Polystyrene-supported TiCl4 as a novel,efficient and reusable polymeric Lewis acid catalyst for the chemoselective synthesis and deprotection of 1,1-diacetates under eco-friendly conditions

Copolymer beads of styrene and divinylbenzene (5–7%) were synthesized and combined with titanium tetrachloride in CS₂ to form a stable complex. The PS/TiCl₄ complex was used as a mild and efficient polymer-supported Lewis acid catalyst for the preparation of 1,1-diacetates from various types of aldehydes under heterogeneous conditions at room temperature. Deprotection of the resulting 1,1-diacetates has also been achieved using the same catalyst in methanol. This new protocol has the advantages of easy availability, stability, reusability of the eco-friendly catalyst, high to excellent yields, chemoselectivity, simple experimental and work-up procedure. Moreover, this polymeric catalyst could be recovered easily and reused several times without significant loss in activity.     

Oxidation of Organosilanes with Nanoporous Copper as a Sustainable Non‐Noble‐Metal Catalyst

Although many noble‐metal catalysts have been used for the oxidation of organosilanes, there has been less success with non‐noble‐metal catalysts. Here, unsupported nanoporous copper (np‐Cu) is used to catalyze the oxidation of organosilanes under mild conditions. It is the first time that this reaction has been achieved with a heterogeneous copper catalyst with high activity and selectivity. Both water and alcohols are used as oxidants and the corresponding organosilanols and organosilyl ethers are obtained in high yield. The possible mechanism was obtained by kinetic studies. The catalyst could be reused at least five times without evident loss of activity. As a novel green catalyst np‐Cu should play a unique role in organic synthesis.     

纳米孔炭负载 MnOx 催化剂上苯甲醇氧化反应性能

 以纳米孔炭 (NC) 为载体, 采用浸渍法制备了一系列 MnOx/NC 催化剂, 并用于以空气为氧源的苯甲醇液相氧化反应. 通过 X 射线衍射、X 射线光电子能谱、N2 吸附-脱附和 H2-程序升温还原等手段对催化剂进行了表征, 考察了催化剂中 Mn 负载量和焙烧温度, 以及反应条件等对反应性能的影响. 结果表明, 10%MnOx/NC 催化剂的活性较高, 反应 4 h 后苯甲醇转化率可达 80.4%; 明显高于活性炭负载的 MnOx 催化剂. 这主要归因于其表面存在大量高分散、且易于还原的 Mn 物种.     

Platinum-coated gold nanoporous film surface: electrodeposition and enhanced electrocatalytic activity for methanol oxidation

This report describes the preparation of Pt-nanoparticle-coated gold-nanoporous film (PGNF) on a gold substrate via a simple "green" approach. The gold electrode that has been anodized under a high potential of 5 V is reduced by freshly prepared ascorbic acid (AA) solution to obtain gold nanoporous film electrode. Then the Pt nanoparticle is grown on the electrode by cyclic voltammetry (CV). The resulting PGNF electrode has highly ordered arrangement and large surface area, as verified by scanning electron microscopy (SEM) and CV, suggesting that the nanoporous gold film electrode provides a good matrix for obtaining PGNF with high surface area. Furthermore, the as-prepared PGNF electrode exhibited high electrocatalytic activity toward methanol oxidation in a 0.5 M H 2SO 4 solution containing 1.5 M methanol. The present novel strategy is expected to reduce the cost of the Pt catalyst remarkably.     

High Catalytic Activity of Nitrogen and Sulfur Co‐Doped Nanoporous Graphene in the Hydrogen Evolution Reaction

Chemical doping has been demonstrated to be an effective way to realize new functions of graphene as metal‐free catalyst in energy‐related electrochemical reactions. Although efficient catalysis for the oxygen reduction reaction (ORR) has been achieved with doped graphene, its performance in the hydrogen evolution reaction (HER) is rather poor. In this study we report that nitrogen and sulfur co‐doping leads to high catalytic activity of nanoporous graphene in HER at low operating potential, comparable to the best Pt‐free HER catalyst, 2D MoS₂. The interplay between the chemical dopants and geometric lattice defects of the nanoporous graphene plays the fundamental role in the superior HER catalysis.     

A simple and clean method for multicomponent synthesis of spiro [indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives using SBA-Pr-SO3H as catalyst under solvent-free conditions

Sulfonic acid functionalized SBA-15 (SBA-Pr-SO₃H) as a new nanoporous solid acid catalyst was applied in the green one-pot synthesis of spiro[indole-tetrahydropyrano(2,3-d)pyrimidine] derivatives via three-component reaction of isatins, malononitrile or cyanoacetic esters and barbituric acids under solvent-free conditions. SBA-Pr-SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm, which could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused several times without any loss of activity. The advantages of this methodology are high product yields, being environmentally benign, short reaction times, and easy handling.     

Three‐component solventless Strecker synthesis of α‐aminonitriles catalysed by a renewable sulfonated nanoporous carbon catalyst (CMK‐5‐SO3H)

The one‐pot three‐component synthesis of a variety of α‐aminonitriles has been studied using a catalytic amount of a sulfonic acid‐functionalized ordered nanoporous carbon catalyst, CMK‐5‐SO₃H, at room temperature under solvent‐free reaction conditions. The heterogeneous catalyst could be readily isolated from the reaction mixture and reused at least ten times without significant loss in activity. A clean, rapid and simple method for the preparation of α‐aminonitriles using the recoverable CMK‐5‐SO3H catalyst is described.     

A Dewetted‐Dealloyed Nanoporous Pt Co‐Catalyst Formed on TiO2 Nanotube Arrays Leads to Strongly Enhanced Photocatalytic H2 Production

Pt nanoparticles are typically decorated as co‐catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co‐catalyst loadings is a key challenge in the field. We explore a dewetting‐dealloying strategy to fabricate on TiO₂ nanotubes nanoporous Pt nanoparticles, aiming at improving the co‐catalyst mass activity for H₂ generation. For this, we sputter first Pt‐Ni bi‐layers of controllable thickness (nm range) on highly ordered TiO₂ nanotube arrays, and then induce dewetting‐alloying of the Pt‐Ni bi‐layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO₂ nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt‐decorated TiO₂ structures show a>6 times higher photocatalytic H₂ generation activity compared to structures modified with a comparable loading of dewetted, non‐porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co‐catalyst, which provides an increased surface‐to‐volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co‐catalyst surface for H₂ evolution.     

A parallel colorimetric method for the rapid discovery and optimization of heterogeneous hydrodesulfurization catalysts

A spectrophotometric based, parallel approach to screen heterogeneous catalysts for hydrodesulfurization has been developed. The method utilizes optical changes resulting from the hydrodesulfurization of 1,1'-binaphthothiophene to 1,1'-binaphthyl to determine catalyst activity. Hydrodesulfurization of 1,1'-binaphthothiophene to 1,1'-binaphthyl results in a loss of conjugation in the binaphthyl ring system. This results in a blue shift of more than 60 nm in the UV-vis spectrum. Since only small amounts of the HDS catalyst and 1,1'-binaphthothiophene are required, a large number of catalysts may be screened simultaneously. The synthesis of the 1,1'-binaphthothiophene and conditions for HDS catalyst screening are described.     

Application of Sulfonic Acid Functionalized SBA‐15 as a New Nanoporous Acid Catalyst in the Green One‐Pot Synthesis of Spirooxindole‐4H‐pyrans

Sulfonic acid functionalized SBA‐15 (SBA‐Pr‐SO₃H) as a new nanoporous solid acid catalyst was applied in the green one‐pot synthesis of spirooxindole‐4H‐pyrans via condensation of isatins, malononitrile or methyl cyanoacetate or ethyl cyanoacetate, and 4‐hydroxycoumarin in water solvent. SBA‐Pr‐SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm that could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused for several times without any loss of activity. The significant merits of present methodology are its simplicity, short reaction time, good yields, and environmentally benign mild reaction condition as water was used as a green solvent.     

Phosphite Ligand Modified Supported Rhodium Catalyst for Hydroformylation of Internal Olefins to Linear Aldehydes

A phosphite ligand modified heterogeneous catalyst was developed for the hydroformylation of internal olefins to linear aldehydes, which showed a high activity and high regioselectivity and could be separated easily by filtration after reaction in an autoclave. Three nanoporous silica sieves were used to investigate the influence of pore structure and shape selective performance of support on the regioselectivity to the linear products.     

High Activity and Selective Fischer–Tropsch Catalysts for Use in a Microchannel Reactor

Each process configuration for practicing the Fischer–Tropsch synthesis places demands particular to that configuration on the catalyst to be used. We discuss how a particular catalyst, prepared by the OMX (organic matrix combustion) method, when used in conjunction with the Velocys microchannel reactor system, results in a very stable, high performance Fischer–Tropsch synthesis system. With the ability to remove heat far more effectively than a conventional reactor system, this microchannel reactor requires a catalyst with much higher volumetric reactive site density. Further, with such a high volumetric reaction rate, mass transfer effects will be important in both the observed activity and selectivity of the operating catalyst. Nevertheless, the catalyst prepared using the OMX method exhibits an apparent turnover frequency which is considerably higher than reported for other catalysts in the literature. In addition to high activity, an economically useful catalyst must exhibit a stable, high selectivity for liquid products and be able to recover near-fresh performance using a regeneration approach which can be carried out with the catalyst in-place. An example of such a stable, multiply regenerated catalyst is given. Finally, further development has focused on a catalyst with even higher C₅₊ selectivity.     

Synthesis of SWNTs over nanoporous Co-Mo/MgO and using as a catalyst support for selective hydrogenation of syngas to hydrocarbon

Single-wall carbon nanotubes (SWNTs) with high surface area were synthesized over nanoporous Co-Mo/MgO by a chemical vapor deposition (CVD) method. The SWNTs were used as catalyst support for selective hydrogenation of syngas to hydrocarbons. Here an extensive study of Fischer-Tropsch synthesis (FTS) on CNT-supported cobalt catalysts with different amounts of cobalt loading up to 40 wt% is reported. The catalysts were characterized by different methods including N2 adsorption-desorption, X-ray diffraction, hydrogen chemisorption, inductively coupled plasma (ICP) and temperature-programmed reduction. Enhancement of the reducibility of Co3O4 to CoO, CoO to Coo and small cobalt oxide particles, dispersion of the cobalt, and activity and selectivity of FTS were investigated and compared with a conventional support. The CNT supported catalysts achieve a high dispersion and high loading of the active metal, cobalt in particular, so that the bulk formation of cobalt metal, which tends to occur in conventional support, can be avoided. The results showed that the specific activity of CNT supported catalysts increase significantly (there is a two fold increase in CO Conversion per gram of the active metal) with respect to the conventional supported catalyst.     

Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst

The lithium–oxygen battery has the potential to deliver extremely high energy densities; however, the practical use of Li‐O₂ batteries has been restricted because of their poor cyclability and low energy efficiency. In this work, we report a novel Li‐O₂ battery with high reversibility and good energy efficiency using a soluble catalyst combined with a hierarchical nanoporous air electrode. Through the porous three‐dimensional network of the air electrode, not only lithium ions and oxygen but also soluble catalysts can be rapidly transported, enabling ultra‐efficient electrode reactions and significantly enhanced catalytic activity. The novel Li‐O₂ battery, combining an ideal air electrode and a soluble catalyst, can deliver a high reversible capacity (1000 mAh g^?1) up to 900 cycles with reduced polarization (about 0.25 V).     

Syntheis of SWNTs over Co-Mo/MgO Nanoporous and using as a catalyst support for selective hydrogenation of syn gas to hydrocarbon

Single-wall carbon nanotubes (SWNTs) with high surface area were synthesized over nanoporous Co-Mo/MgO by a chemical vapor deposition (CVD) method. The SWNTs were used as catalyst support for selective hydrogenation of syngas to hydrocarbons. Here an extensive study of Fischer-Tropsch synthesis (FTS) on CNT-supported cobalt catalysts with different amounts of cobalt loading up to 40 wt% is reported. The catalysts were characterized by different methods including N2 adsorption-desorption, X-ray diffraction, hydrogen chemisorption, inductively coupled plasma (ICP) and temperature-programmed reduction. Enhancement of the reducibility of Co3O4 to CoO, CoO to Coo and small cobalt oxide particles, dispersion of the cobalt, and activity and selectivity of FTS were investigated and compared with a conventional support. The CNT supported catalysts achieve a high dispersion and high loading of the active metal, cobalt in particular, so that the bulk formation of cobalt metal, which tends to occur in conventional support, can be avoided. The results showed that the specific activity of CNT supported catalysts increase significantly (there is a two fold increase in CO Conversion per gram of the active metal) with respect to the conventional supported catalyst.     

银锡双金属催化剂的制备及其对氧还原的催化性能

在乙醇为溶剂和还原剂、碳粉为载体的体系中,采用水热法将Ag+或Ag+-Sn2+还原,形成纳米多孔网状结构的Ag或Ag-Sn双金属纳米颗粒,制备碳粉负载的Ag/C和Ag-Sn/C催化剂。 利用循环伏安和线性扫描技术,研究了碱性溶液中这些催化剂对氧还原反应(ORR)的电活性。 研究表明,Ag/C和Ag-Sn/C对ORR均表现出强的电催化活性,它们对ORR的起始电位约0.05 V（vs.Ag/AgCl）。 在Ag97Sn3/C催化剂上,ORR的电流密度为2.87×10-3 A/cm2(800 r/min),高于Ag/C。 Levich方程分析表明,在Ag-Sn/C催化剂上,ORR转移电子数明显大于Ag/C,说明在Ag-Sn/C催化剂上,氧气能够较为彻底被还原。 此外,在甲醇存在下,Ag/C和Ag-Sn/C对ORR的活性基本保持不变,表明它们对甲醇有较强的耐受力。     

Visible-Light Direct Conversion of Ethanol to 1,1-Diethoxyethane and Hydrogen over a Non-Precious Metal Photocatalyst

Converting renewable biomass and their derivatives into chemicals and fuels has received much attention to reduce the dependence on fossil resources. Photocatalytic ethanol dehydrogenation–acetalization to prepare value-added 1,1-diethoxyethane and H₂ was achieved over non-precious metal CdS/Ni-MoS₂ catalyst under visible light. The system displays an excellent production rate and high selectivity of 1,1-diethoxyethane, 52.1 mmol g⁻¹ h⁻¹ and 99.2 %, respectively. In-situ electron spin resonance, photoluminescence spectroscopy and transient photocurrent responses were conducted to investigate the mechanism. This study provides a promising strategy for a green application of bioethanol.     

离子液体促进四氟硼酸铜催化芳醛和乙酸酐合成1,1-二乙酸酯

在室温条件下, 离子液体1-正丁基-3-甲基六氟磷酸盐([bmim]PF₆)能促进四氟硼酸铜催化一系列芳醛和乙酸酐反应, 以83%～97%的产率生成相应的1,1-二乙酸酯. 在离子液体[bmim]PF₆存在情况下, 催化剂活性远远高于无离子液体存在下的活性. 催化剂用量仅需 0.2 mol%就能使反应顺利进行, 远远少于文献报道的其它催化剂的用量, 反应在3～20 min内完成. 实验结果表明该法催化剂用量少、产率高、反应时间短、离子液体可重复使用、对环境友好.     

Porous triazine polymer: A novel catalyst for the three-component reaction

A new porous triazine-based covalent organic polymer (Triazine-COP) was prepared through the Schiff-base condensation of 2,4,6-tris(4-formyl phenoxy)-1,3,5-triazine and 4,4′-oxydianiline, under sonication. The synthesized Triazine-COP with a high surface area was stable in water and other organic solvents. In the next step, Au (III) ions were immobilized on the nitrogen-rich Triazine-COP that on the reduction with NaBH₄ produced the heterogeneous catalyst of gold clusters in nanosize (Au-NCs@Triazine-COPs). It was applied as an efficient catalyst for the A³ coupling reaction of alkynes, aldehydes with and amines. Both electron-withdrawing/releasing groups produced the corresponding propargylamines with high yields. The high activity of the Au-NCs@Triazine-COPs in this reaction was because of the nanoporous structure of the support that enables the high dispersion and an unhindered open environment for the NCs. The catalyst was reused up to 7 times without significant loss in activity.     

Cyclodextrin nanosponges: a potential catalyst and catalyst support for synthesis of xanthenes

The nanoporous framework of a cyclodextrin nanosponge was used as catalyst for accelerating the one-pot, three-component reaction of dimedone, aldehyde, and phenols for synthesis of xanthene derivatives. Moreover, the nanocavities of cyclodextrin nanosponges were exploited for immobilization of heteropolyacids through the wet impregnation method. This catalyst exhibited superior catalytic performance compared to the bare cyclodextrin nanosponge. Despite the good catalytic activity, the leaching of the catalytic species did not allow efficient recovery and reusability. To circumvent this problem, the cyclodextrin nanosponge was amine-functionalized prior to heteropolyacid immobilization. The results proved that the amine functionalities had an effective role in preserving the catalytic species and improving the reusability through decreasing the leaching time. This catalyst was used for synthesis of a variety of xanthenes in aqueous media. The catalytic amount of catalyst afforded the desired product in excellent yields and with a relatively short reaction time. The results suggested cyclodextrin nanosponge-based catalysts as potential candidates for promoting chemical reactions.