基底表面构建单原子催化剂与催化性能研究进展

近年来,单原子催化剂因其较高的催化活性和选择性等优点而受到了人们的广泛关注.我们综述了以C, Si, Ti, Al为基底的单原子催化剂的制备方法,并对以不同材料基底制备单原子催化剂的制备方法、形成机理及优势特点进行了比较.通过对单原子制备、表征方法及催化活性的概述,以期对制备单原子催化剂提供一定的借鉴和指导.研究表明,单原子催化剂的制备已从贵金属单原子催化剂向过渡金属单原子催化剂进行了转变.单原子催化剂的基底也不再仅仅局限于单一的形式.这些转变为单原子催化剂向传统催化领域迈进提供了可能.我们同时也对单原子催化剂在工业上的应用进行了介绍.     

Single-Atom Catalysts on Covalent Triazine Frameworks: at the Crossroad between Homogeneous and Heterogeneous Catalysis

Heterogeneous single-site and single-atom catalysts potentially enable combining the high catalytic activity and selectivity of molecular catalysts with the easy continuous operation and recycling of solid catalysts. In recent years, covalent triazine frameworks (CTFs) found increasing attention as support materials for particulate and isolated metal species. Bearing a high fraction of nitrogen sites, they allow coordinating molecular metal species and stabilizing particulate metal species, respectively. Dependent on synthesis method and pretreatment of CTFs, materials resembling well-defined highly crosslinked polymers or materials comparable to structurally ill-defined nitrogen-containing carbons result. Accordingly, CTFs serve as model systems elucidating the interaction of single-site, single-atom and particulate metal species with such supports. Factors influencing the transition between molecular and particulate systems are discussed to allow deriving tailored catalyst systems.     

单原子催化的关键进展与未来挑战

单原子催化剂(SACs)兼具均相与多相催化剂的双重优势, 表现出最大化的原子利用率、 超高的本征活性与选择性以及易与产物分离的特点, 受到人们的广泛关注. 然而, 由于单个原子较高的表面能以及不稳定性, 设计与制备单原子催化剂仍是一大挑战. 本文综合评述了近年来单原子催化剂的稳定化策略、 高载量催化剂的制备方法以及批量制备技术等方面的关键研究进展, 并简要分析了单原子催化剂未来发展所面临的问题与挑战, 最后对单原子催化的发展方向进行了展望.     

Single-Atom Catalysis in Organic Synthesis

Single-atom catalysts hold the potential to significantly impact the chemical sector, pushing the boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist in many coordination environments, all of which have shown important functions in specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging the gap between homogeneous and heterogeneous catalysis. This Review outlines the impressive progress made in recent years regarding the use of single-atom catalysts in organic synthesis. We also illustrate potential knowledge gaps in the search for more sustainable, earth-abundant single-atom catalysts for synthetic applications.     

抗烧结的超稳定型单原子催化剂研究进展

传统的负载型金属催化剂在高温环境下或长时间工作后易发生烧结。这种不可逆的过程会导致催化剂活性位点的显著减少,使得催化剂严重失活。因此往往需要将催化剂及时更新才能满足工业生产需求,然而这会极大增加生产成本。与传统的负载型金属催化剂不同,单原子催化剂(Single-atom catalysts,SACs)的中心金属原子可以与杂原子(N、O、S等)形成强键合作用,从而有效抑制金属烧结。基于单原子催化剂的这种特性,我们可以制备抗烧结、耐高温的超稳定型单原子催化剂来应对特殊的工业催化环境。本文总结了近年来抗烧结的超稳定型单原子催化剂的合成与应用进展,为单原子催化领域的研究提供参考。     

金催化作用的结构敏感性

金催化是纳米催化的代表性体系,金催化作用表现出复杂的结构敏感性。这篇综述总结了金催化作用研究的文献结果和我们利用从单晶到纳米晶的模型催化剂研究金催化作用的进展。展示了NO分解,CO氧化,丙烯在氢气和氧气气氛中环氧化等反应中金催化作用的结构敏感性和金催化剂的活性结构,讨论了金纳米粒子几何结构和电子结构、金纳米粒子–氧化物载体相互作用对金催化作用的影响和金表面低温高催化活性的来源,并展望了金催化作用结构敏感性的未来研究方向。     

Inter-Metal Interaction of Dual-Atom Catalysts in Heterogeneous Catalysis

Dual-atom catalysts (DACs) have been a new frontier in heterogeneous catalysis due to their unique intrinsic properties. The synergy between dual atoms provides flexible active sites, promising to enhance performance and even catalyze more complex reactions. However, precisely regulating active site structure and uncovering dual-atom metal interaction remain grand challenges. In this review, we clarify the significance of the inter-metal interaction of DACs based on the understanding of active center structures. Three diatomic configurations are elaborated, including isolated dual single-atom, N/O-bridged dual-atom, and direct dual-metal bonding interaction. Subsequently, the up-to-date progress in heterogeneous oxidation reactions, hydrogenation/dehydrogenation reactions, electrocatalytic reactions, and photocatalytic reactions are summarized. The structure-activity relationship between DACs and catalytic performance is then discussed at an atomic level. Finally, the challenges and future directions to engineer the structure of DACs are discussed. This review will offer new prospects for the rational design of efficient DACs toward heterogeneous catalysis.     

单原子催化在海洋能源领域的应用

海洋是未来人类社会重要的能源宝库, 其中蕴藏了储量庞大且形式多样的能源, 海洋能源与资源的高效转化与获取对实现“双碳目标”具有重要意义. 催化技术是提高能源与资源利用效率和转化速率的关键技术, 对于海洋巨大的资源储量, 其显得更为重要. 单原子催化剂具有优异的可调控性、 高选择性和高活性位点利用率, 与海洋环境相容的单原子催化剂表现出良好的应用潜力. 本文对单原子催化在海洋氢能、 海洋能源转化和海水提铀等海洋能源领域的研究进行了综合评述, 并对单原子催化在海洋能源领域的发展前景进行了展望.     

单原子催化剂在电化学中的研究进展

目前单原子催化剂的研究呈现爆发式增长, 已然成为材料科学和催化领域的明星材料和研究热点. 前期报道的单原子催化剂研究主要针对某一个应用方向进行探讨, 较少研究催化剂的双功能或多功能应用. 近年来, 为了拓展单原子催化剂在更多领域和方向的应用, 具有双功能甚至多功能的单原子催化剂的设计开发备受关注. 本文综合评述了近年来具有双功能活性的单原子催化剂的研究进展, 重点介绍了其在电化学领域中的最新应用研究. 最后, 对具有双功能活性的单原子催化剂发展研究中存在的问题进行了简要分析, 并对未来发展前景进行了展望.     

单原子材料的冷冻合成

近年来, 单原子催化剂因其最大化的金属原子利用效率和高催化性能, 已成为能量存储和转化领域中的研究热点. 单原子催化剂的高活性主要来源于其低配位结构、 量子尺寸效应和原子与载体之间的强相互作用. 因此, 如何根据构-效关系开发通用且简单的制备高效单原子催化剂的方法具有重要的意义. 从实际应用的角度而言, 湿化学法因具有工艺简单和易于大规模生产的特性, 被认为是一种实现工业化制备单原子催化剂的方法, 现已开发了一系列制备负载型单原子催化剂的策略. 本文从独特的抑制反应物前驱体物质形核的角度出发, 总结了冷冻合成方法对形核的抑制机制, 进一步针对不同方面的应用, 探讨了单原子材料的催化机理, 并对其未来的发展进行了展望.     

Single-Site Heterogeneous Catalysts: From Synthesis to NMR Signal Enhancement

Catalysts with well-defined, single, active centers are of great importance and their utilization allows the gap between homo- and heterogeneous catalysis to be bridged and, importantly, the main selectivity problem of heterogeneous catalysis and the main separation challenge of homogeneous catalysis to be overcome. Moreover, the use of single-site catalysts allows the NMR signal to be significantly enhanced through the pairwise addition of two hydrogen atoms from a parahydrogen molecule to an unsaturated substrate. This review covers the fundamentals of the synthesis of single-site catalysts and shows the new aspects of their applications in both modern catalysis and the field of parahydrogen-based hyperpolarization. The different novel aspects of the formation and utilization of single-site catalysts, along with the possibility of NMR signal enhancement observations are described.     

分子筛限域单原子金属催化剂的研究进展

分子筛由于具有规则的微孔孔道结构、 较大的表面积、 优异的(水)热稳定性, 被认为是限域合成超小尺寸金属物种的理想载体. 近年来, 分子筛限域单原子金属催化剂由于超高的金属分散度、 接近100%的金属利用率以及独特的电子结构, 被广泛地应用于重要的催化反应和气体吸附分离过程. 本文系统地总结了近年来分子筛限域不同类型单原子金属催化剂的合成策略, 以及其在多相催化和气体分离等领域的研究进展. 最后, 提出了分子筛限域单原子金属催化剂在合成与表征方面存在的挑战和未来的发展方向.     

Potential Utilization of Metal–Organic Frameworks in Heterogeneous Catalysis: A Case Study of Hydrogen‐Bond Donating and Single‐Site Catalysis

Crystalline solid materials are platforms for the development of effective catalysts and have shown vast benefits at the frontiers between homogeneous and heterogeneous catalysts. Typically, these crystalline solid catalysts outperformed their homogeneous analogs due to their high stability, selectivity, better catalytic activity, reusability and recyclability in catalysis applications. This point of view, comprising significant features of a new class of porous crystalline materials termed as metal‐organic frameworks (MOFs) engendered the attractive pathway to synthesize functionalized heterogeneous MOF catalysts. The present review includes the recent research progress in developing both hydrogen‐bond donating (HBD) MOF catalysts and MOF‐supported single‐site catalysts (MSSCs). The first part deals with the novel designs of urea‐, thiourea‐ and squaramide‐containing MOF catalysts and study of their crucial role in HBD catalysis. In the second part, we discuss the important classification of MSSCs with existing examples and their use in desired catalytic reactions. In addition, we describe the relative catalytic efficiency of these MSSCs with their homogeneous and similarly reported analogs. The precise knowledge of discussed heterogeneous MOF catalysts in this review may open the door for new research advances in the field of MOF catalysis.     

Mechanisms of Asymmetric Heterogeneous Catalysis1

Asymmetric catalysis plays an important role in present-day production of pharmaceuticals. It can be predicted that enantioselective catalysis will dominate in the future, replacing conventional stoichiometric methods. Heterogeneous catalysts offer several advantages compared to their homogeneous counterparts. In the present review mechanisms of asymmetric heterogeneous catalysis are discussed and the different ways of chirality transfer are addressed. Enantioselection is possible over chiral supports and chiral metals exhibiting intrinsic chirality, as well as over modified metal supported catalysts. The interactions between a reactant and a modifier are very specific being critical for achieving high enantioselectivities.     

单原子材料在二氧化碳催化中的技术经济分析与产业化应用前景

近年来, 随着科学研究的不断深入, 单原子催化剂由于具有高活性与高选择性等突出特点被广泛挖掘和应用. 作为连接多相与均相催化的桥梁, 单原子催化剂已经成为催化领域的重要研究对象之一, 具有广泛的工业化应用前景. 本文对单原子催化剂的发展历程、 特点及其在不同领域的应用进行了概括, 综合评述了当前CO₂还原领域的技术经济分析, 并首次对单原子材料催化转化CO₂进行了技术经济分析与计算. 最后, 对单原子催化剂在CO₂还原领域中工业化应用的未来发展方向及亟需解决的关键科学和技术问题进行了展望, 以期推动单原子催化材料的进一步广泛应用.     

Promotion effect of Au single-atom support graphene for CO oxidation

CO oxidation is a vital catalytic reaction for environmental purification, facing challenges due to the catalysts applied to oxidize CO are mainly rare and expensive noble catalysts. Since the high atomic availability, catalytic efficiency, and selectivity of single-atom catalysis, it has been widely studied and proven to be brilliant in CO oxidation. Au single-atom catalysts are regarded as excellent single-atom catalysts in oxidizing CO, whose progress is limited by the indistinct understanding of the reaction mechanism and role of the active atom. Hence, DFT calculation was used to investigate CO oxidation processes, active mechanisms, and the role of Au single-atom. Graphene involving prominent physical and chemical properties was selected as a model supporter. The single-atom support graphene materials exhibit better CO oxidation activities than pristine graphene, among which CO oxidation property on Au/GP is the highest with a 0.38 eV rate-determining barrier following ER mechanism. The outstanding performances including excellent electronic structures, adsorption properties, and strong activation of intermediate products contribute to the high CO oxidation activity of Au/GP, and the Au single-atom is the active center. Our work provides a novel guide for single-atom catalytic CO oxidation, accelerating the development of single-atom catalysis.     

单原子催化:沟通均相催化与多相催化的桥梁（英文）

催化在现代化学工业中占据着极为重要的地位.催化剂是催化过程的核心.均相催化剂由于具有均一、孤立的活性位点,往往具有高活性与高选择性;但是分离困难限制了其实际应用.多相催化剂由于金属原子利用效率低、活性组分不均匀,活性与选择性相对较低;但其稳定易分离的特点使得目前大多数工业催化过程都是多相催化过程.近年来,单原子催化逐渐成为催化领域新的研究热点与前沿,受到相关研究人员的广泛关注.作为一种多相催化剂,单原子催化剂具有稳定易分离的优势.此外,单原子催化剂具有类似均相催化剂的孤立活性位点,可能具有高活性与高选择.因此单原子催化的概念一经提出,便被认为有望成为架起多相催化与均相催化的桥梁;但几年来并未从实验上得到证实.2016年开始,逐渐有单原子催化剂在经典均相催化反应过程中的应用报道,为该观点提供了实验上的证据.本综述概述了2016至2017年单原子催化剂在典型均相催化反应中的成功应用,包括:1)氢甲酰化反应.以烯烃和合成气为原料合成精细化学品醛类化合物的氢甲酰化反应是目前化工生产中典型的均相催化反应之一.2016年,张涛课题组和曾杰课题组先后报道了Rh/ZnO和Rh/CoO单原子催化剂在该反应中的成功应用.催化剂都表现出优异的催化性能,活性与经典均相Wilkinson’s催化剂相当;2)氢硅加成反应.作为合成有机硅产品的重要反应之一,工业上硅氢加成反应主要由Pt基均相催化剂催化.2016年Beller课题组首次报道了将Pt/Al_2O_3单原子催化剂用于烯烃硅氢加成反应中.该催化剂除表现出良好的催化活性和区域选择性外,还具有较高的稳定性和底物普适性;3)C–H键选择性氧化.烷烃部分氧化反应在学术研究和工业应用方面都有重要意义.刘文刚等将M-N-C单原子催化剂(其中M为Fe,Co等金属)成功应用于C–H键的活化反应中,并对催化剂的结构进行了深入剖析.以上实例表明通过调控金属与载体组合、设计开发合适的单原子催化剂,可以达到结合均相催化高活性、高选择性与多相催化稳定易分离的目的,为均相催化多相化提供了一条新途径,也证明单原子催化可望成为沟通均相催化与多相催化的桥梁.     

聚合物单原子光催化剂的载流子分离和表面反应机制

近10年来, 研究者制备了大量的单原子催化剂(SACs), 其在光、 电、 热等催化体系中展现出优异的催化性能及较高的实用性和经济性. 光催化过程的独特性使其在催化本质上明显不同于热催化和电催化过程, 即处于激发态的电子和空穴参与反应, 而非基态的价电子. 本文首先探讨了有机聚合半导体与传统无机金属化合物半导体的区别, 指出聚合物半导体介电常数通常较小且光生电子与空穴的中心距离过短(计算上通常 ^{<1 nm), 导致其界面处几乎不存在明显的能带弯曲. 将金属离子引入聚合物半导体的骨架中可以有效引入给体-受体对, 在提高载流子分离效率的同时延长其寿命. 在高效聚合物基单原子光催化剂的设计过程中, 引入单原子金属位点后的激发态电荷分布及捕获态电子对反应的驱动力是决定催化剂整体性能的关键因素. 时间-空间双因子布局分析法和瞬态吸收光谱可为研究者提供相关信息. 随着人工智能的进一步发展, 建立回归精度接近或达到密度泛函理论水准的能量函数, 从而反推激发态下体系的能量变化, 有望为光催化反应的激发特性与反应活性建立可靠的联系. 此外, 配体和溶剂化效应在今后的研究中也应被仔细考虑.}     

Non-Metal Single-Phosphorus-Atom Catalysis of Hydrogen Evolution

Non-metal-based single-atom catalysts (SACs) offer low cost, simple synthesis methods, and effective regulation for substrates. Herein, we developed a simplified pressurized gas-assisted process, and report the first non-metal single-atom phosphorus with atomic-level dispersion on unique single-crystal Mo₂C hexagonal nanosheet arrays with a (001) plane supported by carbon sheet (SAP-Mo₂C-CS). The SAP-Mo₂C-CS is structurally stable and shows exceptional electrocatalytic activity for the hydrogen evolution reaction (HER). A so-called high-active “window” based on the active sites of P atoms and their adjacent Mo atoms gives a ΔG_H* close to zero for hydrogen evolution, which is the most ideal ΔG_H* reported so far. Meanwhile, the moderate d-band center value of SAP-Mo₂C-CS can be also used as an ideal standard value to evaluate the HER performance in non-metal-based SACs.     

对单原子催化术语的讨论

单原子催化,是由我国化学家提出的一个新概念,近年来在多相催化领域引领了一波研究热潮。单原子气体,是中学化学教育中的重要知识点。单原子催化这一术语,在文字上与单原子气体非常相似,但又有着完全不同的意义,存在一定的误导性,值得商榷。