Search Results (596)

There is increasing interest in structured layered double hydroxide (LDH)-based catalysts because they combine tunable acid–base/redox chemistry with reactor architectures that can reduce diffusion lengths, improve heat management, and lower pressure-drop penalties. This review evaluates LDH, LDH-derived oxide (LDO/MMO), reduced metal/LDO, reconstructed hydroxide-rich, and mixed dynamic states integrated into honeycomb monoliths, open-cell foams, meshes/felts, thin films, washcoats, coated plates, microchannels, capillaries, and additively manufactured lattices. To move beyond descriptive comparison, the literature is assessed using unified evaluation dimensions: operative active state, support architecture, coating/integration route, active-phase loading, coating thickness and uniformity, reactor-volume-normalized productivity or STY, ΔP/L, axial/radial thermal gradients, time-on-stream, coating loss, regeneration recovery, and pilot-readiness. Representative benchmarks illustrate both the promise and reporting gaps of the field: NiFe-LDH-derived monoliths for CO₂ methanation have reached ~70% CO₂ conversion at 300 °C with >90% CH₄ selectivity and only 0.7% post-test mass loss; NiFe-LDH/iron-foam monoliths retained 85% ozone conversion after 168 h; high-entropy LDH-derived oxides showed T50/T90 values of 246/254 °C for toluene oxidation; and Au/LDH capillary films achieved 31.9% glycerol carbonate yield and 3.78 g h⁻¹ g⁻¹ productivity. The strongest current cases are pollution abatement and CO₂ methanation, whereas biomass upgrading, fine-chemical flow, high-entropy coatings, and photo/electrocatalytic films require deeper module-level validation. Overall, structured LDH catalysts should be treated as coupled chemistry–coating–reactor systems whose performance must be judged simultaneously by activity, accessible catalyst inventory, transport efficiency, pressure drop, thermal profile, durability, regeneration, and manufacturability. Full article

p-nitrophenol (p-NP) is a pollutant with environmental persistence, bioaccumulation potential, and significant health risks, and is widely dispersed in wastewater, so efficient removal of p-NP is imperative. Among the various methods, the catalytic reduction of p-NP to p-aminophenol (p-AP) using sodium borohydride (NaBH₄) is a particularly promising one and, herein, catalysts play a crucial role. Among the various metals, Au shows unique catalytic activity for p-NP reduction. However, nanosized Au often exhibit limited activity and stability due to their high surface free energy. To address this challenge, we designed and synthesized Au-SnO_x hybrid nanoparticles confined within hollow mesoporous silica nanoreactors (Au-SnO_x@hm-SiO₂) via a soft-template-assisted co-adsorption strategy. The resulting bimetallic Au-SnO_x@hm-SiO₂ nanoreactor showed significantly enhanced catalytic activity toward the NaBH₄-mediated reduction of p-nitrophenol (p-NP) compared with its monometallic Au@hm-SiO₂ counterpart, owing to the synergistic effect between Au and SnO_x. Among various Au/Sn ratios, the catalyst with an Au/Sn molar ratio of 1:0.1 demonstrated the highest activity, achieving complete conversion of p-NP within 5 min at a p-NP/Au molar ratio of 529:1—a tenfold improvement over Au@hm-SiO₂. Moreover, the catalyst maintained high efficiency over six consecutive cycles, with only slight deactivation, benefiting from the protective silica shell. Full article

A novel transition-metal-free alkyne–thiol click polymerization with 100% atom economy is reported. Using ^tBuOLi as a catalyst at 80 °C, the polymerization efficiently yields poly(vinyl sulfide)s (PVSs) with molecular weights up to 11,800 g/mol and yields up to 91%. These sulfur-rich polymers exhibit high thermal stability (T_d up to 293 °C) and high refractive indices (1.8375–1.6383) across the visible range. By integrating abundant sulfur coordination sites with aggregation-induced emission (AIE) properties, the PVS aggregates serve as high-performance fluorescent chemosensors. The sensor enables exclusive, sensitive trace detection of Pd²⁺ and Au³⁺ with remarkable anti-interference capability and pH robustness (pH 1–7). Notably, an ultrafast response (1–2 min) for Pd²⁺ is achieved, with limits of detection (LOD) reaching 7.11 × 10⁻⁷ M for Pd²⁺ and 1.06 × 10⁻⁶ M for Au³⁺, and corresponding limits of quantification (LOQ) reaching 2.37 × 10⁻⁶ M and 3.53 × 10⁻⁶ M, respectively. This methodology offers a sustainable route to heteroatom-rich macromolecules for next-generation optical engineering and environmental monitoring. Full article

Developing effective catalysts for the epoxidation of propylene with H₂ and O₂ holds significant scientific and industrial significance. This study synthesized a series of Au/TS-1 catalysts modified with alkali metals (Na⁺, Cs⁺) and carefully examined their impact on gas-phase propylene epoxidation, with particular attention to the role of anions. The optimal Au–CsC(1:10)/TS-1 catalyst (Cs₂CO₃ modified, Au/Cs molar ratio = 1:10) achieves a propylene conversion of 16.8%, a PO selectivity of 88.5%, an H₂ efficiency of 40.8%, a record PO formation rate of 383.9 g_po·kg_cat⁻¹·h⁻¹, and unprecedented long term stability (>380 h without deactivation). To the best of our knowledge, no previous study has simultaneously achieved such balanced and outstanding performance across all these key indicators. Comprehensive characterization reveals that Cs⁺ modification suppresses side reactions and coke formation, increases microporosity, tunes surface acid–base properties and hydrophobicity, restricts Au particle size, and stabilizes both Au⁰ and tetra coordinated Ti sites, thereby inhibiting H₂O₂ decomposition and PO isomerization while greatly enhancing reaction efficiency. This holistic advancement represents a significant leap forward for Au based catalysts in gas phase propylene epoxidation, offering both a theoretical foundation and practical guidance for the development of high performance epoxidation catalysts. Full article

Sulfur is a well-known catalyst poison, particularly for catalysts based on transition metals. Herein, we studied the adsorption of sulfur species on small nanoparticles (~1 nm in size) of the face centered cubic (fcc) transition metals (Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) using density functional theory (DFT) modeling. At low sulfur coverage (one S atom per nanoparticle), sulfur preferentially occupies the surface hollow sites of the nanoparticles. At higher coverage, however, the subsurface diffusion of S in Ni, Pd, and Ag nanoparticles becomes energetically favorable with low activation energies. Among the considered metals, sulfur binds most strongly to Rh and Ir, and most weakly to Ag and Au. The present results shed light on the facility of S-poisoning on such metal nanoparticles, either by surface blocking or by underlying sulfurization of the metal. Full article

A novel citric acid-assisted in situ reduction method has been developed for the synthesis of bimetallic AuPd alloy nanoparticles supported on amine–phosphate-functionalized carbon nanotubes (AuPd/NH₂-P-CNTs). In this strategy, formic acid acts not only as the reducing agent for reducing metal precursors, but also as the hydrogen source for the subsequent catalytic dehydrogenation. The introduction of citric acid significantly accelerates the reduction kinetics and promotes the uniform formation of ultrafine AuPd nanoparticles (∼1.8 nm). As a result, the optimized Au_0.5Pd_0.5/NH₂-P-CNTs exhibit an extraordinary catalytic activity and 100% H₂ selectivity during hydrogen generation from FA with sodium formate as an additive, affording a remarkable initial turnover frequency of 5663.94 mol H₂ mol Pd⁻¹ h⁻¹ at 303 K. The experimental results reveal that the -NH₂ and -P functional groups on the support are crucial for stabilizing and uniformly dispersing the alloy nanoparticles. Furthermore, the enhanced reaction rate can be attributed to the strong metal–support interaction established between AuPd nanoparticles and -NH₂-P-CNT supports. This work provides a new perspective on the design of highly efficient Pd-based catalysts for hydrogen production from formic acid. Full article

Biotemplated strategies inspired by natural architecture have emerged as an effective strategy to improve the performance of photocatalytic materials. In this work, TiO₂-based photocatalysts were synthesized using olive leaves as a biological template to reproduce their hierarchical microstructure and enhance photocatalytic hydrogen production. The artificial olive leaf (AOL) support was obtained through a biotemplated ion-exchange process followed by hydrolysis and calcination. It was then modified by photodeposition of Au or Pt nanoparticles. The materials were characterized by SEM, XRD, N₂ adsorption–desorption, UV–Vis spectroscopy, and XPS to evaluate their structural and optical properties. SEM confirmed the successful replication of both the external morphology and internal architecture of the olive leaf, while XRD revealed low crystallinity with anatase as the only TiO₂ phase. Optical characterization showed a reduced band gap (~2.97 eV), and extended absorption toward the visible region, with Au nanoparticles exhibiting a plasmonic band at ~550 nm, whereas Pt enhanced light-harvesting efficiency. XPS indicated the presence of oxygen vacancies and Ti³⁺ species that promote metal–support interactions. Photocatalytic glycerol photoreforming showed a strong enhancement in hydrogen production after noble metal incorporation, reaching up to 14-fold under UV irradiation and 23-fold under simulated solar light for the Pt-modified catalyst, highlighting the synergy between biotemplated structuring and noble metal deposition. Full article

A series of bifunctional hierarchical HZSM-5 catalysts modified with Zn, Ga, Ni, Cr, or Ag were synthesized via impregnation, and their performance in the catalytic fast pyrolysis of walnut shells was systematically evaluated. The influence of the metal species and concentration of NaOH used for desilication (0.20–0.40 mol·L⁻¹) on the yield of light aromatics was assessed. Ga/HZSM-5 and Zn/HZSM-5 exhibited the most pronounced enhancement at 0.35 mol·L⁻¹, significantly outperforming the unmodified HZSM-5. Building on this finding, Zn-Ga bimetallic hierarchical catalysts were developed, and the effect of the Zn:Ga loading ratio (1%:2%, 1.5%:1.5%, 2%:1%) was investigated. The 1%Zn/2%Ga catalyst delivered the highest performance, achieving a total aromatic yield of 3.876 × 10⁴ a.u.·mg⁻¹, with 82% BTX (benzene, toluene, and xylenes) selectivity. The term “a.u.” stands for “arbitrary units,” typically derived from peak area counts obtained through GC-MS analysis. These values represent the relative signal intensity detected by the instrument, rather than absolute quantities of the substance. To more accurately characterize the aromatic hydrocarbon yield, these data are normalized to the yield of aromatic hydrocarbons per unit mass. These findings demonstrate that the combination of Zn-Ga modification and tailored mesoporosity can markedly enhance the production of high-value benzene, toluene, and xylene (BTX) aromatics from lignocellulosic biomass. Full article

Mixed-halide perovskite solar cells with the composition Cs_0.1(MA_0.17FA_0.83)_0.9Pb(I_0.83Br_0.17)₃ were fabricated obtaining solar cells as glass/ITO/SnO₂/triple-cation perovskite/HTL/Au, and subsequently used as photoanodes for efficient solar-driven water splitting by attaching commercial catalytic nickel foils to the Au back-contact pads of solar cells. To enable operation in alkaline media, the devices were encapsulated using commercial PET–EVA multilayer films, providing an effective barrier while leaving the Ni foils exposed as the electrochemically active interface. Two operating configurations were investigated and compared: (i) an outside configuration, where the perovskite device powered the external electrochemical cell, and (ii) an immersed configuration, in which the encapsulated perovskite solar cell was directly integrated, together with the Ni catalyst, into the electrolyte. In both configurations, the onset potential for the oxygen evolution reaction shifted from ~1.32 V vs. RHE, when the Ni electrode was not powered by the perovskite solar cell, to ~0.34 V vs. RHE, when the perovskite device powered the Ni foil for both immersed and outside configurations. The immersed configuration delivered the highest performance, achieving a maximum Applied Bias Photon-to-Current Efficiency of ~20% under AM 1.5 G illumination (100 mW cm⁻²), among the highest values reported for perovskite-based photoanodes. Importantly, the enhanced performance does not arise from changes in catalyst composition or direct semiconductor–electrolyte interaction, but from improved photovoltage delivery and reduced resistive losses enabled by the integrated device architecture. These results demonstrate that device architecture is a key factor in controlling photovoltage utilization and charge-transfer kinetics, providing a viable strategy for efficient and scalable perovskite-based photoelectrochemical systems. Full article

The reaction mechanism of the gold-catalyzed hydrothiolation of alkenes (1) with thiols (2) has been investigated in detail. The tetranuclear gold complex, (PPh₃)₄Au₄(SPh)₂(NTf)₂ (A), is a key intermediate in the catalytic hydrothiolation of alkenes. It forms instantaneously when PPh₃AuNTf₂ and PhSH are mixed in THF. Monitoring the reaction over time using ³¹P NMR spectroscopy revealed that gold complex A remained stable in the reaction system throughout the hydrothiolation process. In addition, we successfully observed a rapid ligand-exchange reaction between the thiolate group of gold complex A and thiols in solution. The gold-catalyzed alkene hydrothiolation reaction has been applied to the catalytic hydrothiolation of allenes, which have degenerate double bonds. Hydrothiolation of allenes proceeded regioselectively at the terminal double bond. However, the yield was lower than that observed for alkenes, and catalyst deactivation occurred. The hydrothiolation products of allenes were difficult to detach from the gold catalyst, necessitating an increase in the reaction temperature. Since high periodic transition metals such as gold and platinum are effective for hydrothiolation of alkenes and allenes, it is interesting to clarify whether iridium complexes, which belong to the same period as gold and platinum, could also catalyze alkene hydrothiolation. Through a detailed investigation of iridium ligands and reaction conditions, it was found that, in iridium systems, disulfide formation via oxidative coupling of thiols occurs preferentially over hydrothiolation reactions. This is likely due to steric hindrance around the iridium center, which inhibits alkene coordination to the iridium. Additionally, the hydrothiolation proceeding at low yields is believed to be a radical reaction involving electron transfer through the iridium complex. Full article

The development of efficient and non-toxic fuels for direct liquid fuel cells has highlighted ascorbic acid (AA) as a sustainable energy source. This study presents a combined theoretical and experimental investigation of ascorbate oxidation on an Au-Pt electrode in alkaline medium. Density functional theory (DFT) calculations reveal that Au deposition on Pt creates a more homogeneous and active surface, significantly enhancing the adsorption energy of ascorbate (−7.54 eV vs. −5.80 eV on bare Pt). Electrochemically, this translates to a superior performance, where the Au-Pt electrode achieves a 38% reduction in charge-transfer resistance, a higher current density, and a lower Tafel slope of 77 mV dec⁻¹, indicating accelerated kinetics. The electrode also retains its activity over 1000 cycles, confirming exceptional durability. This synergistic combination of theoretical and experimental results establishes Au-Pt as a premier catalyst for sustainable ascorbate-based energy conversion. Full article

Direct borohydride fuel cells (DBFCs) are emerging as a promising source of clean energy; however, their performance depends heavily on efficient anode catalysts for the oxidation reaction of sodium borohydride (BOR). In this study, we developed and tested the Au–NiZn/Ti electrocatalyst designed to improve the performance of DBFCs. Electrodeposition and alkaline leaching were utilized to transform a zinc-rich nickel coating into a porous dendritic structure on a titanium substrate. By adding a small amount of gold crystallites through galvanic displacement, the surface roughness and the number of active sites available for the reaction were significantly increased. Electrochemical tests confirmed that this modification enhances BOR and effectively suppresses unwanted side reactions like hydrogen evolution. The resulting catalyst demonstrated high stability, maintaining over 88% of its current density during extended operation. Ultimately, the study positions this gold-modified material as a cost-effective and durable solution for clean energy conversion technologies. Full article

The plasma-catalytic conversion of CO₂ is a promising route toward sustainable fuel and chemical production under mild operating conditions. However, many aspects still need to be better understood to improve performance and better understand the catalyst-plasma synergies. Among them, one aspect concerns understanding whether photons emitted by plasma discharges could induce changes in the catalyst, thereby promoting interaction between plasma species and the catalyst. This question was addressed by investigating the CO₂ splitting reaction in a planar dielectric barrier discharge (pDBD) reactor using titania-based catalysts that simultaneously act as discharge electrodes. Four systems were examined feeding pure CO₂ at different flow rates and applied voltage: bare titanium gauze, anodically formed TiO₂ nanotubes (TiNT), TiNT decorated with Ag–Au nanoparticles (TiNTAgAu), and TiNT supporting Ag–Au nanoparticles coated with polyaniline (TiNTAgAu/PANI). The TiNTAgAu exhibited the highest CO₂ conversion (35% at 10 mL min⁻¹ and 5.45 kV) and the most intense optical emission, even in the absence of external light irradiation, suggesting that the improvement is primarily attributed to plasma–nanoparticle interactions and self-induced localized surface plasmon resonance (si-LSPR) rather than conventional photocatalytic pathways. SEM analyses indicated severe plasma-induced degradation of TiNT and TiNTAgAu surfaces, leading to performance decay over time. In contrast, the TiNTAgAu/PANI catalyst retained structural integrity, with the polymeric coating mitigating plasma etching while maintaining competitive efficiency. There is thus a complex behavior with catalytic performance governed by nanostructure stability, plasmonic enhancement, and the interfacial protection. The results demonstrate how integrating plasmonic nanoparticles and conductive polymers can enable the rational design of durable and efficient plasma-photocatalysts for CO₂ valorization and other plasma-assisted catalytic processes. Full article

The development of non-noble metal catalysts provides a cost-effective and sustainable route for glucose oxidation to gluconic acid. In this study, a series of catalysts based on inexpensive transition metals (Cr, Cu, Ni, Fe) and/or Au were synthesized using siliceous supports (SiO₂ and MCM-41) and systematically evaluated. The aim was to partially or fully replace noble metals with lower-cost alternatives, while maintaining high catalytic performance. Comprehensive characterization—including ICP-AES for composition, N₂ adsorption–desorption for porosity, XRD for structure, H₂-TPR for reducibility, and NH₃-TPD for acidity—was conducted to establish structure–property relationships. Among the tested catalysts, Ni- and Fe-based systems exhibited superior stability, with NiO/SiO₂ achieving gluconic acid yields comparable to Au. The bimetallic Au–Ni/SiO₂ catalyst displayed enhanced metal–support interactions and minimal leaching (<2%), while Au–Fe/SiO₂ improved selectivity, yielding up to 23% gluconic acid, surpassing 5Fe/SiO₂ (18%) and 0.3Au/SiO₂ (15%), albeit with lower stability. These results highlight the potential of low-cost transition-metal and bimetallic catalysts as efficient and economically viable systems for selective glucose oxidation, providing insights for rational catalyst design in sustainable carbohydrate valorization. Full article

This paper demonstrates the results of constructive technological research on the development of a catalyst with a Ni/PSi@Pt structure. This catalyst eliminates the use of gold in the structure of μ-FC electrodes. This work uses the main technological solutions for the formation of a gold-containing “core–shell” structure on the inner surface of pores. Comparative data on the results of assessing the durability of porous silicon electrodes with both Pt catalysts and composite catalysts of the Pt/In₂O₃, Pt/SnO₂, Pt/Au and Pt/Ni types are also presented. Full article