Recent Development of Bio-inspired Porous Materials for Catalytic Applications

Nature has served as a source of inspiration for chemists to design the catalysts with superior performance via mimicking their characteristics, such as active sites, reaction microenvironment and electron transfer behaviors. Over a few decades, many different types of materials have been widely used to construct the biomimetic catalysts. Among these materials, the porous materials have been demonstrated to be powerful platforms for constructing the biomimetic catalysts owing to their high surface area, controllable composition and easy functionalization. In this review, we briefly showed recent advances in the construction of various biomimetic porous catalysts using porous materials for the design of excellent catalysts. In addition, we also present the challenge and opportunities in this emerging field.     

基于单原子催化剂的光热催化转化：原理和应用

在以碳中和为目标的全球共识下,太阳能作为一种取之不竭用之不尽的绿色环保能源被认为是替代传统化石燃料最有潜力的方式。在各种太阳能转换技术中,光热催化不仅可以最大化利用太阳能,在光场和热场双重驱动力作用下,还可以显著提升化学反应速率,引起广泛的研究兴趣。以孤立的单个原子均匀分散在载体上形成的单原子催化剂具有100%原子利用率、优异的催化活性、热稳定性等优势。因此,将单原子催化剂应用于光热催化开始受到越来越多的关注。本综述介绍了光催化、热催化和光热催化的基本原理和特征,同时列举一些典型的例子。随后以不同载体作为分类标准,总结了单原子光热催化应用的前沿研究进展。最后,提出了该催化体系所面临的挑战和未来的发展方向。本文旨在全面了解单原子催化剂在太阳能驱动光热催化领域的研究现状并为未来发展提供可行的建议。     

Shining light on the role of shape-controlled nanomaterials in photocatalysis

Shape-controlled nanomaterials have been in the spotlight of photocatalysis for nearly two decades as they afford a unique level of energetic and structural tunability while possessing many desirable characteristics of both homogeneous and heterogeneous catalysts, such as solution stability, high turnover number, and facile catalyst isolation. However, they come with their own set of challenges. Fundamentally, photocatalysis can be thought of as an analog to electrocatalysis, wherein thermodynamic driving force is provided by photosensitizer-originated excited charge carriers as opposed to an external circuit. In this minireview, recent advances and challenges in the development of shape-controlled nanomaterials for photocatalysis are highlighted, drawing attention to emerging areas of research and development such as nontoxic heavy metal–free photocatalysts, nanocrystal–ligand–solution interface engineering, and biohybrid systems for improved activity in challenging redox reactions.     

Recent advances in 1D nanostructured catalysts for photothermal and photocatalytic reduction of CO2

The development of photocatalysts that can efficiently convert CO₂ into other valuable chemicals via photocatalytic and photothermal processes is critical to the current energy and climate change problems. However, low separation of charge carriers, short light absorption, and low activation of CO₂ molecules in photocatalysis limit the catalysts’ performance. Designing 1D heterostructures containing multiple materials can be a viable solution as their unique properties, such as high surface area, short diffusion paths of charge carriers, and enhanced light absorption properties, can potentially promote the reaction rate and product selectivity. In this review, we summarize the general features of heterostructures involving nanotubes, nanowires, nanorods, and nanobelts. Next, the main synthesis strategies are briefly highlighted, followed by the most important findings concerning their catalytic activity in the photothermal and photocatalytic CO₂ reduction processes. The article concludes with some of the current challenges and potential solutions.     

TiO2光催化反应机理及动力学研究进展

光催化处理环境污染物是基于催化反应过程中的一些自由基对污染物的氧化或还原作用，反应途径通常是HO·攻击或穴直接攻击，对可见光敏感的化合物也可能通过激发态来分解。动力学的表述多数符合L－H模式，广泛研究了L－H模式下的吸附与催化活性的关系，对动力学的研究也是了解其反应机理的重要途径。     

金属锗酸盐微纳米材料的研究进展

金属锗酸盐微纳米材料是一类非常重要的功能材料,展现出特殊的物理与化学性质,近年来已引起国内外学者浓厚的研究兴趣。迄今为止,人们已经利用多种合成方法制备了不同尺寸和形貌的锗酸盐微纳米材料。本文综述了目前这些材料制备方面的研究现状,简单比较了各种方法的优缺点;介绍了金属锗酸盐微纳米材料在光催化、重金属离子吸附、电化学传感、锂离子电池负极材料和光学器件等领域的应用,并展望了可能的发展趋势。     

模板辅助合成氮掺杂的多孔碳基氧还原电催化剂的研究进展

氮掺杂的多孔碳材料有望能取代当前普遍应用于质子交换膜燃料电池和金属-空气电池阴极中的贵金属氧还原催化剂,因而备受关注. 模板辅助合成技术作为一种可靠、通用的方法已经在多孔碳电催化剂的制备中得到了广泛的应用. 在碳基ORR电催化剂中,其ORR活性受到诸多因素的影响,如掺杂剂的浓度及其在碳上的分子掺杂态、孔洞结构、比表面积以及碳基材料的导电性等. 本文对近期氮掺杂多孔碳电催化剂的设计、制备、功能化及其在氧还原电催化中的应用研究进展进行了总结,同时展望了模板辅助合成法的一些发展趋势.     

纳米黑磷的改性及其在光催化析氢领域的应用

黑磷作为一种新型的二维材料,具有高载流子迁移率、强大的光吸收性、高比表面积以及各向异性等特点,在光催化领域表现出极强的应用潜力,如光催化析氢、光催化降解有机污染物和生物医学光热、光动力学治疗等。但黑磷存在易氧化且光生电子-空穴复合严重等问题,需要通过改性提高黑磷光催化剂的性能。本文综述了表面修饰、掺杂、复合以及构建异质结等黑磷改性方法,着重对黑磷基材料在光催化产氢领域的应用进行了详细介绍,并指出了黑磷基材料在光催化领域应用需要克服的问题并展望及前景。     

TiO2光催化反应机理及动力学研究进展

光催化处理环境污染物是基于催化反应过程中的一些自由基对污染物的氧化或还原作用,反应途径通常是HO·攻击或穴直接攻击,对可见光敏感的化合物也可能通过激发态来分解。动力学的表述多数符合L－H模式,广泛研究了L－H模式下的吸附与催化活性的关系,对动力学的研究也是了解其反应机理的重要途径。     

Progress of Copper-based Nanocatalysts in Advanced Oxidation Degraded Organic Pollutants

To address global pollution caused by contaminants in water bodies, it is crucial to develop an efficient and environmentally friendly treatment process for wastewater from various industries. Advanced oxidation processes (AOPs) have proven to be highly effective in wastewater treatment due to their high oxidation efficacy and the absence of secondary pollutants. Different methods such as ozone, Fenton, electrochemical, photolysis, and sonolysis can be used in AOPs to degrade emerging pollutants that are resistant to conventional methods. In recent years, nanotechnology has emerged as a viable solution, with various nanomaterials being developed for wastewater treatment. Among them, copper-based nanocatalysts have shown great potential in AOPs. This review focuses on the progress and mechanisms of copper-based nanocatalysts in wastewater treatment via AOPs. It also discusses the challenges associated with oxidation, electrochemistry, Fenton, and photocatalysis in wastewater treatment processes. Copper-based nanocatalysts can be modified to enhance their catalytic activity, selectivity, and stability, leading to improved performance in wastewater treatment. They have shown promising results in degrading pollutants like pharmaceuticals, pesticides, and dyes. However, the practical application of these nanocatalysts still faces challenges, including the high cost of synthesis, potential nanoparticle toxicity, and scalability issues. More research is needed to address these challenges and improve the utilization of copper-based nanocatalysts in wastewater treatment. In addition, Cu-based catalysts with magnetic properties offer the advantage of easy recovery and reusability in wastewater treatment. They can also be incorporated into catalytic membranes, forming efficient systems for recycling. Heterogeneous catalysts with diverse structures, including ternary or quaternary systems, are widely used. However, challenges remain in identifying suitable coupling pairs and understanding the complex processes involved in constructing heterogeneous interfaces without generating defects. Therefore, a thorough understanding of the catalyst‘s band structure is crucial for developing efficient heterogeneous structures. Furthermore, cost implications of synthesis methods and raw materials should be considered in the preparation of transition metal catalysts, and relevant cost analysis data is needed for optimizing the degradation of pollutants. In conclusion, copper-based nanocatalysts hold great potential in AOPs for wastewater treatment. With their magnetic properties, Cu-based catalysts offer the advantage of easy recovery and reusability. However, challenges such as high synthesis costs, nanoparticle toxicity, and scalability issues need to be addressed. Further research is needed to overcome these challenges and optimize the utilization of copper-based nanocatalysts in wastewater treatment processes.     

Immobilized polyoxometalates onto mesoporous organically-modified silica aerogels as selective heterogeneous catalysts of anthracene oxidation

Immobilized molybdovanadophosphoric acids onto organically surface-modified silica aerogels were successfully prepared and investigated in heterogeneous catalysis of anthracene oxidation. The catalysts were obtained by supporting mono- and di-vanadium substituted molybdophosphoric acids on hybrid silica materials synthesized via the sol–gel process followed by surface amino-functionalization. The FTIR, DR UV–vis, and AA spectroscopy confirmed the loading and distribution of the polyoxometalate molecules on the surface of the aerogels. The nitrogen adsorption–desorption technique revealed a systematic decrease in the specific surface area and pore volume after the immobilization of the polyoxometalates. The application of the supported molecules as catalysts for anthracene oxidation showed 100% selectivity for 9,10-anthraquinone as opposed to the reactions conducted under homogeneous conditions. Moreover, at certain conditions, the catalytic activity of the supported polyoxometalates was greater than their corresponding free polyoxometalates with a clear effect of the surface chemical groups of the supporting silica aerogels. Additionally, the oxidant and solvent nature showed a crucial effect on the catalytic activity and selectivity of the immobilized polyoxometales. The heterogeneous catalysts were regenerated and reused over consecutive catalytic cycles reflecting a potential economic interest in these materials besides their high efficiency in heterogeneous catalysis.     

Employing high-resolution materials characterization to understand the effects of Pd nanoparticle structure on their activity as catalysts for olefin hydrogenation

Recent developments in nanotechnology have led to the production of new materials with a wide array of applications, particularly in catalysis. Because of their small size, nanoparticles have a maximized surface-to-volume ratio, thus making them attractive targets for use as catalytic structures; however, the number of analytical techniques available to fully characterize materials on such a size scale is quite limited. As a result, a complete understanding of the entire nanoparticle structure remains unclear, especially when considering the active structural motif from which the specific activity arises. Metallic Pd materials have been widely studied due to their immense potential as catalysts for reactions such as olefin hydrogenation and C–C bond synthesis. These materials require surface passivants to act as ligands and stabilize the nanoparticles against aggregation and bulk formation. These ligands have the added value to function as gates that selectively allow reagents to reach the active surface of the Pd nanoparticles for chemical turnover. This accounts for the observed selectivities of the catalysts with the corresponding changes in the turnover frequency values. Here we present a broad overview of recent advances in the use of Pd nanoparticles for the industrially important hydrogenation reaction with a focus on characterizing and understanding the base structural effects that give rise to the catalytic activity.     

An Overview on Graphene-Metal Oxide Semiconductor Nanocomposite: A Promising Platform for Visible Light Photocatalytic Activity for the Treatment of Various Pollutants in Aqueous Medium

Graphene is one of the most favorite materials for materials science research owing to its distinctive chemical and physical properties, such as superior conductivity, extremely larger specific surface area, and good mechanical/chemical stability with the flexible monolayer structure. Graphene is considered as a supreme matrix and electron arbitrator of semiconductor nanoparticles for environmental pollution remediation. The present review looks at the recent progress on the graphene-based metal oxide and ternary composites for photocatalysis application, especially for the application of the environmental remediation. The challenges and perspectives of emerging graphene-based metal oxide nanocomposites for photocatalysis are also discussed.     

Enhanced Enzyme Reuse through the Bioconjugation of L-Asparaginase and Silica-Based Supported Ionic Liquid-like Phase Materials

L-asparaginase (ASNase) is an amidohydrolase that can be used as a biopharmaceutical, as an agent for acrylamide reduction, and as an active molecule for L-asparagine detection. However, its free form displays some limitations, such as the enzyme’s single use and low stability. Hence, immobilization is one of the most effective tools for enzyme recovery and reuse. Silica is a promising material due to its low-cost, biological compatibility, and tunable physicochemical characteristics if properly functionalized. Ionic liquids (ILs) are designer compounds that allow the tailoring of their physicochemical properties for a given task. If properly designed, bioconjugates combine the features of the selected ILs with those of the support used, enabling the simple recovery and reuse of the enzyme. In this work, silica-based supported ionic liquid-like phase (SSILLP) materials with quaternary ammoniums and chloride as the counterion were studied as novel supports for ASNase immobilization since it has been reported that ammonium ILs have beneficial effects on enzyme stability. SSILLP materials were characterized by elemental analysis and zeta potential. The immobilization process was studied and the pH effect, enzyme/support ratio, and contact time were optimized regarding the ASNase enzymatic activity. ASNase–SSILLP bioconjugates were characterized by ATR-FTIR. The bioconjugates displayed promising potential since [Si][N₃₄₄₄]Cl, [Si][N₃₆₆₆]Cl, and [Si][N₃₈₈₈]Cl recovered more than 92% of the initial ASNase activity under the optimized immobilization conditions (pH 8, 6 × 10⁻³ mg of ASNase per mg of SSILLP material, and 60 min). The ASNase–SSILLP bioconjugates showed more enhanced enzyme reuse than reported for other materials and immobilization methods, allowing five cycles of reaction while keeping more than 75% of the initial immobilized ASNase activity. According to molecular docking studies, the main interactions established between ASNase and SSILLP materials correspond to hydrophobic interactions. Overall, it is here demonstrated that SSILLP materials are efficient supports for ASNase, paving the way for their use in the pharmaceutical and food industries.     

Application of supported perovskite-type catalysts for vehicular emission control

Catalytic control of auto-exhaust emissions is one of the most successful applications of heterogeneous catalysis, both in commercial and environmental point of views. Although noble metal-based catalysts have dominated this area, efforts were always put in towards development of low cost non-noble metal-based catalysts. With the recent need of closed-coupled catalytic converter, thermal stability requirements have also become more severe, leading to the search for stable catalytic materials. Mixed oxides, including those perovskite type compounds with ABO₃ structure have been extensively studied, mainly for their catalytic and electrical properties. Low surface area of these catalysts has so far been the most important limitation for their catalytic applications involving high space velocities, e.g. auto-exhaust catalysis. Various synthesis routes have been earlier attempted to improve their surface area, yet this was much inferior than the noble metal catalysts, dispersed on high surface area alumina. The in situ synthesis of these oxides on alumina is often associated with the formation of undesired phases, due to the reactive nature of perovskite precursors. However, alumina washcoat, commonly used for improving the surface area of ceramic and metallic catalyst supports, can be modified for perovskite applications. In situ synthesis of stabilized perovskites on modified alumina-washcoated supports offer high surface area and excellent catalyst adhesion. Although, it is difficult to ascertain the presence of pure perovskite type materials on support, such improved synthesis has resulted in remarkable improvement in their catalytic activity for their applications in auto-exhaust catalytic converters. This review presents our work on synthesis of various improved perovskite-type mixed oxides supported on modified alumina-washcoated cordierite honeycomb, their characterization, and detailed catalytic evaluations for possible application in automobile pollution control.     

分子氧为氧化剂的Au?Ag/TS-1光催化剂协同光催化丙烯气相环氧化

近年来,丙烯环氧化已引起人们广泛的兴趣;然而,大多数过程仍面临分离困难等问题.此外,丙烯转化率和环氧丙烷(PO)的选择性仍然非常低.从环境和经济观点来看,分子氧是丙烯选择性环氧化的理想氧化剂.开发一种气相光催化环氧化方法,即在光能和多相光催化剂存在的情况下,用于化学品生产.因此,本文探讨了通过光催化O2选择氧化丙烯环氧化.传统的制备方法存在环境污染及能耗大等缺点,而利用氧气直接进行光催化丙烯环氧化制备环氧丙烷是相当具有前景的化学品生产途径.本文采用水热法制备了微球状TS-1载体,再通过浸渍还原法制备了不同Au/Ag质量比的Au–Ag/TS-1双金属催化剂.通过X射线衍射、扫描电镜、紫外-可见吸收光谱、透射电镜、X射线光电能谱、荧光光谱和N2吸脱附法等手段对合成的催化剂的组成、形貌和性质进行了研究,通过气相色谱在线分析得到光催化反应结果.结果表明,通过浸渍还原法可以很好的将贵金属分散到载体表面上.对于Au–Ag/TS-1双金属催化剂,当Au/Ag质量比为4/1时,反应温度为443 K时,环氧丙烷生成速率最大(68.3μmol/(g·h)),其选择性达52.3%.对于Au–Ag/TS-1光催化剂,双金属负载有利于O2吸附活化,同时促进了电子的传递,从而抑制电子空穴的复合,有利于氧自由基的形成.结果表明,Au,Ag双金属之间存在协同催化作用,根据实验现象提出了一种可能的反应机理.     

介孔硅材料及其负载型催化剂去除挥发性有机物的最新进展

介孔硅材料由于具有大的比表面积,均一的孔结构和大的孔径,常被用于分离、吸附和催化等领域.本文综述了近年来国内外介孔硅材料及其负载型催化剂去除各类挥发性有机物(VOCs)的研究进展,主要包括烃类、甲醇、甲醛、丙酮、苯、甲苯、萘、乙酸乙酯等.讨论了介孔硅材料的结构对VOCs吸附过程的影响;介绍了不同催化剂消除各类VOCs的催化性能及反应机理,并重点评述了甲苯在不同催化剂上的研究进展.分析结果表明,介孔硅材料的表面环境、孔道结构以及宏观形貌是影响VOCs分子在介孔硅材料上吸附的主要因素;贵金属催化剂的应用需要提高其抗中毒性以及降低成本;过渡金属的研究应着重于研发高活性的负载型过渡金属复合氧化物催化剂.最后对国内外介孔硅材料及其负载型催化剂的发展进行了展望,今后催化剂的设计可以从“氧化硅载体”和“介孔孔道”两个方面展开,这将为设计合适的催化剂处理各类VOCs污染物提供一定参考.     

The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction

Cost‐effective carbon‐based catalysts are promising for catalyzing the electrochemical N₂ reduction reaction (NRR). However, the activity origin of carbon‐based catalysts towards NRR remains unclear, and regularities and rules for the rational design of carbon‐based NRR electrocatalysts are still lacking. Based on a combination of theoretical calculations and experimental observations, chalcogen/oxygen group element (O, S, Se, Te) doped carbon materials were systematically evaluated as potential NRR catalysts. Heteroatom‐doping‐induced charge accumulation facilitates N₂ adsorption on carbon atoms and spin polarization boosts the potential‐determining step of the first protonation to form *NNH. Te‐doped and Se‐doped C catalysts exhibited high intrinsic NRR activity that is superior to most metal‐based catalysts. Establishing the correlation between the electronic structure and NRR performance for carbon‐based materials paves the pathway for their NRR application.     

Ion exchangeable layered niobates as a noble series of photocatalysts

Some characteristic behaviors of ion-exchangeable layered niobate photocatalysts are described. The main feature of this type of photocatalysts comes from the intercalation of the reactant and the reaction proceeding at the interlayer space. In this point of view, these catalysts are regarded as “two dimensional” photocatalysts. Judging from the wide variety of these families including not only niobates but also other early transition metal oxides such as titanate, and also their unique structures, ion-exchangeable layered oxides will be an interesting subject to be used in the field of photocatalysis.     

Recent Progress in ZIF-Derived Carbons for Enhanced Oxygen Reduction Reaction Electrocatalysis

The oxygen reduction reaction (ORR) represents a cornerstone for many clean energy conversion technologies such as fuel cells and metal-air batteries. Nevertheless, the commercialization of these technologies is largely impeded by the slow kinetics of ORR, for which active, durable and cost-effective ORR catalysts are needed. In recent years, zeolitic imidazolate framework (ZIF) derived carbon materials emerge as a new class of non-precious metal catalysts (NPMCs) toward ORR, largely benefiting from their high surface area, abundant porosity, tunable chemical/electronic structure, and superior ORR activity which is comparable or even surpasses those state-of-the-art Pt-based ORR catalysts. This review offers a comprehensive overview of the recent advances in ZIF-derived carbons for ORR. The synthesis strategies and the key factors affecting the ORR performance of ZIF-derived carbon materials are discussed. Future research directions and perspectives on exploring ZIF derived carbons as efficient ORR catalysts are highlighted, with a focus on the principles of rationally engineering the coordination structures of active sites.