance, giving a state-of-the-art PO formation rate of 382.9 g_PO·kg_cat⁻¹·h⁻¹ with 87.8% selectivity at 200 °C. The catalyst stability was sustainable for 150 h, far surpassing reported Ni-based catalysts. Ni/TS-1 exhibited low catalytic activity. However, the Cs modification significantly enhanced the performance of Ni/TS-1. Furthermore, the intrinsic reason for the enhanced performance was elucidated by multiple techniques such as XPS, N₂ physisorption, TEM, ²⁹Si NMR, NH₃-TPD-MS, UV–vis, and so on. The findings indicated that the incorporation of Cs⁺ markedly boosted the reduction of Ni, enhanced Ni⁰ formation, strengthened Ni-Ti interactions, reduced acid sites to inhibit PO isomerization, improved the dispersion of Ni nanoparticles, reduced particle size, and improved the hydrophobicity of Ni/TS-1 to facilitate propylene adsorption/PO desorption. The 9%Ni-Cs/TS-1 catalyst demonstrated exceptional performance characterized by a low cost, high activity, and long-term stability, offering a viable alternative to Au-based systems. Full article

The electrocatalytic decomposition of ammonia represents a promising route for sustainable hydrogen production, yet current systems rely heavily on noble metal catalysts with prohibitive costs and limited durability. A critical challenge lies in developing non-noble electrocatalysts that simultaneously achieve high active site exposure, optimized electronic configurations, and robust structural stability. Addressing these requirements, this study strategically engineered Cu-doped ZIF-8 architectures via in situ growth on nickel foam (NF) substrates through a facile room-temperature hydrothermal synthesis approach. Systematic optimization of the Cu/Zn molar ratio revealed that Cu_0.7Zn_0.3-ZIF/NF achieved optimal performance, exhibiting a distinctive nanoflower-like architecture that substantially increased accessible active sites. The hybrid catalyst demonstrated superior electrocatalytic performance with a current density of 124 mA cm⁻² at 1.6 V vs. RHE and a notably low Tafel slope of 30.94 mV dec⁻¹, outperforming both Zn-ZIF/NF (39.45 mV dec⁻¹) and Cu-ZIF/NF (31.39 mV dec⁻¹). Combined XPS and EDS analyses unveiled a synergistic electronic structure modulation between Zn and Cu, which facilitated charge transfer and enhanced catalytic efficiency. A gas chromatography product analysis identified H₂ and N₂ as the primary gaseous products, confirming the predominant occurrence of the ammonia oxidation reaction (AOR). This study not only presents a noble metal-free electrocatalyst with exceptional efficiency and durability for ammonia decomposition but also demonstrates the significant potential of MOF-derived materials in sustainable hydrogen production technologies. Full article

This study presents the development of a novel Cu–Co–O-codoped graphitic carbon nitride (g-C₃N₄) catalyst for efficient peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX) in aqueous environments. The synthesized Cu–Co–O-g-C₃N₄ catalyst demonstrated exceptional catalytic performance, achieving 90% SMX removal within 10 min—significantly outperforming pristine g-C₃N₄ (14%) and O-doped g-C₃N₄ (22%)—with a reaction rate constant of 0.63 min⁻¹. The superior activity was attributed to the synergistic effects of Cu-Co bimetallic doping and oxygen incorporation, which enhanced the active sites, stabilized metal ions, and minimized leaching. Mechanistic studies revealed a dual-pathway degradation process: (1) a radical pathway dominated by sulfate radicals (SO₄•⁻) and (2) a non-radical pathway driven by singlet oxygen (¹O₂), with the latter identified as the dominant species through quenching experiments. The catalyst exhibited broad pH adaptability and optimal performance at neutral to alkaline conditions. Characterization techniques (XRD, FTIR, XPS) confirmed successful doping and revealed that oxygen incorporation modified the electronic structure of g-C₃N₄, improving charge carrier separation. This work provides a sustainable strategy for antibiotic removal, addressing key challenges in advanced oxidation processes (AOPs), and highlights the potential of multi-heteroatom-doped carbon nitride catalysts for water purification. Full article

Due to its persistence and potential negative effects on ecosystems and human health, microplastic pollution in aquatic environments has become a major worldwide concern. Photocatalytic degradation is a sustainable manner to degrade microplastics to non-toxic by-products. In this review, comprehensive discussion focuses on the synergistic effects of various photocatalytic materials including TiO₂, ZnO, WO₃, graphene oxide, and metal–organic frameworks for producing heterojunctions and involving multidimensional nanostructures. Such mechanisms can include the generation of reactive oxygen species and polymer chain scission, which can lead to microplastic breakdown and mineralization. The advancements of material modifications in the (nano)structure of photocatalysts, doping, and heterojunction formation methods to promote UV and visible light-driven photocatalytic activity is discussed in this paper. Reactor designs, operational parameters, and scalability for practical applications are also reviewed. Photocatalytic systems have shown a lot of development but are hampered by shortcomings which include a lack of complete mineralization and production of intermediary secondary products; variability in performance due to the fluctuation in the intensity of solar light, limited UV light, and environmental conditions such as weather and the diurnal cycle. Future research involving multifunctional, environmentally benign photocatalytic techniques—e.g., doped composites or composite-based catalysts that involve adsorption, photocatalysis, and magnetic retrieval—are proposed to focus on the mechanism of utilizing light effectively and the environmental safety, which are necessary for successful operational and industrial-scale remediation. Full article

Electrochemical water splitting is an efficient and eco-friendly method for hydrogen production, offering a sustainable energy solution. Currently, the noble metal platinum is considered to be the most efficient catalyst for electrochemical hydrogen evolution reactions (HERs). Due to the scarcity and high cost of noble metal materials, there is an urgent need to find abundant and cost-effective non-noble metal catalysts to reduce the overpotential of HERs. In recent years, significant scientific advancements have been reported in non-noble metal HER catalysts. This review categorizes and reviews the recent non-noble metal HER catalysts and their reaction mechanisms. An exhaustive overview of proven effective catalyst categories is provided, offering early-career researchers a panoramic understanding of this dynamic research field. Finally, we address current challenges and future directions in this field to encourage further research efforts and the development of non-noble metal catalysts. Full article

Anion exchange membranes (AEMs) are vital for electrochemical energy devices such as alkaline fuel cells and water electrolyzers, enabling the use of non-precious metal catalysts despite challenges from alkaline degradation. Hyperbranched polymers (hbPs) with their globular structure, high functional group density, and simple synthesis, offer a promising platform for enhancing transport and stability. In this study, multifunctional hbPs were synthesized from 4-vinylbenzyl chloride (VBC) and 2-hydroxyethyl methacrylate (HEMA) via atom transfer radical self-condensing vinyl polymerization (ATR-SCVP) and crosslinked into polyurethane-based AEMs. Characterization confirmed successful copolymerization and crosslinking, with excellent alkaline stability. Membranes crosslinked with higher molecular weight (MW) and VBC-richer hbPs (e.g., OH-hbP1-PU) exhibited high water uptake (75%) but low ion-exchange capacity (1.54 mmol/g) and conductivity (186 µS/cm), attributed to steric hindrance and insufficient ionic network connectivity. In contrast, OH-hbP2-PU exhibited optimal properties, with the highest OH⁻ conductivity (338 µS/cm) and IEC (2.64 mmol/g), highlighting a balanced structure for efficient ion transport. This work offers a tunable strategy for high-performance AEM development through tailored hbP architecture. Full article

The sludge produced by the Fenton process contains mixed-valence iron particulates (hereafter called Fenton wastes). Using a solvothermal method, we fabricated a new heterogeneous photo-Fenton catalyst using Fenton wastes and metal–organic frameworks (MOFs). Nanoporous metal carboxylate (MIL-88) MOF impregnated with Fenton waste was functionalized using 2,5-dihydroxyterephthalic acid (x-HO-MIL-88-C, x, concentration of the 2,5-dihydroxyterephthalic acid). The efficiency of x-HO-MIL-88-C was examined under visible light radiation using methylene blue (MB) as an index pollutant. We observed the best catalytic performance for MB degradation by 4-HO-MIL-88-C. In the photo-Fenton process, the simultaneous presence of singlet oxygen, superoxide, and hydroxyl radicals is confirmed by free radical quenching and electron spin resonance spectral data. These free radicals associate with holes in the non-selective degradation of MB. The 4-HO-MIL-88-C catalyst shows good stability and reusability, maintaining over 80% efficiency at the end of five consecutive cycles. This work opens up a new path for recycling Fenton wastes into usable products. Full article