Ni-Pd纳米涂层整体式催化剂加氢性能研究

采用浸涂法将自制的介孔空心SiO2纳米粉体涂覆到堇青石基体上,然后采用微波法负载活性组分Pd和助剂Ni制备了纳米涂层整体式加氢催化剂,并考察空速、涂层增重、Ni助剂添加量等因素对其乙炔选择性加氢催化性能的影响。结果表明:经过涂覆后的堇青石整体式催化剂加氢性能与未涂覆时相比有了显著提高,且添加适量的助剂Ni有助于催化性能的进一步改进。在反应温度为54℃、压力为0.1 MPa、空速为3 800 h-1的条件下,使用涂层增重质量分数为6%、Ni与Pd物质的量比为4∶1的催化剂,当乙炔接近完全转化时,乙烯选择性能够到达40.9%。     

Porous hollow silica nanoparticles as carriers for controlled delivery of ibuprofen to small intestine

With two different methods, ibuprofen was entrapped into porous hollow silica nanoparticles (PHSNs) carriers, which were synthesized through a sol-gel route by using CaCO3 nanoparticles as the inorganic templates. By employing pressured CO2 as the loading medium, the amount of ibuprofen that was pressed into the carriers was approximately 52% higher than that by simply soaking. The drug release behaviors of the ibuprofen-loaded PHSNs were investigated in a simulated intestine juice and an artificial gastric fluid, respectively, and it demonstrated a sustained release pattern in all cases and the sample prepared under high pressure had a lower release rate in both fluids and thus owned a greater sustained drug release capacity. In the acidic artificial gastric fluid, no silica was degraded and only 16% of the loaded ibuprofen was released from the matrix in 300 min. However, much more silica was degraded in the simulated intestine juice in a shorter time and almost all the loaded ibuprofen was dissolved into the solution eventually, resulting in a quicker and complete ibuprofen release. Therefore, the PHSNs can be utilized for applications of controlled drug delivery to small intestine.     

Porous hollow silica nanoparticles as controlled delivery system for water-soluble pesticide

Porous hollow silica nanoparticles (PHSNs) were prepared and applied as controlled delivery system of water-soluble pesticide validamycin. PHSNs were loaded with validamycin through a specially designed supercritical fluid loading method. It was demonstrated that a high loading capacity (36 wt.%) of validamycin could be achieved, which was found to be more effective than that of the simple immersing method in this study. The loaded PHSNs were characterized by TG, IR and XPS analysis. The validamycin release profile from PHSNs was investigated and showed a multi-staged release pattern probably due to the different adsorption locations of validamycin on PHSNs. This release behavior makes PHSNs a promising carrier in agriculture, especially for pesticide controlled delivery whose immediate as well as prolonged release is needed. In addition, factors influencing the validamycin release rate, including pH and temperature, were investigated.     

Pd Single‐Atom Catalysts on Nitrogen‐Doped Graphene for the Highly Selective Photothermal Hydrogenation of Acetylene to Ethylene

The selective hydrogenation of acetylene to ethylene in an ethylene‐rich gas stream is an important process in the chemical industry. Pd‐based catalysts are widely used in this reaction due to their excellent hydrogenation activity, though their selectivity for acetylene hydrogenation and durability need improvement. Herein, the successful synthesis of atomically dispersed Pd single‐atom catalysts on nitrogen‐doped graphene (Pd₁/N‐graphene) by a freeze‐drying‐assisted method is reported. The Pd₁/N‐graphene catalyst exhibits outstanding activity and selectivity for the hydrogenation of C₂H₂ with H₂ in the presence of excess C₂H₄ under photothermal heating (UV and visible‐light irradiation from a Xe lamp), achieving 99% conversion of acetylene and 93.5% selectivity to ethylene at 125 °C. This remarkable catalytic performance is attributed to the high concentration of Pd active sites on the catalyst surface and the weak adsorption energy of ethylene on isolated Pd atoms, which prevents C₂H₄ hydrogenation. Importantly, the Pd₁/N‐graphene catalyst exhibits excellent durability at the optimal reaction temperature of 125 °C, which is explained by the strong local coordination of Pd atoms by nitrogen atoms, which suppresses the Pd aggregation. The results presented here encourage the wider pursuit of solar‐driven photothermal catalyst systems based on single‐atom active sites for selective hydrogenation reactions.     

Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with macroporous shells for enhanced catalytic hydrogenation of NBR

In this work, a stable and recyclable Pd catalyst supported on N-containing silane coupling agent modified silica hollow microspheres with macroporous shells (Pd/N-SHMs) was successfully prepared and used for the selective hydrogenation of nitrile-butadiene rubber (NBR) with enhanced catalytic performance. The results showed that Pd/N-SHMs possessed small-sized and well-dispersed Pd nanoparticles (NPs) and the macroporous shells were beneficial for the diffusion of macromolecular NBR, and thus with such a catalyst, the reaction could occur under mild conditions and high hydrogenation degree (96.6%) with 100% selectivity to C=C was obtained. The prepared catalyst could be easily recycled and reused with a high efficiency. More importantly, because of the strong coordination between Pd and diamine ligands, Pd NPs could be anchored steadily over the support and only 5.0 ppm Pd residues was detected in products. This reaction was considered as pseudo-first order at high H₂ pressures, and the reaction activation energy was calculated to be as low as 18.1 kJ/mol. Our contribution is to provide an efficient and recyclable supported Pd catalyst, which may promote the development of heterogeneous catalytic systems for unsaturated macromolecular hydrogenation.     

Self-assembled spherical palladium/HMS nanocomposites and their catalytic application

A novel palladium catalyst immobilised the mesoporous molecular sieve Hexagonal Mesoporous Silica (HMS) was prepared via a self-assembly process. The catalytic activity and recycle ability of the spherical palladium/HMS nanocomposites were examined for the Heck reaction. Palladium nanoparticles incorporated into HMS are characterised by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The morphology of HMS is predominated with spheres, and Pd nanoparticles are randomly distributed throughout the entire silica framework without severe agglomeration. The heterogeneous catalyst is proved to be an active and reusable catalyst in the coupling of ethyl acrylate with aryl halides because of combination, the advantages of stabilising agent and mesoporous silica support.     

Palladium supported on functionalized mesoporous silica as an efficient catalyst for Heck reaction

Pd nanoparticles supported in functionalized mesoporous silica were prepared. Mesoporous silica support was modified with [3-(2-aminoethyl aminopropyl)] trimethoxysilane. Palladium ions were grafted onto the functionalized mesoporous silica and reduced with hydrazine hydrate to obtain the Pd nanoparticles supported on functionalized mesoporous silica. The Pd loading in the nanocomposite of Pd supported on the functionalized mesoporous silica is 4.30 wt%. CO chemisorption analysis on the nanocomposite shows a Pd dispersion as high as 35% and a Pd surface area of 156 m²/g. The surface area, pore size, and pore volume decrease slightly with the incorporation of the Pd nanoparticles into the functionalized mesoporous silica. Pd supported on the functionalized mesoporous silica with controlled molar ratio of amino groups to palladium exhibits an excellent catalytic activity and low Pd leaching for the Heck carbon-carbon coupling reaction. The catalyst can be reused for at least six recycles in air with only a minor loss of activity.     

Metal-oxide-doped silica nanoparticles for the catalytic glycolysis of polyethylene terephthalate

Polyethylene terephthalate (PET) was depolymerized to monomer bis(2-hydroxyethyl) terephthalate (BHET) using excess ethylene glycol (EG) in the presence of metal oxides that were impregnated on different forms of silica support [silica nanoparticles (SNPs) or silica microparticles (SMPs)] as glycolysis catalysts. The reactions were carried out at 300 degrees C and 1.1 MPa at an EG-to-PET molar ratio of 11:1 and a catalyst-to-PET-weight ratio of 1.0% for 40-80 min. Among the four prepared catalysts (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nanocomposite had the highest monomer yield (> 90%). This high yield may be explained by the high surface area, amorphous and porous structure, and existence of numerous active sites on the nanocomposite catalyst. The BHET yield increased with time and reached the highest level where equilibrium was established between BHET and its dimer. The catalysts were characterized by their SEM, TEM, and BET surface areas, and via XRD, whereas the monomer BHET was characterized by HPLC and FT-IR. The glycolysis with the Mn3O4/SNPs nanocomposite as the glycolysis catalyst produced a maximum BHET in a short reaction time.     

Enhanced catalytic activity and thermal stability by highly dispersed Pd-based nanocatalysts embedded in ZrO2 hollow spheres

Sintering resistant noble metal nanoparticles are critical to the development of advanced catalysts with high activity and stability. Herein, we reported the construction of highly dispersed Pd nanoparticles loaded at the inner wall of ZrO₂ hollow spheres (Pd@HS-ZrO₂), which shows improved activity and thermal stability over references in the Pd-ZrO₂ (catalyst-support) system. Even after 800 °C high temperature calcination, the Pd nanoparticles and ZrO₂ hollow spheres did not undergo morphological changes. The Pd@HS-ZrO₂ manifests batter catalytic activity and thermal stability than the counterpart Pd/ZrO₂ catalysts. In comparison to Pd/ZrO₂-800, Pd@ZrO₂-800 exhibits a 25°C reduction in the temperature required for complete conversion of CO. The enhanced catalytic activity and thermal stability of Pd@HS-ZrO₂ can be attributed to the nanoconfinement effect offered by the 10 nm wall thickness of the ZrO₂ hollow spheres, which suppresses the coarsening of the Pd nanoparticles (active center for catalysis).     

Pd Nanosheet‐Covered Hollow Mesoporous Silica Nanoparticles as a Platform for the Chemo‐Photothermal Treatment of Cancer Cells

A versatile system combining chemotherapy with photothermal therapy for cancer cells using Pd nanosheet‐covered hollow mesoporous silica nanoparticles is reported. While the hollow mesoporous silica core can be used to load anticancer drugs (i.e., doxorubicin) for chemotherapy, the Pd nanosheets on the surface of particles can convert NIR light into heat for photothermal therapy. More importantly, the loading of Pd nanosheets on hollow mesoporous silica nanospheres can dramatically increase the amount of cellular internalization of the Pd nanosheets: almost 11 times higher than the unloaded Pd nanosheets. The as‐prepared nanocomposites efficiently deliver both drugs and heat to cancer cells to improve the therapeutic efficiency with minimal side effects. Compared with chemotherapy or photothermal therapy alone, the combination of chemotherapy and phototherapy can significantly improve the therapeutic efficacy, exhibiting a synergistic effect.     

Preparation of silica/polyacrylamide/polyethylene nanocomposite via in situ polymerization

SiO₂/polyacrylamide (PAM) composite was prepared via the polymerization of acrylamide in the presence of silica sol in water/hexane emulsion, and pure SiO₂ was also prepared without the use of acrylamide in the same way. Field emission scanning electron micrographs (FESEM) showed that PAM covered the silica nanoparticles to form SiO₂/PAM nanospheres, which loosely agglomerated to form SiO₂/PAM secondary particles, while SiO₂ secondary particles were made up of tightly agglomerated silica nanoparticles. Metallocene catalyst was then immobilized over SiO₂ and SiO₂/PAM respectively to prepare supported metallocene catalyst for ethylene polymerization. Transmission electron micrographs (TEM) showed that support particles broke up to smaller particles and even nanoparticles in polyethylene (PE) matrix when the support particles were the fragile SiO₂/PAM secondary particles, which shows a novel way to prepare silica/polyacrylamide/polyethylene nanocomposite.     

50 ppm of Pd dispersed on Ni(OH)2 nanosheets catalyzing semi-hydrogenation of acetylene with high activity and selectivity

Nano Research - We report a highly efficient Pd/Ni(OH)2 catalyst loaded with ultra-low levels of palladium (50 ppm Pd by mass) for the selective hydrogenation of acetylene to ethylene. The turnover...     

Zinc-doped ferrite nanoparticles as magnetic recyclable catalysts for scale-up glycolysis of poly(ethylene terephthalate) wastes

Innovations of catalyst design are critical to industrial implementation of poly(ethylene terephthalate) (PET) upcycling by glycolysis. A primary challenge that affects the purity of products and increases the recycling cost is the difficulty in catalyst separation and reusability. Here, magnetically isolable zinc ferrite nanoparticles (Zn-MNPs) were prepared and fabricated for higher catalytic activity in PET glycolysis. Results reveal that the substitution of zinc into the spinel structure of Fe₃O₄ significantly enhances its catalytic selectivity in PET glycolysis. Besides, the Zn-rich surface and hollow internal structure of the prepared catalysts create more active sites for reactants, relative to pure Fe₃O₄. Under mild conditions, PET chains experienced a powerful nucleophilic attack from ethylene glycol when catalyzed by Zn-MNPs, achieving 79.82% monomer yield and 100% PET degradation in 2 h with low consumption of ethylene glycol. The recovered catalysts can be reused for five consecutive cycles with high PET conversion. It is anticipated that the synthesized low-cost and recoverable Zn-MNPs are promising alternatives for the industrial upcycling of PET wastes.     

High-Dispersive Pd Nanoparticles on Hierarchical N-Doped Carbon Nanocages to Boost Electrochemical CO2 Reduction to Formate at Low Potential

Electrochemical CO₂ reduction reaction (CO₂RR) to value-added chemicals/fuels is an effective strategy to achieve the carbon neutral. Palladium is the only metal to selectively produce formate via CO₂RR at near-zero potentials. To reduce cost and improve activity, the high-dispersive Pd nanoparticles on hierarchical N-doped carbon nanocages (Pd/hNCNCs) are constructed by regulating pH in microwave-assisted ethylene glycol reduction. The optimal catalyst exhibits high formate Faradaic efficiency of >95% within −0.05–0.30 V and delivers an ultrahigh formate partial current density of 10.3 mA cm⁻² at the low potential of −0.25 V. The high performance of Pd/hNCNCs is attributed to the small size of uniform Pd nanoparticles, the optimized intermediates adsorption/desorption on modified Pd by N-doped support, and the promoted mass/charge transfer kinetics arising from the hierarchical structure of hNCNCs. This study sheds light on the rational design of high-efficient electrocatalysts for advanced energy conversion.     

Chemical fluid deposition of monometallic and bimetallic nanoparticles on ordered mesoporous silica as hydrogenation catalysts

A simple and green method of depositing monometallic (Ru, Rh, Pd) and bimetallic nanoparticles (Ru-Rh, Ru-Pd and Rh-Pd) on an ordered mesoporous silica support (MCM-41) in supercritical carbon dioxide (scCO2) is described. Metal acetylacetonates were used in the experiments as CO2-soluble metal precursors. Suitable temperature and pressure conditions for synthesizing each kind of nanoparticles were applied in this study. The characterizations of these nanocomposites were performed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The nanoparticles had average sizes varying from 2 nm to 8 nm. The Ru nanoparticles were clearly shown to be inside the mesopores of MCM-41 from the TEM image. These nanocomposites used as catalysts for hydrogenation was demonstrated. The efficiency of the scCO2 prepared Ru/MCM-41 catalyst was nearly 8 times than that of a Ru/MCM-41 catalyst prepared by conventional impregnation method.     

Polymeric hybrid mesoporous silica hollow nanospheres as a support for palladium and application of the PdNPs@PANI/HNS nanocomposite for aerobic benzyl alcohol oxidation

The polyaniline composition by silica based mesoporous hollow nanosphere (silica-HNS) was synthesized and selected as a promising solid support for palladium nanoparticle stabilization. Then the nanocomposite was applied as a nanocatalyst for aerobic benzyl alcohol oxidation reactions. Catalyst recyclability showed six successful runs for the reaction. TEM and SEM-EDX/mapping images were used to study the structure and morphology of the Pd_NPs@PANI/HNS. FT-IR spectroscopy, Thermal gravimetric analysis (TGA), and BET were used to characterize and investigate the catalyst nature. In addition, the amounts of Pd loading were characterized by ICP-AES technique.     

Novel Aerosol-Based Approach toward Mesoporous Silica Nanoparticles

This study introduces a novel gas-phase method for the synthesis of mesoporous silica nanoparticles (MSNs). The method is a two-step templating approach by first forming silicon-coated carbon structures in a hybrid microwave-plasma/hot-wall reactor followed by an annealing step to produce mesoporous silica with distinct nanostructure and porosity. Two different (sacrificial) carbonaceous templates have been prepared (plasma reactor) and coated (hot-wall reactor), 2D few-layer graphene (FLG) flakes and soot-like fractal aggregates. Results show that the wall thickness of the porous silica structures can be adjusted by changing the concentration of the silicon precursor (monosilane). High monosilane concentrations, however, result in solid silica particles after annealing. Using soot-like particle templates permitted to control of the shell thickness of the hollow porous particles, while the FLG template results in ultrathin silica sheets after heat treatment. The pore volume and specific surface area increase up to 263 m² g⁻¹ and 0.6 cm³ g⁻¹, respectively, by the formation of hollow porous particles. An adsorption study on carbamazepine reveals up to ≈86% removal. The gas-phase aerosol-based template method presented here offers scalability and versatility, and it is capable of producing MSNs with a controlled structure and porosity by modifying the carbonaceous templates.     

用化工软件研究碳二前加氢催化剂及其工艺

用Material Studio化工软件计算、研究了碳二前加氢催化剂及其工艺,结果证实α-Al2O3为适宜的碳二前加氢催化剂载体,Pd为适宜的主活性组分,Ag为适宜的助活性组分。确定的碳二前加氢催化剂的最佳使用温度为70℃,适当提高CO含量可以提高碳二前加氢催化剂的选择性。利用Material Studio软件可以进行碳二前加氢催化剂的制备设计及其使用工艺参数的优化计算。     

Galvanic Replacement–Mediated Synthesis of Ni‐Supported Pd Nanoparticles with Strong Metal–Support Interaction for Methanol Electro‐oxidation

Herein, well‐defined Pd nanoparticles (NPs) developed on Ni substrate (Pd NPs/Ni) are synthesized via a facile galvanic replacement reaction (GRR) route performed in ethaline‐based deep eutectic solvent (DES). For comparison, a Pd NPs/Ni composite is also prepared by the GRR method conducted in an aqueous solution. The Pd NPs/Ni obtained from the ethaline‐DES is catalytically more active and durable for the methanol electro‐oxidation reaction (MOR) than those of the counterpart derived from conventional aqueous solution and commercial Pd/C under alkaline media. Detailed kinetic analysis indicates that the unique solvent environment offered by ethaline plays vital roles in adjusting the reactivity of the active species and their mass transport properties to control over the genesis of the Pd NPs/Ni nanocomposite. The resulting Pd NPs/Ni catalyst possesses a homogeneous dispersion of Pd NPs with a strong Pd (metal)–Ni (support) interaction. This structure enhances the charge transfer between the support and the active phases, and optimizes the adsorption energy of OH^? and CO on the surface, leading to superior electrocatalytic performance. This work provides a novel GRR strategy performed in ethaline‐DES to the rational design and construction of advanced metal/support catalysts with strong interaction for improving the activity and durability for MOR.     

Pd embedded in porous carbon （Pd@CMK-3） as an active catalyst for Suzuki reactions： Accelerating mass transfer to enhance the reaction rate

Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon （Pd@CMK-3） has been prepared by a strategy involving immersion, ammonia- hydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd（0） and Pd（I1） species co-exist and were embedded in the matrix of the porous carbon （CMK-3）. The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency （TOF） could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.