Highly Stable and Efficient Oxygen Evolution Electrocatalyst Based on Co Oxides Decorated with Ultrafine Ru Nanoclusters

Exploring highly active and durable electrocatalysts for oxygen evolution reaction (OER) is significant to achieve efficient anion exchange membrane (AEM) water electrolysis. Herein, hollow Co-based N-doped porous carbon spheres decorated with ultrafine Ru nanoclusters (HS-RuCo/NC) are reported as efficient OER electrocatalysts via the pyrolysis of carboxylate-terminated polystyrene-templated bimetallic zeolite imidazolate frameworks accommodating Ru (III) ions. The unique hollow structure with hierarchically porous characteristics contributes to the electrolyte penetration for fast mass transport and the exposure of more metal sites. Theoretical and experimental studies reveal the synergistic effect between the in situ formed RuO₂ and Co₃O₄ as another critical factor for the high OER performance, where the coupling of RuO₂ with Co₃O₄ can optimize the electronic configuration of RuO₂/Co₃O₄ heterostructure and decrease the energy barrier during OER. Meanwhile, the presence of Co₃O₄ can efficiently suppress the over-oxidation of RuO₂, endowing the catalysts with high stability. As expected, when the resultant HS-RuCo/NC was integrated into an AEM water electrolyzer, the obtained electrolyzer exhibits a cell voltage of 2.07 V to launch the current density of 1 A cm⁻² and excellent long-term stability at 500 mA cm⁻² under room temperature in alkaline solution, outperforming the commercial RuO₂-based AEM water electrolyzer (2.19 V).     

Manipulating the Rectifying Contact between Ultrafine Ru Nanoclusters and N-Doped Carbon Nanofibers for High-Efficiency pH-Universal Electrocatalytic Hydrogen Evolution

The rational design of ingenious strategies to boost the intrinsic activity and stability of ruthenium (Ru) is of great importance for the substantial progression of water electrolysis technology. Based on Mott–Schottky effect, electronic regulation within a metal/semiconductor hybrid electrocatalyst represents a versatile strategy to boost the electrochemical performance. Herein, a typical Mott–Schottky hydrogen evolution reaction (HER) electrocatalyst composed of uniform ultrafine Ru nanoclusters in situ anchored on N-doped carbon nanofibers (abbreviated as Ru@N-CNFs hereafter) through a feasible and scalable “phenolic resin-bridged” strategy is reported. Both spectroscopy analyses and density functional theory calculations manifest that such rectifying contact can induce the spontaneous electron transfer from Ru to N-doped carbon nanofibers to generate a built-in electric field, thus enormously promoting the charge transfer efficiency and HER intrinsic activity. Moreover, the seamless immobilization of Ru nanoclusters on the substrate can prevent the active sites from unfavorable migration, coarsening, and detachment, rendering the excellent structural stability. Consequently, the well-designed Ru@N-CNFs afford prominent pH-universal HER performances with small overpotentials of 16 and 17 mV at 10 mA cm⁻² and low Tafel slopes of 31.8 and 28.5 mV dec⁻¹ in acidic and alkaline electrolytes, respectively, which are superior to the state-of-the-art commercial Pt/C and Ru/C benchmarks.     

Catalytic activity of polymer-bound Ru(III)-EDTA complex

Chloromethylated styrene-divinylbenzene copolymer was chemically modified with ethylenediaminetetraacetic acid ligand. Catalytically active polymer containing Ru(III) moieties were synthesized from this polymeric ligand. They were characterized using FTIR, UV-vis, SEM, ESR and TGA. Other physico-chemical properties such as bulk density, surface area, moisture content and swelling behaviour in different solvents were also studied. The polymer bound complex was used to study hydrogenation of 1-hexene ton-hexane under mild conditions. Influence of [1-hexene], [catalyst], temperature and nature of the solvent on the rate of the reaction was investigated. A rate expression is proposed based on the observed initial rate data. Recycling efficiency of the catalyst has also been studied.     

Miscible-Solvent-Assisted Two-Phase Synthesis of Monolayer-Ligand-Protected Metal Nanoclusters with Various Sizes

Effective yet versatile synthetic strategies for size-tunable metal nanoclusters (NCs) are scarce. This has hampered the development of this unique class of nanomaterials. Here, a general protocol is reported for the synthesis of high-quality metal NCs protected by a variety of organic ligands (e.g., selenolate, thiolate, and phosphine) based on a miscible-solvent-assisted phase transfer between water and organic solution. This method is demonstrated to be facile, rapid (≤3 h), scalable (gram-scale), and versatile. The size of the selenolated and thiolated Au NCs can be tuned from Au₁₀ to Au₆₁ by simply varying the miscible solvent in proportions and types. The advantages of this method, such as quick phase separation and no need for purification treatment, enable real-time monitoring of metal NC growth within the NaBH₄ reduction system. The results show that the size of Au NCs gradually increases with increasing valence electron count by a stepwise 2x e^- hopping mechanism (x = 0–5), i.e., 0 e^- → 2 e^- → 4 e^- → 8 e^- → 18 e^- → 22 e^- → 32 e^-.     

Sub‐10 nm Ag Nanoparticles/Graphene Oxide: Controllable Synthesis,Size‐Dependent and Extremely Ultrahigh Catalytic Activity

While tremendous advancements in Ag nanoparticle (AgNP)‐based materials have been made, the development of a facile protocol for preparing sub‐10 nm AgNPs with controllable size and ultrahigh performance remains a formidable challenge. It is shown that AgNPs/graphene oxide (AgNPs/GO) bearing 2.5, 4.3, and 6.2 nm AgNPs (2.5‐AgNPs/GO, 4.3‐AgNPs/GO, and 6.2‐AgNPs/GO, respectively) could be fabricated via light‐induced synthesis. Their catalytic activity toward 4‐nitrophenol (4‐NP) reduction, which is a “gold standard” for evaluating the performance of noble metal–based catalysts, is studied. When normalized by mole and area, the activity exhibits an order of 4.3‐AgNPs/GO > 6.2‐AgNPs/GO > 2.5‐AgNPs/GO and 6.2‐AgNPs/GO > 4.3‐AgNPs/GO > 2.5‐AgNPs/GO, respectively. This trend is a result of GO‐induced electron concentration reduction with decreasing AgNP size. Significantly, under similar conditions, the activity of 4.3‐AgNPs/GO is substantially superior to that of numerous state‐of‐the‐art noble metal–based catalysts. The ultrafine size of the AgNPs and their surface accommodation on the unobstructed 2D GO scaffolds without capping reagents/covers, which make the abundantly exposed catalytically active sites highly accessible to substrate molecules, play an important role in their extremely ultrahigh performance. This work paves a new avenue for high‐performance AgNP‐based materials, and by taking 4‐NP reduction as a proof‐of‐concept, provides new scientific insights into the rational design of surface‐based advanced materials.     

Phosphine‐Based Covalent Organic Framework for the Controlled Synthesis of Broad‐Scope Ultrafine Nanoparticles

In this work, a phosphine‐based covalent organic framework (Phos‐COF‐1) is successfully synthesized and employed as a template for the confined growth of broad‐scope nanoparticles (NPs). Ascribed to the ordered distribution of phosphine coordination sites in the well‐defined pores, various stable and well‐dispersed ultrafine metal NPs including Pd, Pt, Au, and bimetallic PdAuNPs with narrow size distributions are successfully prepared as determined by transmission electron microscopy, X‐ray photoelectron spectroscopy, inductively coupled plasma, and powder X‐ray diffraction analyses. It is also demonstrated that the as‐prepared Phos‐COF‐1‐supported ultrafine NPs exhibit excellent catalytic activities and recyclability toward the Suzuki–Miyaura coupling reaction, reduction of nitro‐phenol and 1‐bromo‐4‐nitrobenzene, and even tandem coupling and reduction of p‐nitroiodobenzene. This work will open many new possibilities for preparing COF‐supported ultrafine NPs with good dispersity and stability for a broad range of applications.     

Size-Defined Ru Nanoclusters Supported by TiO2 Nanotubes Enable Low-Concentration Nitrate Electroreduction to Ammonia with Suppressed Hydrogen Evolution

Anthropogenic nitrate pollution has an adverse impact on the environment and human health. As part of a sustainable nitrate management strategy, electrochemical denitrification is studied as an innovative strategy for nutrients recycling and recovering. It is, however, challenging to selectively electro-reduce nitrate with low-concentration for ammonia. Herein, the photo-deposition of size-defined Ru nanoclusters (NCs, average size: ≈1.66 nm) on TiO₂ nanotubes (NTs) is demonstrated, which show improved performance for nitrate-to-ammonia electroreduction with a maximum yield rate of ≈600 µg h⁻¹ cm⁻² and a faradic efficiency (FE) of > 90.0% across a broad range of potentials in comparison with electrodeposited Ru nanoparticles (NPs, average size: ≈23.78 nm) on TiO₂ NTs. Experimental and theoretical evidence further suggests the small-size Ru NCs with the intrinsically enhanced selectivity and activity because of the strong metal/substrate interaction and unsaturated coordination state. The findings highlight the size effect on Ru-based catalyst supported on metal oxides, a versatile catalytic model, which allows the regulation of hydrogen adsorption to favor ammonia production over the competing hydrogen evolution reaction.     

Aerosol Spray Drying Guided Synthesis of Ultrasmall Alloyed Bimetallic Nanoparticles Supported on Silica for Catalytic Semihydrogenation

Supported bimetallic nanoparticles (NPs) with ultrasmall sizes and homogeneous alloying are attractive for catalysis. However, facile synthesis of this type of material remains very challenging. Here, the aerosol drying impregnation method for rapid, scalable, and general synthesis of silica-supported bimetallic NPs is proposed. The method relies on aerosol spray drying to promote the mixing and dispersing of binary metal precursors on SiO₂. It is capable of controlling the composition and size of bimetallic NPs and avoids the use of expensive metal complex salts and complicated experiment procedures. Twelve permutations combining a noble metal (Pd, Ru, and Pt) and a base one (Fe, Co, Ni, and Cu) with ultrasmall sizes (1.4–2.2 nm in average size), uniform dispersion, and good alloying are synthesized. Interesting activity and selectivity trends in catalytic semihydrogenation of phenylacetylene over the supported Pd-based NPs can be observed. The silica-supported PdNi NPs deliver both high activity and styrene selectivity. Spectroscopic and density functional theory calculation results reveal the improved chemoselectivity originated from the suitably down-shifted d-band center of the PdNi NPs inducing an increased energy barrier for overhydrogenation and a weakened styrene adsorption.     

Co‐operative Formation of Monolithic Tungsten Oxide–Polybenzylene Hybrids via Polymerization of Benzyl Alcohol and Study of the Catalytic Activity of the Tungsten Oxide Nanoparticles

Hard and brittle monolithic tungsten oxide‐polybenzylene nanohybrids can be obtained in one step by reacting tungsten iso‐propoxide with benzyl alcohol. In a first step, crystalline tungsten oxide W₁₈O₄₉ nanowires with a diameter of about 1.5 nm form via ether elimination reaction. Subsequently, the large residue of the benzyl alcohol is transformed to dibenzyl ether, which then polymerizes to polybenzylene, incorporating the nanoparticles into the forming polymer. The catalytic effect of the tungsten oxide nanowires on the quantitative formation of polybenzylene is proven by reacting them in different concentrations and at varying temperatures either with benzyl alcohol or with dibenzyl ether. Complete polymerization of benzyl alcohol is achieved within just 30 min by using a particle‐to‐monomer molar ratio of 1:115 at 160 °C. Lower reaction temperatures (100–130 °C) or higher ratios (1:340 and 1:680) prolong the reaction time to several hours. Further studies show that the tungsten oxide nanoparticles are able to completely polymerize various other alcohols with an aryl methanol group.     

Ru改性的铁基钙钛矿体系的催化性能研究

为研究Ru改性的铁基钙钛矿体系的催化性能,用溶胶-凝胶法分别制备了不同x、y、n值的La1-xCexFe1-y-nCoy RunO3系列化合物,在模拟条件下,以起燃温度和气体转化效率为90%时的温度为评价指标测定了HC、CO及NOx的三效催化活性.研究表明:改性催化剂具有更高的催化活性和抗老化能力;Ru的引入可大幅度提高催化活性,且催化活性与Ru离子的掺杂量成正比;La0.8Ce0.2Fe0.7Co0.2Ru0.1O3样品的催化性能较佳,起燃温度分别可达到HC 295℃、CO 280℃,NOx 280℃.     

New Strategies for the Preparation of Sinter‐Resistant Metal‐Nanoparticle‐Based Catalysts

Supported metal nanoparticles are widely used as catalysts in the industrial production of chemicals, but still suffer from deactivation because of metal leaching and sintering at high temperature. In recent years, serious efforts have been devoted to developing new strategies for stabilizing metal nanoparticles. Recent developments for preparing sinter‐resistant metal‐nanoparticle catalysts via strong metal–support interactions, encapsulation with oxide or carbon layers and within mesoporous materials, and fixation in zeolite crystals, are briefly summarized. Furthermore, the current challenges and future perspectives for the preparation of highly efficient and extraordinarily stable metal‐nanoparticle‐based catalysts, and suggestions regarding the mechanisms involved in sinter resistance, are proposed.     

Recent Progress in Syntheses and Applications of Dumbbell‐like Nanoparticles

This paper reviews the recent research progress in the syntheses and applications of dumbbell‐like nanoparticles (NPs). It first describes the general synthesis of dumbbell‐like NPs that contain noble metal and magnetic NPs/or quantum dots. It then outlines the interesting optical and magnetic properties found in these dumbbell NPs. The review further highlights several exciting application potentials of these NPs in catalysis and biomedicine.