Search Results (102)

Sustainable water remediation requires catalytic strategies that remove contaminants efficiently while reducing chemical input, byproduct formation, and ecological disturbance. Conventional radical-dominated advanced oxidation processes can rapidly degrade pollutants, but their reliance on high oxidant dosages and freely diffusing reactive oxygen species often causes matrix quenching, non-selective oxidation, low oxidant utilization, and potential ecological risks. Mild interfacial catalysis provides a materials-chemistry strategy to regulate oxidative intensity and direct contaminant transformation under environmentally relevant conditions. In this review, mild catalysts are defined by pathway-selective, interfacially confined, and environmentally compatible oxidation rather than by low dosage alone. Representative non-radical or low-intensity pathways, including singlet oxygen generation, surface-mediated electron transfer, high-valent metal–oxo species, and direct oxidative transfer processes, are discussed in relation to active-site structure, oxidant utilization, matrix tolerance, and byproduct control. We further summarize how coordination environments, defect chemistry, heteroatom configurations, nanoconfinement, and immobilized interfaces regulate reactive-species formation and interfacial charge transfer. Key material platforms, including single-atom catalysts, heteroatom-doped carbons, defect-engineered oxides, catalytic membranes, hydrogels, and floating or immobilized composites, are evaluated from mechanistic and application-oriented perspectives. Finally, catalyst regeneration, cost, microbial community responses, algae–bacteria balance, ecotoxicity, and long-term safety are discussed to guide sustainable aquatic ecosystem restoration. Full article

The Fenton reaction remains one of the most widely investigated advanced oxidation processes for wastewater treatment due to its ability to generate highly reactive oxygen species capable of degrading persistent organic pollutants. However, classical homogeneous Fenton systems suffer from significant limitations, including narrow pH applicability, iron sludge generation, and poor catalyst reusability. In response, extensive research has focused on the development of heterogeneous and advanced Fenton-like catalysts aimed at overcoming these challenges while enhancing catalytic efficiency and operational stability. This review provides a comprehensive and critical analysis of the evolution of Fenton catalysis, from classical homogeneous systems to advanced materials, including nanostructured catalysts, carbon-based Fe–N–C systems, metal–organic frameworks, and single-atom catalysts. A unified evaluation framework is proposed, integrating key performance parameters such as catalytic activity, manufacturability, stability, and catalyst lifespan. Comparative analysis reveals that improvements in activity are often accompanied by trade-offs in cost and scalability, indicating that the most advanced materials do not necessarily provide the best practical performance. A life cycle-oriented perspective is incorporated, emphasizing catalyst reuse, lifespan, and iron leaching, and providing quantitative insight into cumulative catalytic performance. The results demonstrate that long-term efficiency is governed not only by intrinsic activity but also by durability and operational stability under realistic conditions. Finally, current challenges and future directions are discussed, including scalable synthesis, improved mechanistic understanding, and integration into hybrid treatment systems. This review bridges the gap between fundamental research and practical application by highlighting the importance of balancing performance, stability, and sustainability in the design of next-generation Fenton catalysts. Full article

Two-dimensional antimonene has recently emerged as a promising electrocatalytic platform; however, its oxygen reduction reaction (ORR) activity and modulation strategies remain largely unexplored. Herein, density functional theory (DFT) calculations are employed to systematically investigate ORR catalysis on antimonene co-doped with transition metal (TM) and nonmetal (C, P) dual atoms. The results reveal that Pd@C–Sb, Pt@C–Sb, and Pd@P–Sb exhibit remarkably enhanced ORR activity, delivering low overpotentials of 0.31 V, 0.32 V, and 0.38 V, respectively, significantly outperforming their single-atom-doped counterparts. Mechanistic analyses demonstrate that nonmetal dopants induce strong synergistic interactions with TM centers, leading to charge redistribution and effective regulation of the TM d-band center, which optimizes the adsorption energetics of key ORR intermediates. Notably, the number of d-electrons of TM atoms is identified as a reliable electronic descriptor governing intermediate binding strength and catalytic activity. Furthermore, ab initio molecular dynamics simulations confirm the excellent thermodynamic stability of the optimized dual-atom catalysts. This work elucidates the atomic-scale origin of synergistic enhancement in dual-atom-doped antimonene and provides a rational design strategy for high-performance ORR electrocatalysts based on two-dimensional main-group materials. Full article

Catalysis has entered everyday life through a range of technological processes that rely on different catalytic systems. The increasing demand for such systems requires rationalization of the use of their expensive components, such as noble-metal catalysts. As such, a catalyst with low noble-metal concentration, in which each one of the noble atoms is active, would reach the lowest price possible. Nevertheless, no clear reactivity descriptors have been outlined for this type of low-coordinated supported atom. Using DFT calculations, we consider three diverse systems as models of single-atom catalysts. We investigate monomers and bimetallic dimers of Ru, Rh, Pd, Ir, and Pt on MgO(001), Cu adatom on thin Mo(001)-supported films (NaF, MgO, and ScN), and single Pt adatoms on oxidized graphene surfaces. The reactivity of these metal atoms was probed by CO. In each case, we see the interaction through the donation–backdonation mechanism. In some cases, CO adsorption energies can be linked to the position of the d-band center and the adatom’s charge. A higher-lying d-band center and less-charged, supported single atoms bind CO more weakly. Also, in some cases, metal atoms that are less strongly bound to the substrate bind CO more strongly. The results suggest that the identification of common activity descriptor(s) for single metal atoms on foreign supports is a difficult task with no unique solution. However, it is also suggested that the stability of adatoms and strong anchoring to the support are prerequisites for the application of descriptor-based search to novel single-atom catalysts. Full article

Metallaphotoredox catalysis merges the powerful bond-forming abilities of transition metal catalysis with unique electron or energy transfer pathways accessible in photoexcited states, injecting new vitality into organic synthesis. However, most transition metal catalysts cannot be excited by visible light. Thus, prevalent metallaphotoredox catalytic systems require dual catalysts: a transition metal catalyst and a separate photosensitizer. This leads to inefficient electron transfer between these two low-concentration catalytic species, which often limits overall photocatalytic performance. Single-atom site catalysts (SASCs) offer a promising solution, wherein isolated and quasi-homogeneous transition metal sites are anchored on heterogeneous supports. When semiconductors are employed as the support, the photosensitive unit and transition metal catalytic site can be integrated into one system. This integration switches the electron transfer mode from intermolecular to intramolecular, thereby significantly enhancing photocatalytic efficiency. Furthermore, such heterogeneous catalysts are easier to separate and reuse. This review summarizes recent advances in the application of SASCs for photocatalytic organic synthesis, with a particular focus on elucidating structure–activity relationships of the single-atom sites. Full article

Staphylococcus aureus (S. aureus) is a major Gram-positive pathogen, and treatment of S. aureus infections is often challenging due to widespread antibiotic resistance. In Gram-positive bacteria such as S. aureus, D-alanylation of teichoic acids (TA) reduces the net negative charge of the cell envelope and contributes to resistance to diverse antibiotics, particularly cationic antimicrobial peptides. D-alanylation is mediated by the dltABCD operon, which encodes four proteins (DltA, DltB, DltC, and DltD), all of which is essential for the multistep transfer of D-alanine to teichoic acids. Here, we present the first crystal structure of the S. aureus D-alanyl carrier protein DltC and analyze its interaction with DltA using AlphaFold3 and all-atom molecular dynamics simulations. We further show that single substitutions of SaDltA-SaDltC interface residues abolish SaDltC mediated enhancement of SaDltA catalysis. Together, these findings define a catalytically critical S. aureus DltA-DltC interface and provide a structural insight for targeting the D-alanylation pathway as a potential anti-Staphylococcus strategy. Full article

Nitrate (NO₃⁻), as a stable nitrogen-containing compound, has caused serious harm to the ecological environment and human health. To reduce nitrate pollution, the catalytic reduction of nitrate (NO₃RR) to ammonia (NH₃) is a very promising solution. Recently, single-atom catalysts (SACs) have received extensive attention due to their excellent activity and stability. Here, we study the nitrate catalytic reduction properties of hexagonal-boron-nitride-(h-BN)-supported single-atom Cu systematically and theoretically and compare it with monolayer h-BN. We find that (1) due to the stronger electronegativity of the N atom, Cu atom is preferentially doped at the N top site, resulting in the significant electron rearrangement; (2) the doped Cu atom at the N top site for monolayer h-BN can provide extra 3d-orbital electrons at the Fermi level, which can significantly enhance the conductivity, reduce the bandgap width, and increase the reducibility; (3) the NO₃⁻ ion preferentially adsorbs at the hollow site of monolayer h-BN, while the NO₃⁻ ion is adsorbed more strongly at the Cu top site of h-BN-supported single-atom Cu due to the abundant d-electron supply from the Cu atom; (4) single-atom Cu can significantly reduce the energy barrier of the rate-determining step (RDS) and increase the probability of nitrate reduction. In conclusion, h-BN-supported single-atom Cu exhibits excellent catalytic performance of NO₃RR. Full article

Single-atom catalysts are highly efficient electrocatalysts for water splitting with exceptional atomic utilization, but atomic aggregation can impair their catalytic performance. To address this challenge, a Fe-Co-Ni single-atom bifunctional catalyst supported on nitrogen-doped graphene oxide was designed and employed for overall water splitting in alkaline electrolyte. The catalyst’s composition, structure, and morphology were systematically characterized using XRD, XPS, SEM, and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Electrochemical evaluations were performed to assess its activity and stability toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The results demonstrate that strong metal-nonmetal interactions between the Fe, Co and Ni single atoms and the nitrogen-doped graphene oxide support facilitate stable and uniform anchoring of the metal centers on the wrinkled carbon framework. The total metal loading reaches approximately 6.78 wt%, ensuring a high density of accessible active sites. Furthermore, synergistic electronic coupling among the Fe, Co, and Ni centers enhances charge transfer kinetics and modulates the D-band electronic states of the metal atoms. This effect weakens the adsorption strength of hydrogen and oxygen-containing intermediates, thus promoting faster reaction kinetics for both HER and OER. Consequently, the FeCoNi/CNG catalyst delivers low overpotentials of 77 mV for HER and 355 mV for OER at a current density of 10 mA cm⁻² in alkaline conditions. When integrated into an alkaline water electrolyzer, the system achieves a cell voltage of only 1.68 V to attain a current density of 10 mA cm⁻², underscoring its outstanding bifunctional catalytic performance. Full article

This article reviews recent advances in heterogeneous hydroformylation, with a particular focus on rhodium-based catalysts supported on oxide surfaces. The hydroformylation reaction is a vital industrial process for producing aldehydes from petrochemicals. This reaction involves the addition of carbon monoxide (CO) and hydrogen (H₂) to alkenes, resulting in the formation of aldehydes. Aldehydes serve as essential building blocks for various downstream products in the chemical industry, including alcohols, esters, and amines. Although homogeneous catalysts such as rhodium complexes coordinated with phosphorus-based ligands (e.g., [RhCl(PPh₃)₃]) are highly active and selective, their separation and recovery remain significant challenges. This has fueled growing interest in the development of heterogeneous catalysts, which offer advantages in terms of sustainability, reusability, and catalyst recovery. This review highlights recent progress in the design of heterogeneous hydroformylation catalysts, with emphasis on rhodium-based systems on oxide supports. Key challenges and emerging strategies for enhancing catalytic performance and stability are also discussed. Full article

The production of green hydrogen by microalgae is a promising strategy to convert energy of sun light into a carbon-free fuel. Many problems must be solved before large-scale industrial applications. One solution is to find a microalgal species that is easy to grow, easy to manipulate, and that can produce hydrogen open-air, thus in the presence of oxygen, for periods of time as long as possible. In this work we investigate by means of predictive computational models, the [FeFe] hydrogenase enzyme of Nannochloropsis salina, a promising microcalga already used to produce high-value products in salt water. Catalysis of water reduction to hydrogen by [FeFe] hydrogenase occurs in a peculiar iron-sulfur cluster (H-cluster) contained into a conserved H-domain, well represented by the known structure of the single-domain enzyme in Chlamydomonas reinhardtii (457 residues). By combining advanced deep-learning and molecular simulation methods we propose for N. salina a two-domain enzyme architecture hosting five iron-sulfur clusters. The enzyme organization is allowed by the protein size of 708 residues and by its sequence rich in cysteine and histidine residues mostly binding Fe atoms. The structure of an extended F-domain, containing four auxiliary iron-sulfur clusters and interacting with both the reductant ferredoxin and the H-domain, is thus predicted for the first time for microalgal [FeFe] hydrogenase. The structural study is the first step towards further studies of the microalga as a microorganism producing pure hydrogen gas. Full article

Chemiresistive gas sensors are extensively employed in environmental monitoring, disease diagnostics, and industrial safety due to their high sensitivity, low cost, and miniaturization. However, the high cross-sensitivity and poor selectivity of gas sensors limit their practical applications in complex environmental detection. In particular, the mechanisms underlying the selective response of certain chemiresistive materials to specific gases are not yet fully understood. In this review, we systematically discuss material design strategies and system integration techniques for enhancing the selectivity and sensitivity of gas sensors. The focus of material design primarily on the modification and optimization of advanced functional materials, including semiconductor metal oxides (SMOs), metallic/alloy systems, conjugated polymers (CPs), and two-dimensional nanomaterials. This study offers a comprehensive investigation into the underlying mechanisms for enhancing the gas sensing performance through oxygen vacancy modulation, single-atom catalysis, and heterojunction engineering. Furthermore, we explore the potential of emerging technologies, such as bionics and artificial intelligence, to synergistically integrate with functional sensitive materials, thereby achieving a significant enhancement in the selectivity of gas sensors. This review concludes by offering recommendations aimed at improving the selectivity of gas sensors, along with suggesting potential avenues for future research and development. Full article

Graphitic carbon nitride is recognized as a very promising support structure to anchor single atoms and small, sub-nanometric metal clusters, with vast applications in catalysis. In the current manuscript, we aim to study the geometry and electronic structures of the small, sub-nanometric monometallic (copper or nickel) and bimetallic (copper–nickel) clusters anchored to the graphitic carbon nitride. Our Density Functional Theory (DFT) study reveals that Cu and Ni, when in the form of isolated single atoms, lie in the plane of the support. Once the atoms agglomerate and form small clusters, they tend to bind above the carbon nitride (C₃N₄) plane. The nickel atoms form shorter bonds with the support than the copper atoms do, which is reflected by the binding energies. Atoms directly bound to the support become oxidized, forming electrophilic sites at the surface. The computed negative metal–support binding energies mean that the investigated Cu/Ni-C₃N₄ composites are stable, and the metal species will not easily leach from the support. Full article

Supported metal catalysts are extensively applied in the heterogeneous catalysis field. However, metal species are prone to migration and aggregation during catalytic reactions due to their high surface energy, which leads to deactivation. In recent years, the use of porous materials, particularly zeolites, to anchor metal species has gained significant attention. By confining metal single atoms, subnanometer metal clusters, and nanoparticles within the pores or nanocavities of these materials, the dispersion and stability of the metal species can be greatly enhanced, thereby improving the catalytic performance. This review systematically discussed the synthesis principles and diverse methodologies to fabricate zeolite-encapsulated metal catalysts. It further outlined their catalytic applications across various catalysis fields, emphasizing enhanced stability and selectivity enabled by confinement effects. Finally, the review provided critical perspectives on future developments, addressing challenges in precise structural control and scalability for industrial implementation. Full article

The recent COVID-19 pandemic has made the public aware of the importance of combating pathogenic microorganisms before they enter the human body. This growing threat from microorganisms prompted us to conduct research into a new type of coating that would be an alternative to the continuous disinfection of touch surfaces. Our goal was to design, synthesise and thoroughly characterise such a coating. In this work, we present a nanocomposite material composed of a thin-layer mesoporous SBA-15 silica matrix containing copper phosphonate groups, which act as catalytic centres responsible for the generation of reactive oxygen species (ROS). In order to verify the structure of the material, including its molecular structure, microscopic observations and Raman spectroscopy were performed. The generation of ROS was confirmed by fluorescence microscopy analysis using a fluorogenic probe. The antimicrobial activity was tested against a wide spectrum of Gram-positive and Gram-negative bacteria, while cytotoxicity was tested on BALB/c3T3 mouse fibroblast cells and HeLa cells. The studies fully confirmed the expected structure of the obtained material, its antimicrobial activity, and the absence of cytotoxicity towards fibroblast cells. The results obtained confirmed the high application potential of the tested nanocomposite coating. 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