Smart Solution Chemistry to Sn‐Containing Intermetallic Compounds through a Self‐Disproportionation Process

Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn‐containing intermetallics is challenging. In this work, we demonstrated for the first time that a self‐disproportionation‐induced in situ process produces cavernous Sn?Cu intermetallics (Cu₃Sn and Cu₆Sn₅). The successful synthesis is realized by introducing inorganic metal salts (SnCl₂ ? 2 H₂O) to NaOH aqueous solution to form an intermediate product of reductant (Na₂SnO₂) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn?Cu case. Moreover, this method could be extended to other Sn‐containing materials (Sn?Co, Sn?Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu₃Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials.     

Synthesis and Adsorption/Catalytic Properties of the Metal Organic Framework CuBTC

CuBTC (Copper(II) benzene-1,3,5-tricarboxylate) is one of the most well characterized and widely studied metal organic framework (MOF) structures for potential use in industrial applications due to its relatively easy synthesis and excellent textural and physicochemical properties. In this comprehensive review, a different perspective on MOF materials for future sustainability is presented by critically examining the recent works that have considered the synthesis and adsorption/catalytic applications of CuBTC as a model case.     

Recent advances of Rh-based intermetallic nanomaterials for catalytic applications

Rhodium (Rh) has received widespread attention in fundamental catalytic research and numerous industrial catalytic applications. Compared to homogeneous catalysts, Rh-based nanomaterials as heterogeneous catalysts are much easier to separate and collect after usage, making them more suitable for commercial use. To this purpose, there has been a constant demand in constructing stable and highly active Rh-based nanomaterials. In contrast to Rh-based solid solutions with a random distribution of metallic atoms in the lattice, Rh-based intermetallic compounds (IMCs) with a fixed stoichiometric ratio and an ordered atomic arrangement can ensure the homogenous distribution of active sites and structural stability in the catalytic process. In this review, we concentrate on the fabrication of Rh-based IMCs for catalytic applications. Various synthetic methods and protocols for the controlled preparation of Rh-based IMC are illustrated. Meanwhile, the catalytic applications and corresponding catalytic mechanisms are discussed. In addition, personal perspectives about the remaining challenges and prospects in this field are provided. We believe this review will be useful in directing the development of Rh-based IMC catalysts for heterogeneous catalysis.     

Main-chain organometallic polymers: synthetic strategies, applications, and perspectives

Main-chain organometallic polymers utilize transition metal-organic ligand complexes as primary components of their backbones. These hybrid materials effectively integrate the physical and electronic properties of organic polymers with the physical, electronic, optical, and catalytic properties of organometallic complexes. Combined with the rich and continuously growing array of ligands for transition metals, these materials have outstanding potential for use in a broad range of applications. This tutorial review discusses the major classes of main-chain organometallic polymers, including coordination polymers, poly(metal acetylide)s, and poly(metallocene)s. Emphasis is placed on their synthesis, characterization, physical properties, and applications, as well as ongoing challenges and limitations. These discussions are supplemented with highlights from the recent literature. The review concludes with perspectives on the current status of the field, as well as opportunities that lie just beyond its frontier.     

Single-atom site catalysts supported on two-dimensional materials for energy applications

Single-atom site catalysts (SACs) and two-dimensional materials (2DM) have gradually become two hot topics in catalysis over the past decades. Their combination with each other can further endow the derived SACs with extraordinary properties such as high loading, identical active sites, uniform coordination environment, distinctive metal-support interaction, and enhanced catalytic activities. In this review, we highlight the recent development in this specific research topic according to the types of substrates and focus on their applications in energy conversion field. Additionally, we also make a brief introduction to the synthesis and characterization methods for SACs supported on 2DM (SACs/2DM). Finally, the challenges and perspectives are summarized based on the current development status. It is believed that this work will make contributions to the rational design and fabrication of novel SACs/2DM, promoting their practical energy applications in the future.     

Pd纳米晶的调控合成及其在燃料电池中的应用

贵金属Pd纳米晶体的催化性能与其表面结构有着密切联系。基于目前Pd多面体纳米晶体可控合成技术的发展,Pd纳米晶体催化性能的进一步优化及其在催化领域的应用前景依然广阔。本文主要阐述了关于Pd多面体纳米晶的制备及其作为电催化剂在燃料电池中应用的最新研究进展。在介绍纳米晶体的生长机理及其表面结构与晶体形状的关系之后,重点描述了Pd多面体纳米晶体常见的几种制备方法,概述了Pd多面体纳米晶体作为催化剂在燃料电池阴极和阳极中的应用。最后总结展望了Pd多面体纳米晶体作为催化剂的研究方向及其发展前景。     

Three-phase electrodes: simple and efficient tool for analysis of ion transfer processes across liquid-liquid interface—twenty years on

In this review, we focus on major achievements of the three-phase electrode methodology applied for studying ion transfers across an interface between two immiscible liquids. Exactly 20 years ago, the group of electrochemists led by Fritz Scholz, invented an elegant and simple set up suitable to get access to the thermodynamics of ion transfers across liquid/liquid interface. Within the last two decades, besides determination of thermodynamics of the transfer of many important ionic substances, three-phase electrodes have been applied for many other purposes. Thermodynamics of interfacial chemical reactions, kinetics of ion and electron transfer, interfacial catalysis, recognition of chiral ions, synthesis of nano-particles, and biosensor development are some of the milestones achieved by application of three-phase electrodes. While elaborating briefly major achievements, future perspectives of this simple, but powerful electrochemical tool, have been also envisaged.

     

Recent development and applications of semipinacol rearrangement reactions

As has been well-recognized, semipinacol rearrangement functions as an exceptionally useful methodology in the synthesis of β-functionalized ketones, creation of quaternary carbon centers, and construction of challenging carbocycles. Due to their versatile utilities in organic synthesis, development of novel rearrangement reactions has been a vibrant topic that continues to shape the research field. Recent breakthroughs in novel electrophiles, tandem processes, and enantioselective catalytic transformations further enrich the toolbox of this chemistry and spur the strategic applications of this methodology in natural product synthesis. These achievements will be discussed in this minireview.

The recent development of semipinacol rearrangement is reviewed, highlighting its application in β-functionalized ketone synthesis, quaternary carbon formation and total synthesis.     

层状材料及催化

LDHs（1ayered double hydroxides）是一类结构可调的阴离子层状及插层结构功能材料,近些年来在催化领域得到了广泛的关注．本文综述了有关LDHs材料构筑原则的理论研究、组装方法及其在多相催化领域应用的最新进展．     

基于非贵金属催化剂常温常压电化学合成氨

氨是一种重要的化工原料和能量载体,“哈伯反应”是工业上合成氨最主要的方法,但是该方法存在着能耗高,大量排放温室气体CO₂以及转化率低等问题。近年来,常温常压下基于多相催化剂的电化学还原N₂反应(NRR)来制备氨因其原料(N₂ + H₂O)易得,不依赖传统化石能源以及条件温和等原因而表现出巨大的应用潜能,并受到了科学家的广泛关注。然而目前NRR仍存在着如催化剂以贵金属材料为主,催化效率低和催化机理未明确等问题亟待解决。本综述主要总结了电催化NRR的最新研究成果,首先介绍了电催化NRR热力学和催化机理,接着重点列举了基于非贵金属催化剂的研究进展,包括过渡金属氧化物、氮化物、硫化物、非金属催化剂及单原子催化剂等,然后讨论了几种NRR电催化剂的改性方法,以及常见的产物氨的定性定量方法,最后,就目前该研究方向中仍待解决的问题进行了总结,并对下一步的研究进行了展望。     

One-dimensional inorganic nanostructures: synthesis, field-emission and photodetection

One-dimensional inorganic nanostructures have drawn prime attention due to their potential for understanding fundamental physical concepts and constructing nanoscale electronic and optoelectronic devices. This critical review mainly focuses on our recent research progresses in 1D inorganic nanostructures, including their rational synthesis and potential applications, with an emphasis on field-emitter and photodetector applications. Firstly, we will discuss the rational design of synthetic strategies and the synthesis of 1D nanostructures via a vapour phase approach. Secondly, we will present our recent progresses with respect to several kinds of important inorganic nanostructures and their field-emission and photoconductivity characteristics. Finally, we conclude this review with some perspectives/outlook and future research in these fields (212 references).     

Complex three-dimensional microparticles from microfluidic lithography

Complex 3D microparticle, as an emerging and attractive field, has attracted more and more attention due to its versatile morphologies and broad range of applications. In this review, we provide an overall recent progress in 3D microparticles fabricated by microfluidic lithography. This review will focus on the synthesis mechanisms, synthesis process, the resultant 3D microparticles, and their applications. Finally, we will look into the future trends in complex 3D microparticles. This review will be beneficial for researchers in numerous fields, including functional materials, sensors, encryption, and biomedical engineering.     

Recent Advances in Multifunctional Capsule Catalysts in Heterogeneous Catalysis?

Capsule catalysts composed of pre-shaped core catalysts and layer zeolites have been widely used in the tandem reactions where multiple continuous reactions are combined into one process. They show excellent catalytic performance in heterogeneous catalysis, including the direct synthesis of middle isoparaffins or dimethyl ether from syngas, as compared to the conventional hybrid catalysts. The present review highlights the recent development in the design of capsule catalysts and their catalytic applications in heterogeneous catalysis. The capsule catalyst preparation methods are introduced in detail, such as hydrothermal synthesis method, dual-layer method, physically adhesive method and single crystal crystallization method. Furthermore, several new applications of capsule catalysts in heterogeneous catalytic processes are presented such as in the direct synthesis of liquefied petroleum gas from syngas, the direct synthesis of para-xylene from syngas and methane dehydroaromatization. In addition, the development in the design of multifunctional capsule catalysts is discussed, which makes the capsule catalyst not just a simple combination of two different catalysts, but has some special functions such as changing the surface hydrophobic or acid properties of the core catalysts. Finally, the future perspectives of the design and applications of capsule catalysts in heterogeneous catalysis are provided.     

Perspective on intermetallics towards efficient electrocatalytic water-splitting

Intermetallic compounds exhibit attractive electronic, physical, and chemical properties, especially in terms of a high density of active sites and enhanced conductivity, making them an ideal class of materials for electrocatalytic applications. Nevertheless, widespread use of intermetallics for such applications is often limited by the complex energy-intensive processes yielding larger particles with decreased surface areas. In this regard, alternative synthetic strategies are now being explored to realize intermetallics with distinct crystal structures, morphology, and chemical composition to achieve high performance and as robust electrode materials. In this perspective, we focus on the recent advances and progress of intermetallics for the reaction of electrochemical water-splitting. We first introduce fundamental principles and the evaluation parameters of water-splitting. Then, we emphasize the various synthetic methodologies adapted for intermetallics and subsequently, discuss their catalytic activities for water-splitting. In particular, importance has been paid to the chemical stability and the structural transformation of the intermetallics as well as their active structure determination under operating water-splitting conditions. Finally, we describe the challenges and future opportunities to develop novel high-performance and stable intermetallic compounds that can hold the key to more green and sustainable economy and rise beyond the horizon of water-splitting application.

This perspective provides an overview of the versatility of intermetallic compounds for electrochemical water splitting along with their synthetic strategies, catalytic efficiencies as well as their active structures under operating conditions.     

Valorization of Oceanic Waste Biomass: A Catalytic Perspective

Efficacious waste utilization is vital in context of sustainability. The past decade has witnessed attempts of usage of land biomass and wastes for various applications, contributing towards a sustainable society. Exploitation of the marine biomass, which does not compete with habitation and food production like land biomass has been largely unnoticed and therefore not being utilized judiciously. Researchers have mainly exploited these resources as functional materials having significant potential applications. However, a catalytic perspective for the valorisation of these polymers arising from oceanic waste widens their scope and ameliorates its use. The objective of the present review is to demonstrate the effectiveness of chitin/chitosan as a catalyst and as a feedstock for deriving important fuels and chemicals. It displays all the reactions heterogeneously catalyzed by them along with the strategic methodology. Their important catalytic organic transformations attempted so far, have also been discussed. The future perspectives are also presented which if inculcated would improve the value addition of the waste, paving a way for greener and imperishable world.     

有机硼酸类催化剂在有机合成中的应用

综述了有机硼酸类作为催化剂应用于有机合成反应中的最新研究进展, 重点介绍了所发现的各种有机硼酸催化剂在缩合反应、羧酸还原反应、Diels-Alder反应中的催化活性以及反应机理. 硼酸催化剂因具有催化效率高、反应条件温和、可重复使用等优点, 必将在有机合成催化领域中得到更广泛的应用.     

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom‐economical and energy‐efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value‐added chemicals from biomass resources.     

Poly(ether ether ketone) derivative membranes—a review of their preparation, properties and potential

The present paper gives an overview of the properties and performance of membranes of a poly(ether ether ketone) derivative with a cardo group in the chain, known in the literature as PEEKWC or PEK-C. This is one of the typical examples of a new polymer, emerged in the last two decades, with the potential to be applied as a membrane material in a wide range of application fields. Due to the presence of the cardo group in the backbone, the polymer is soluble in several common organic solvents, in contrast to the traditional poly(ether ketone) (PEK) and poly(ether ether ketone) (PEEK). It is therefore more versatile and its solubility allows the use of nonsolvent-induced phase inversion techniques to prepare membranes with a wide range of different morphologies and transport characteristics. The present review will show the current state of the art and will testify that PEEKWC offers interesting perspectives in especially the fields of gas separation, biomedical applications and—in its sulfonated form-in fuel cells. Examples of successful application in microfiltration, ultrafiltration, nanofiltration, pervaporation, membrane contactors, catalytic membranes and some other applications, such as packaging and molecular imprinting will also be shown.     

Biological entities as chemical reactors for synthesis of nanomaterials: Progress,challenges and future perspective

Synthesis of nanomaterials is being gained extensive attention in the fields of chemistry, applied physics, catalysis, drug delivery and the most important in diagnosis and therapeutic applications. Recently, many reports have been published on physical and chemical synthesis of magnetic as well as metallic nanoparticles (NPs) with viable surface functionalization, but still there is a dire need of such strategies that can combine synthetic methodology with stable surface modification found in nature. Synthesis of NPs via biological methods is the possible way to solve these barriers. However, systematized summary and outlooks of NPs synthesis via biological entities with various influencing factors e.g. temperature, pH, concentration of reactants and reaction time has rarely been reported. This review will present the distinct advantages of biological synthesis of NPs over physical and chemical methods. It will also highlight the recent progress on synthesis of NPs via various biological systems i.e. plant, fungus, bacteria, and yeast. Furthermore, it will explain various factors that control the size, shape, and morphology of these NPs. Finally, it would present the future perspectives of green chemistry for the development of nano-science and -biotechnology.