聚合物负载金属纳米粒子型核壳结构催化剂的研究

核壳结构聚合物负载型催化剂因其载体材料独特的结构、形貌和性质而具有优异的催化活性,成为了催化化学领域研究的热点。本文综述了聚合物负载金属纳米粒子型核壳结构催化剂,包括球形聚合物刷负载金属纳米粒子、聚合物中空微球负载金属纳米粒子、聚合物实心微球表面包覆金属纳米粒子等类型催化剂的制备及其相应的催化性能,强调了各类载体的组成和结构特点对催化活性及其稳定性的影响。最后总结了该类催化材料的优势和不足,并对其性能和应用进行了展望。     

负载钯纳米粒子聚电解质空心微球的制备及其还原对硝基苯酚的催化活性

用表面引发原子转移自由基聚合法(SI-ATRP)在二氧化硅纳米粒子表面接枝聚碘化甲基丙烯酸三甲基胺基乙酯(PMETAI),原位还原静电吸附的PdCl62-后刻蚀除去二氧化硅模板,成功制备了Pd纳米粒子复合聚电解质空心微球(air@PMETAI@Pd)。 用透射电子显微镜(TEM)、红外光谱仪(FTIR)、能谱仪(EDX)、热重分析仪(TGA)等技术手段对所制备的空心微球进行表征。 结果表明,Pd纳米粒子均匀负载在聚电解质微球上,其直径约为(1.5±0.2) nm。 将负载Pd纳米粒子的微球作为催化剂应用于硼氢化钠还原4-硝基苯酚反应,显示出很好的催化效果且具有较好的回收利用性。     

Hollow Carbon Sphere Nanoreactors Loaded with PdCu Nanoparticles: Void-Confinement Effects in Liquid-Phase Hydrogenations

Nanoreactors with hollow structures have attracted great interest in catalysis research due to their void-confinement effects. However, the challenge in unambiguously unraveling these confinement effects is to decouple them from other factors affecting catalysis. Here, we synthesize a pair of hollow carbon sphere (HCS) nanoreactors with presynthesized PdCu nanoparticles encapsulated inside of HCS (PdCu@HCS) and supported outside of HCS (PdCu/HCS), respectively, while keeping other structural features the same. Based on the two comparative nanoreactors, void-confinement effects in liquid-phase hydrogenation are investigated in a two-chamber reactor. It is found that hydrogenations over PdCu@HCS are shape-selective catalysis, can be accelerated (accumulation of reactants), decelerated (mass transfer limitation), and even inhibited (molecular-sieving effect); conversion of the intermediate in the void space can be further promoted. Using this principle, a specific imine is selectively produced. This work provides a proof of concept for fundamental catalytic action of the hollow nanoreactors.     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

Nitrogen and Oxygen Co-Doping Assisted Synthesis of Highly Dispersed Pd Nanoparticles on Hollow Carbon Spheres as Efficient Electrocatalysts for Oxygen Reduction Reaction

Electrochemical reduction of O₂ (oxygen reduction reaction; ORR) provides an opportunity to achieve the commercial application of clean energy, but it remains challenging, so the rational design of inexpensive and efficient electrocatalysts is required. Palladium-based electrocatalysts have emerged as a class of the most promising candidates for the ORR, which could accelerate O₂ adsorption, dissociation, and electron transfer. However, the metal Pd atoms tend to aggregate into nanoparticles, driven by the tendency of the metal surface free energy to decrease, which significantly reduces the atom utilization efficiency and the catalytic performance. Herein, a facile double solvent impregnation method is developed for the synthesis of highly dispersed Pd nanoparticles supported on hollow carbon spheres (Pd-HCS), which could act as efficient electrocatalysts for the ORR in basic solution. Systematic investigation reveals that the nitrogen-containing and oxygen-containing functional groups (especially −COOH groups) are essential for achieving the homogenous dispersion of Pd nanoparticles. Significantly, the optimized Pd-HCS electrocatalyst with homogeneously dispersed Pd nanoparticles and Pd−N sites delivers high electrocatalytic activity for the ORR and excellent stability, without significant decay in onset potential and half-potential and good resistance to methanol crossover. This work offers a new route for the rational design of efficient ORR electrocatalysts toward advanced materials and emerging applications.     

Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.     

One-Pot Fabrication of Pd Nanoparticles@Covalent-Organic-Framework-Derived Hollow Polyamine Spheres as a Synergistic Catalyst for Tandem Catalysis

Facile fabrication of nanocatalysts consisting of metal nanoparticles (NPs) anchored on a functional support is highly desirable, yet remains challenging. Covalent organic frameworks (COFs) provide an emerging materials platform for structural control and functional design. Here, a facile one-pot in situ reduction approach is demonstrated for the encapsulation of small Pd NPs into the shell of COF-derived hollow polyamine spheres (Pd@H-PPA). In the one-pot synthetic process, the nucleation and growth of Pd NPs in the cavities of the porous shell take place simultaneously with the reduction of imine linkages to secondary amine groups. Pd@H-PPA shows a significantly enhanced catalytic activity and recyclability in the tandem dehydrogenation of ammonia borane and selective hydrogenation of nitroarenes through an adsorption–activation–reaction mechanism. The strong interactions of the secondary amine linkage with borane and nitroarene molecules afford a positive synergy to promote the catalytic reaction. Moreover, the hierarchical structure of Pd@H-PPA allows the accessibility of active Pd NPs to reactants.     

Highly active nanoreactors: nanomaterial encapsulation based on confined catalysis

It happens inside: highly active nanoreactors are prepared by encapsulating dendritic Pt nanoparticles (NPs) grown on a polystyrene template inside hollow porous silica capsules. The catalytic activity of these Pt NPs is preserved after encapsulation and template removal. Different metals, such as Ni, can thus be reduced inside the capsules, thereby leading to the formation of composites with tunable magnetic properties.     

In Situ Formation of Au–Pd Bimetallic Active Sites Promoting the Physically Mixed Monometallic Catalysts in the Liquid‐Phase Oxidation of Alcohols

The catalytic oxidation of alcohols with molecular oxygen on supported nanometallic catalysts represents one of the green methods in a crucial process for the synthesis of fine chemicals. We have designed an experiment using physically mixed Au/AC and Pd/AC (AC=activated carbon) as the catalyst in the liquid‐phase oxidation of benzyl alcohol by aerobic oxygen. The evolution of the physically mixed catalyst structures at different stages in the catalytic reaction was investigated by aberration‐corrected high‐resolution transmission electron microscopy and spatially resolved element mapping techniques at the nanometre scale, and they were also compared with the structure of the bimetallic alloy. For the first time we show the formation of surface Au–Pd bimetallic sites by reprecipitation of Pd onto Au nanoparticles. Negligible Au leaching was observed. The in situ structural evolution can be directly correlated to the great enhancement of the catalyst activity. Moreover, we distinguish the different behaviours of Au and Pd, thus suggesting an oxygen differentiating mechanism for Au and Pd sites. The findings are of great importance to both the understanding of the structure–activity correlation and the design of highly active catalysts in green chemistry.     

Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors

We report the synthesis of chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface (capped with 3‐chloropropyl groups) and a hydrophilic interior surface for spatially selective cargo loading, and for application as nanoreactors and nanomotors. The silica NBs, which have a “flask bottle” shape with an average diameter of 350 nm and an opening of ca. 100 nm, are prepared by anisotropic sol–gel growth in a water/n‐pentanol emulsion. Due to their chemically asymmetric properties, nanoparticles (NPs) with hydrophilic or hydrophobic surface properties can be selectively loaded inside the NBs or on the outside of the NBs, respectively. A high‐performance nanomotor is constructed by selectively loading catalytically active hydrophilic Pt NPs inside the NBs. It is also demonstrated that these NBs can be used as vessels for various reactions, such as the in situ synthesis of Au NPs, and using Au NP‐loaded NBs as nanoreactors for catalytic reactions.     

A yolk-shell nanoreactor with a basic core and an acidic shell for cascade reactions

Smart yolk-shell nanoparticles (hollow nanoparticles with a movable core) with an acidic shell and a basic core were fabricated through an organosilane-assisted selective etching method and acted as efficient nanoreactors for catalyzing a deacetalization-Henry cascade reaction with high activity and high selectivity. This strategy is very promising for the design of multifunctional nanoreactors for cascade reactions.     

Constructing magnetic polyaniline/metal hybrid nanostructures using polyaniline/Fe3O4 composite hollow spheres as supports

Polyaniline (PANI)/Fe₃O₄ composite hollow spheres have been successfully synthesized in one step using sulfonated polystyrene (PS) spheres as templates. The magnetic PANI hollow spheres were used as supports for noble metal nanoparticles (NPs) such as Au and Pd. The morphology, composition and magnetic properties of the resulting products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, inductively coupled plasma (ICP) atomic spectra and vibrating sample magnetometer. The catalytic activity of magnetic PANI/Au composite shells on the oxidation of dopamine was investigated by cyclic voltammetry. The obtained results provide our product with a practical application for the detection of dopamine. On the other hand, the catalytic activity of magnetic PANI/Pd composite shells on the reduction of 4-nitroaniline was investigated by spectroscopic methods and compared with Pd/C catalyst which was already widely used in industrial production.     

Polydimethylsiloxane Coating for a Palladium/MOF Composite: Highly Improved Catalytic Performance by Surface Hydrophobization

Surface wettability of active sites plays a crucial role in the activity and selectivity of catalysts. This report describes modification of surface hydrophobicity of Pd/UiO‐66, a composite comprising a metal–organic framework (MOF) and stabilized palladium nanoparticles (NPs), using a simple polydimethylsiloxane (PDMS) coating. The modified catalyst demonstrated significantly improved catalytic efficiency. The approach can be extended to various Pd nanoparticulate catalysts for enhanced activity in reactions involving hydrophobic reactants, as the hydrophobic surface facilitates the enrichment of hydrophobic substrates around the catalytic site. PDMS encapsulation of Pd NPs prevents aggregation of NPs and thus results in superior catalytic recyclability. Additionally, PDMS coating is applicable to a diverse range of catalysts, endowing them with additional selectivity in sieving reactants with different wettability.     

In-situ deposition of Pd/Pd_4S heterostructure on hollow carbon spheres as efficient electrocatalysts for rechargeable Li-O_2 batteries

The sluggish kinetics of oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) have always restricted the development of lithium oxygen batteries(LOBs).Herein,hollow carbon spheres loaded with Pd/Pd_4S heterostructure(Pd/Pd_4S@HCS) were successfully prepared via the in-situ deposition to improve the electrocatalytic activities for both ORR and OER in LOBs.With the welldispersed Pd/Pd_4S nanoparticles,the hierarchical composite with large specific surface area offers favorable transport channels for ions,electron and oxygen.Especially,the Pd/Pd_4S nanoparticles could exhibit excellent electrochemical performance for ORR and OER due to their intrinsic catalytic property and interfacial effect from the heterostructure.Therefore,the LOBs with Pd/Pd_4S@HCS as cathode catalyst show improved specific capacities,good rate ability and stable cycling performance.     

有序介孔碳载钯的制备、表征及对甲酸的电催化氧化性能

通过浸渍法和硫引入贵金属法分别制备了主要负载在介孔碳主孔道(MPC/Pd-1)和负载在介孔碳孔壁上小介孔中[MPC/(S)Pd-2]的两类负载型钯电催化剂, 用XRD, SEM, TEM和电化学等方法表征了其结构和电催化性能. 循环伏安结果表明, 有序介孔碳载钯催化剂MPC/Pd-1和MPC/(S)Pd-2对甲酸氧化的催化活性分别是商用钯黑催化剂的4.0和2.4倍. MPC/Pd-1中的钯位于介孔碳的主孔道上, 增加了催化剂/电解质/反应物三相界面的面积, 使得其比MPC/(S)Pd-2的催化活性更高.     

Kinetics Driven by Hollow Nanoreactors: An Opportunity for Controllable Catalysis

As a novel class of catalytic materials, hollow nanoreactors offer new opportunities for improving catalytic performance owing to their higher controllability on molecular kinetic behavior. Nevertheless, to achieve controllable catalysis with specific purposes, the catalytic mechanism occurring inside hollow nanoreactors remains to be further understood. In this context, this Review presents a focused discussion about the basic concept of hollow nanoreactors, the underlying theory for hollow nanoreactor-driven kinetics, and the intrinsic correlation between key structural parameters of hollow nanoreactors and molecular kinetic behaviors. We aim to provide in-depth insights into understanding kinetics occurred within typical hollow nanoreactors. The perspectives proposed in this paper may contribute to the development of the fundamental theoretical framework of hollow nanoreactor-driven catalysis.     

Biomolecule-coated metal nanoparticles on titanium

Immobilizations of nanoparticles and biomolecules on biocompatible substrates such as titanium are two promising approaches to bringing new functionalities to Ti-based biomaterials. Herein, we used a variety of X-ray spectroscopic techniques to study and better understand metal-thiolate interactions in biofunctionalized metal nanoparticle systems supported on Ti substrates. Using a facile one-step procedure, a series of Au nanoparticle samples with varied biomolecule coatings ((2-mercatopropionyl)glycine (MPG) and bovine serum albumin (BSA)) and biomolecule concentrations are prepared. Ag and Pd systems are also studied to observe change with varying metal composition. The structure and properties of these biomolecule-coated nanoparticles are investigated with scanning electron microscopy (SEM) and element-specific X-ray techniques, including extended X-ray absorption fine structure (Au L(3)-edge), X-ray absorption near-edge structure (Au L(3), Ag L(3), Pd L(3), and S K-edge), and X-ray photoelectron spectroscopy (Au 4f, Ag 3d, Pd 3d, and S 2p core level). It was found that, by comparison of SEM and X-ray spectroscopy results, the coating of metal nanoparticles with varying model biomolecule systems can have a significant effect on both surface coverage and organization. This work offers a facile chemical method for bio- and nanofunctionalization of Ti substrates as well as provides a physical picture of the structure and bonding of biocoated metal nanoparticles, which may lead to useful applications in orthopedics and biomedicine.     

Water‐dispersible Hollow Microporous Organic Network Spheres as Substrate for Electroless Deposition of Ultrafine Pd Nanoparticles with High Catalytic Activity and Recyclability

Microporous organic networks (MONs) have been considered as an ideal substrate to stabilize active metal nanoparticles. However, the development of highly water‐dispersible hollow MONs nanostructures which can serve as both the reducing agent and stabilizer is highly desirable but still challenging. Here we report a template‐assisted method to synthesize hollow microporous organic network (H‐MON) spheres using silica spheres as hard template and 1,3,5‐triethynylbenzene as the building blocks through a Glaser coupling reaction. The obtained water‐dispersible H‐MON spheres bearing sp‐ and sp²‐hybridized carbon atoms possess a highly conjugated electronic structure and show low reduction potential; thus, they can serve as a reducing agent and stabilizer for electroless deposition of highly dispersed Pd clusters to form a Pd/H‐MON spherical hollow nanocomposite. Benefitting from their high porosity, large surface area, and excellent solution dispersibility, the as‐prepared Pd/H‐MON hollow nanocomposite exhibits a high catalytic performance and recyclability toward the reduction of 4‐nitrophenol.     

合理设计具有空间分离催化位点的中空立方体顺序材料作为高效的全解水光催化剂

通过精细的纳米结构和化学组成控制,开发高效的全解水纳米光催化剂是一项具有挑战性的任务.此外,在光催化水氧化的半反应过程中,抑制纳米材料严重光腐蚀也是一项艰巨的任务,需要有效地提高纳米材料光生空穴转移的动力学.为此,本文通过可控的化学反应,设计制备了具有空间催化活性位点分布的Co-MnO₂@CdS/CoS中空立方体顺序材料,并用作可见光催化全解水催化剂.采用MOFs作为自模板,经过连续的阴离子交换和阳离子交换反应,将Co掺杂的氧化助催化剂(纳米片Co-MnO₂)和还原助催化剂(纳米粒子CoS)同时整合到中空的立方体CdS纳米材料中,使得超薄的二维纳米片Co-MnO₂与立方体的内部界面均匀接触,能够有效地提高空穴的转移效率.同时,CoS纳米粒子均匀分散在CdS纳米材料的壁上,能够有效地转移光生电子,从而提高光生电子-空穴对的分离效率.实验测试表明,Co-MnO₂@CdS/CoS中空立方体顺序材料可以为表面氧化-还原反应提供丰富的反应活性位点,同时有助于提高CdS纳米材料光生电子-空穴对的分离和迁移效率.特别是分散在CdS中空立方体壁面上的CoS纳米颗粒被确定为加速氢气生成的还原型助催化剂,能够促进水中氢离子生成氢气;而附着在CdS中空立方体内壁上的Co-MnO₂纳米片被确定为促进氧演化动力学的氧化型助催化剂,能够促进水生成氧气.因此,在本实验中,得益于理想的纳米结构和化学组成方面的优势,Co-MnO₂@CdS/CoS纳米立方体显示了高效的光催化全解水性能:在没有贵金属作为助催化剂存在时,它显示了很好的整体光催化水分解效率(735.4(H₂)和361.1(O₂)μmol h^-1 g^-1),超过了大多数文献报道的CdS基催化剂光解水效率.此外,以420 nm单波长光为入射光,进行了量子效率(AQE)测试,最优的Co-MnO₂@CdS/CoS纳米材料的表观AQE达1.32%.本文合成的顺序材料为构筑具有活性位点空间分布的高效全解水催化剂提供了新的思路.     

Palladium nanoparticles in carbon thin film-lined SBA-15 nanoreactors: efficient heterogeneous catalysts for Suzuki-Miyaura cross coupling reaction in aqueous media

Embedding Pd nanoparticles in carbon thin film-lined SBA-15 nanoreactors provides highly efficient catalysts for heterogeneous cross coupling reactions in aqueous media. No leaching or aggregation of Pd nanoparticles was found in these nanoreactors after reusing them several times. The carbon thin film lining of these nanoreactors was further confirmed with small molecular arene probing experiments.