Search Results (89)

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

Hydroformylation is one of the most widely applied homogeneous catalytic processes in the chemical industry, constituting the predominant manufacturing platform for aldehyde synthesis at commercial scales. Nevertheless, hydroformylation shares with traditional homogeneous catalysis the inherent limitation of difficult catalyst recovery and recycling. Developing heterogeneous catalysts for such reactions is thus critically needed. Herein, a stable nitrogen-rich covalent triazine framework (CTF) was synthesized via a mild Friedel–Crafts alkylation method and employed as a support for Rh single-atom catalysts (Rh/CTF-TPA). In the hydroformylation of 1-decene, the Rh/CTF-TPA catalyst exhibits an exceptional reaction efficiency (TOF > 1900 h⁻¹), outperforming the homogeneous Rh(CO)₂(acac). Experimental and characterization results revealed that the CTF support enhances catalytic performance through two key mechanisms: (1) strong enrichment of reactants within its special structure, and (2) efficient dispersion of Rh single-atom sites stabilized by abundant nitrogen coordination. This work demonstrates a rational design strategy for heterogeneous hydroformylation catalysts by leveraging nitrogen-rich porous frameworks to synergistically optimize metal anchoring and reactant enrichment, offering a promising alternative to conventional homogeneous systems. Full article

Micropollutants (MPs), which include both natural and manmade substances, are becoming more prevalent in aquatic habitats as a result of the insufficient removal of these compounds in wastewater treatment plants (WWTPs). Advanced remediation techniques are required due to their persistence and potential ecotoxicological hazards. Although adsorption and photo(electro)catalysis exhibit potential in laboratory-scale investigations, the effects of their use in actual WWTP systems are still poorly understood. However, before large-scale application can be implemented, a number of issues need to be resolved, including material limitations, reactor design and optimization, and actual wastewater complexities. This study critically evaluates the application of adsorption and photo(electro)catalysis to actual wastewater, as well as recent advancements in adsorption and photo(electro)catalytic systems for the removal of micropollutants. We also explore the particular difficulties and strategies involved in the large-scale use of adsorption and photo(electro)catalysis in the treatment of wastewater. Emerging trends such as nanocomposites, metal–organic frameworks (MOFs), heterojunctions, and single-atom catalysts (SACs) are highlighted by the bibliometric analysis. We also evaluate MPs’ ecological effects in aquatic environments and the incorporation of artificial intelligence (AI) for process optimization. A strategy for transferring nanotechnologies from laboratory-scale research to wastewater treatment implementation is presented in this paper. In this strategy, implementation is proposed based on actual wastewater conditions, focusing on the development of adsorbents and catalysts, reactor design and optimization, synergy between adsorption and catalysis, life cycle analysis, and cost–benefit studies. Full article

With the increasing detection of antibiotics such as sulfamethoxazole (SMX) in water bodies, developing efficient and eco-friendly treatment technologies is critical. This study employs a hydrothermal impregnation method to prepare a NiFe₂O₄/granular activated carbon (GAC) composite catalyst, optimized for use in a proton exchange membrane (PEM) electrolytic ozonation system to degrade SMX. Single-factor experiments optimized preparation conditions with a Fe:Ni molar ratio of 3:1, a GAC:Fe + Ni mass ratio of 2:1, and calcination at 500 °C for 3 h. The catalyst was characterized using XRD, SEM, TEM, XPS, and FT-IR, confirming a spinel NiFe₂O₄ structure (crystal size ~15.2 nm) uniformly dispersed on GAC, with an Fe:Ni atomic ratio of ~2.1:1. In the PEM system, the optimized catalyst achieved a 99.15% ± 0.3% SMX degradation rate (50 mg/L) within 25 min, compared to 95.06% ± 0.6% in 30 min without a catalyst. The catalyst maintained 98.45% ± 0.5% efficiency after three cycles, demonstrating excellent stability. The synergy between GAC adsorption and NiFe₂O₄ catalysis, driven by Fe³⁺/Fe²⁺ redox cycling, enhances ·OH generation from ozone decomposition, boosting SMX degradation. This work provides a robust catalyst for antibiotic wastewater treatment and a foundation for scaling up catalytic ozonation. Full article

Metalloporphyrins and porphyrins (MPs) have garnered increasing attention as potential candidates for molecular-based electronic devices and single-atom catalysis. Recent studies have found that electronic structure calculations are important factors in controlling the performance of MPs as building blocks for single-molecule devices. Our study investigates metalloporphyrins with central 3d-metals from Sc to Cu and chalcogen containing anchoring groups such as -SH, -SeH, and -TeH substituted at the meso-position of the porphyrin rings. We carried out Density Function Theory (DFT)-based calculations to determine the ground state geometry, spin multiplicity, spatial distribution of the molecular orbitals, and electronic structure descriptors to gain insights into the reactivity trends and possible impact on factors influencing electron transport properties. The results suggest that the central metal shapes the spin multiplicity, while variations between sulfur, selenium, and tellurium play a role in charge distribution. This study provides insights into how the selection of the central metal and control of spin channels influence the electronic structure and reactivity of metalloporphyrin molecules. The knowledge provided here can play a role in the design of porphyrin-based molecular materials for diverse applications in molecular junctions, catalysis, photovoltaics, and sensing. Full article

Catalysis requires extrapolations from computational models to the catalytic activity observed under practical operating conditions, especially for single-atom catalysts, to be made. Thus, it is necessary to understand the fundamental interactions at an atomistic level to rationally design systems for targeted practical applications. With that in mind, the key aspects and parameterization of these model systems are especially important as they will heavily affect the validity of those extrapolations. Rigorously developed models and protocols with well-defined and understood metrics and interactions are reviewed to begin to provide an overview of the best theoretical practices for designing nitrogen-doped carbon supports. Full article

Herein, we report the use of a nanotechnology-based approach for the study of enzyme-functionalized mica surfaces. Atomic force microscopy (AFM) has been employed for the determination of the catalytic activity of single molecules of heme-containing cytochrome P450 CYP102A1 (CYP102A1) enzyme, which was immobilized on the surface of a mica chip. Height fluctuations in individual molecules of the enzyme were measured under near-native conditions by AFM measurements in liquid using a cantilever with a 10 to 20 nm tip curvature radius. We have found that in the process of enzymatic catalysis, the mean amplitude of height fluctuations in individual enzyme molecules is 1.4-fold higher than that of enzyme molecules in an inactive state. The temperature dependence of the mean amplitude of height fluctuations in cytochrome CYP102A1 has been revealed, and the maximum of this dependence has been observed at 22 °C. The proposed nanotechnology-based approach can be employed in studies of a wide variety of enzymes, which are important for the development of novel diagnostic tests and systems for pharmaceutical analysis. The approach developed in our work will favor further miniaturization of enzyme-based biosensors and the transition from traditional sensors to nanobiosensors. Full article

Under mild conditions, the effective conversion of carbon dioxide (CO₂) into formic acid (HCOOH) and carbon monoxide (CO) represents a promising avenue for mitigating greenhouse gas emissions and addressing energy crises. In this work, we analyzed the electro-catalytic activities of six metals (Ti, Fe, Ni, Cu, Zn, and Cr) anchored on monolayer molybdenum telluride (TM@MoTe₂) for the CO₂ reduction reaction (CO₂RR) from CO₂ to HCOOH and CO. Compared to the reversible hydrogen electrode, the limiting potential for HCOOH production on Ni@MoTe₂ is only about −0.38 V, and it is only about −0.20 V for the CO production on Cu@MoTe₂. The limiting potential is concerned with the free energies of *OCHO and *COOH. Both the CO₂RRs suppress the competing hydrogen evolution reaction (HER) and exhibit good selectivity for the desired reaction products. These features enable the efficient conversion of CO₂ into HCOOH on Ni@MoTe₂ or CO on Cu@MoTe₂. Our calculations could provide valuable insights for the design and synthesis of high-performance catalysts based on MoTe₂. Full article

The electrochemical reduction of carbon dioxide (CO₂RR) utilizing intermittent electricity from renewable energy sources represents an emerging and promising approach to achieve carbon neutrality and mitigate the greenhouse effect. This review comprehensively summarizes recent advances in Cu-based metal–organic framework (MOF) electrocatalysts for CO₂RR, focusing on their applications in producing C₁ and C₂₊ products. This paper highlights key strategies such as nanostructure manipulation, multi-component tandem catalysis, single-atom alloying, and ligand functionalization to optimize the binding energies of intermediate species and promote selective CO₂RR pathways. Numerous examples are presented, showcasing remarkable Faradaic efficiencies and product selectivities achieved through rational catalyst design. Furthermore, the use of MOF-derived materials and composites with other materials, like carbon nanotubes, graphene, and metal oxides, is discussed to enhance conductivity, stability, and selectivity. Despite the significant progress, challenges remain in achieving stable and scalable catalysts with high activity and selectivity towards specific C₂₊ products. This review underscores the importance of precise control of catalyst composition, structure, and surface properties to tackle these challenges and provides valuable insights for future research directions in developing advanced Cu-based MOF electrocatalysts for practical applications in CO₂ conversion technologies. Full article

Developing stable and effective catalysts for the hydrogen evolution reaction (HER) has been a long-standing pursuit. In this work, we propose a series of single-atom catalysts (SACs) by importing transition-metal atoms into the carbon and vanadium vacancies of tetragonal V₂C₂ and V₃C₃ slabs, where the transition-metal atoms refer to Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. By means of first-principles computations, the possibility of applying these SACs in HER catalysis was investigated. All the SACs are conductive, which is favorable to charge transfer during HER. The Gibbs free energy change (ΔG_H*) during hydrogen adsorption was adopted to assess their catalytic ability. For the V₂C₂-based SACs with V, Cr, Mn, Fe, Ni, and Cu located at the carbon vacancy, excellent HER catalytic performance was achieved, with a |ΔG_H*| smaller than 0.2 eV. Among the V₃C₃-based SACs, apart from the SAC with Mn located at the carbon vacancy, all the SACs can act as outstanding HER catalysts. According to the ΔG_H*, these excellent V₂C₂- and V₃C₃-based SACs are comparable to the best-known Pt-based HER catalysts. However, it should be noted that the V₂C₂ and V₃C₃ slabs have not been successfully synthesized in the laboratory, leading to a pure investigation without practical application in this work. Full article

Palladium-doped silver nanoclusters (NCs) have been highlighted for their unique physicochemical properties and potential applications in catalysis, optics, and electronics. Anion-directed synthesis offers a powerful route to control the morphology and properties of these NCs. Herein, we report a novel Pd-doped Ag NC, [Pd(H)Ag₁₃(S){S₂P(OⁱPr)₂}₁₀] (PdHAg₁₃S), synthesized through the inclusion of sulfide and hydride anions. This NC features a unique linear S-Pd-H axis enclosed in a 4-5-4 stacked arrangement of silver atoms. The distinctive hydride environment was characterized by NMR spectroscopy, and the total structure was determined by single-crystal X-ray diffraction (SCXRD) and supported by computational studies. Mass spectrometry and X-ray photoelectron spectroscopy (XPS) further confirmed the assigned composition. This unique construct exhibits promising hydrogen evolution reaction (HER) activity. Our findings highlight the potential of anion-directed synthesis for creating novel bimetallic NCs with tailored structures and catalytic properties. Full article

Developing low-cost, efficient alternatives to catalysts for bifunctional oxygen electrode catalysis in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is critical for advancing the practical applications of alkaline fuel cells. In this study, Co particles and single atoms co-loaded on nitrogen-doped carbon (CoNC) were synthesized via pyrolysis of a C₃N₄ and cobalt nitrate mixture at varying temperatures (900, 950, and 1000 °C). The pyrolysis temperature and precursor ratios were found to significantly influence the ORR/OER performance of the resulting catalysts. The optimized CoNC-950 catalyst demonstrated exceptional ORR (E_1/2 = 0.85 V) and OER (E_j10 = 320 mV) activities, surpassing commercial Pt/C + RuO₂-based devices when used in a rechargeable zinc–air battery. This work presents an effective strategy for designing high-performance non-precious metal bifunctional electrocatalysts for alkaline environments. Full article

This study explores the application of Atomic Layer Deposition (ALD) to functionalize high-surface-area carbon supports with metal and metal oxide films and particles for applications in catalysis and electrocatalysis. The work reported here demonstrates that, through careful choice of precursors and absorption and reaction conditions, self-limited ALD growth on a high-surface-area carbon support can be achieved. Specific examples presented include the growth of conformal films of ZrO₂ and SnO₂ and the deposition of Ga₂O₃ and Pt particles on a carbon black support with a surface area of 250 m²·g⁻¹. A novel strategy for controlling the Pt weight loading and producing sub-nanometer Pt particles on a carbon support using a single ALD cycle is also presented. Full article

This study investigated the electronic structure of single-atom Rhodium (Rh) and Iridium (Ir) adsorbed on defective and impurity-doped ZnO(0001) surfaces, and assessed their activity towards the CO oxidation reaction. Our findings reveal that surface impurities significantly influence the binding energies and electronic properties of the metal atoms, with Al and Cr serving as particularly effective promoters. While Rh and Ir acquire a positive charge upon incorporation on the unpromoted Zn(0001) surface, adsorption directly on the promoter results in a net negative charge, thus facilitating the activation of both CO and O₂ species. These results highlight the potential of impurity-promoted ZnO surfaces in modulating and tailoring the electronic properties of SACs, which can be used for a rational design of active single-atom catalysts. Full article