Manipulating metal atoms in a controllable way for the synthesis of materials with the desired structure and properties is the holy grail of chemical synthesis. The recent emergence of single atomic site catalysts (SASC) demonstrates that we are moving toward this goal. Owing to the maximum efficiency of atom-utilization and unique structures and properties, SASC have attracted extensive research attention and interest. The prerequisite for the scientific research and practical applications of SASC is to fabricate highly reactive and stable metal single atoms on appropriate supports. In this review, various synthetic strategies for the synthesis of SASC are summarized with concrete examples highlighting the key issues of the synthesis methods to stabilize single metal atoms on supports and to suppress their migration and agglomeration. Next, we discuss how synthesis conditions affect the structure and catalytic properties of SASC before ending this review by highlighting the prospects and challenges for the synthesis as well as further scientific researches and practical applications of SASC.

Chemical Synthesis of Single Atomic Site Catalysts.

Single-atom photocatalysts have shown their compelling potential and arguably become the most active research direction in photocatalysis due to their fascinating strengths in enhancing light-harvesting, charge transfer dynamics, and surface reactions of a photocatalytic system. While numerous comprehensions about the single-atom photocatalysts have recently been amassed, advanced characterization techniques and vital theoretical studies are strengthening our understanding on these fascinating materials, allowing us to forecast their working mechanisms and applications in photocatalysis. In this review, we begin by describing the general background and definition of the single-atom photocatalysts. A brief discussion of the metal-support interactions on the single-atom photocatalysts is then provided. Thereafter, the current available characterization techniques for single-atom photocatalysts are summarized. After having some fundamental understanding on the single-atom photocatalysts, their advantages and applications in photocatalysis are discussed. Finally, we end this review with a look into the remaining challenges and future perspectives of single-atom photocatalysts. We anticipate that this review will provide some inspiration for the future discovery of the single-atom photocatalysts, manifestly stimulating the development in this emerging research area.

Heterogeneous Single-Atom Photocatalysts: Fundamentals and Applications.

Isolated atoms featuring unique reactivity are at the heart of enzymatic and homogeneous catalysts. In contrast, although the concept has long existed, single-atom heterogeneous catalysts (SACs) have only recently gained prominence. Host materials have similar functions to ligands in homogeneous catalysts, determining the stability, local environment, and electronic properties of isolated atoms and thus providing a platform for tailoring heterogeneous catalysts for targeted applications. Within just a decade, we have witnessed many examples of SACs both disrupting diverse fields of heterogeneous catalysis with their distinctive reactivity and substantially enriching our understanding of molecular processes on surfaces. To date, the term SAC mostly refers to late transition metal-based systems, but numerous examples exist in which isolated atoms of other elements play key catalytic roles. This review provides a compositional encyclopedia of SACs, celebrating the 10th anniversary of the introduction of this term. By defining single-atom catalysis in the broadest sense, we explore the full elemental diversity, joining different areas across the whole periodic table, and discussing historical milestones and recent developments. In particular, we examine the coordination structures and associated properties accessed through distinct single-atom-host combinations and relate them to their main applications in thermo-, electro-, and photocatalysis, revealing trends in element-specific evolution, host design, and uses. Finally, we highlight frontiers in the field, including multimetallic SACs, atom proximity control, and possible applications for multistep and cascade reactions, identifying challenges, and propose directions for future development in this flourishing field.

Single-Atom Catalysts across the Periodic Table.

Electrocatalysis plays a central role in clean energy conversion, enabling a number of processes for future sustainable technologies. Atomic site electrocatalysts (ASCs), including single-atomic site catalysts (SASCs) and diatomic site catalysis (DASCs), are being pursued as economical alternatives to noble-metal-based catalysts for these reactions by virtue of their exceptionally high atom utilization efficiencies, well-defined active sites and high selectivities. In this review, we start from a systematic review on the fabrication routes of ASCs followed by an overview of some new and effective characterization methods to precisely probe the atomic structure. Then we give a comprehensive summary on the current advances in some typical clean energy reactions: water splitting, including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER); oxygen reduction reaction (ORR), including selective 4e- - ORR toward H2O/OH- and 2e- - ORR toward H2O2/HO2-; selective electrooxidation of formic acid, methanol and ethanol (FAOR, MOR and EOR). At the end of this paper, we present a brief conclusion, and discuss the challenges and opportunities on the further development of more selective, active, stable and less expensive ASCs.

Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation.

Designing efficient electrocatalysts for hydrogen evolution reaction is significant for renewable and sustainable energy conversion. Here, we report single-atom platinum decorated nanoporous Co0.85 ...

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Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction

Designing efficient single-atom catalysts (SACs) for oxygen evolution reaction (OER) is critical for water-splitting. However, the self-reconstruction of isolated active sites during OER not only influences the catalytic activity, but also limits the understanding of structure-property relationships. Here, we utilize a self-reconstruction strategy to prepare a SAC with isolated iridium anchored on oxyhydroxides, which exhibits high catalytic OER performance with low overpotential and small Tafel slope, superior to the IrO2. Operando X-ray absorption spectroscopy studies in combination with theory calculations indicate that the isolated iridium sites undergo a deprotonation process to form the multiple active sites during OER, promoting the O–O coupling. The isolated iridium sites are revealed to remain dispersed due to the support effect during OER. This work not only affords the rational design strategy of OER SACs at the atomic scale, but also provides the fundamental insights of the operando OER mechanism for highly active OER SACs. Direct observation of the atomic and electronic structure of a single-atom catalyst is essential. Here, the authors report an oxyhydroxide stabilized iridium catalyst with superior oxygen evolution catalytic activity and identify the isolated iridium sites which promote the H2O attack and O–O coupling.

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Dynamic active-site generation of atomic iridium stabilized on nanoporous metal phosphides for water oxidation

Spontaneous Atomic Ruthenium Doping in Mo2CTX MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

Terahertz technology promises broad applications, which calls for terahertz electromagnetic interference (EMI) shielding materials to alleviate radiation pollution. 2D transition metal carbides and/or nitrides (MXenes) with metallic conductivity are promising for EMI shielding, but simultaneously realizing light weight, high stability, and foldability in a MXene shielding material to meet the requirements of increasingly popular portable and wearable equipment has remained a great challenge. Herein, an ion-diffusion-induced gelation method is demonstrated to synthesize free-standing, light-weight, foldable, and highly stable MXene foams, in which MXene sheets are cross-linked by multivalent metal ions and graphene oxide to form an oriented porous structure. The method is highly efficient, controllable, and versatile for scalable generation of functional 3D MXene structures with arbitrary shapes and synergistic properties. The distinctive cross-linked porous structure endows the light-weight MXene foam with good foldability, outstanding durability and stability in wet environments, and an excellent terahertz shielding effectiveness of 51 dB at a small thickness of 85 μm. This work not only provides an insight for the on-target design of high-performance terahertz shielding materials but also expands the applications of MXenes in 3D macroscopic form.

Highly Stable 3D Ti3C2Tx MXene-Based Foam Architectures toward High-Performance Terahertz Radiation Shielding.

Maximizing the catalytic activity of single-atom catalysts is vital for the application of single-atom catalysts in industrial water-alkali electrolyzers, yet the modulation of the catalytic properties of single-atom catalysts remains challenging. Here, we construct strain-tunable sulphur vacancies around single-atom Ru sites for accelerating the alkaline hydrogen evolution reaction of single-atom Ru sites based on a nanoporous MoS2-based Ru single-atom catalyst. By altering the strain of this system, the synergistic effect between sulphur vacancies and Ru sites is amplified, thus changing the catalytic behavior of active sites, namely, the increased reactant density in strained sulphur vacancies and the accelerated hydrogen evolution reaction process on Ru sites. The resulting catalyst delivers an overpotential of 30 mV at a current density of 10 mA cm−2, a Tafel slope of 31 mV dec−1, and a long catalytic lifetime. This work provides an effective strategy to improve the activities of single-atom modified transition metal dichalcogenides catalysts by precise strain engineering. The modulation of single-atom catalyst properties for industrial applications remains challenging. Here, authors use strain engineering to amplify the synergistic effect between MoS2’s sulphur vacancies and single-atom Ru sites and accelerate H2 evolution electrocatalysis.

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Kang Jiang

Papers

Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction

Dynamic active-site generation of atomic iridium stabilized on nanoporous metal phosphides for water oxidation

Spontaneous Atomic Ruthenium Doping in Mo2CTX MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

Highly Stable 3D Ti3C2Tx MXene-Based Foam Architectures toward High-Performance Terahertz Radiation Shielding.

Rational strain engineering of single-atom ruthenium on nanoporous MoS2 for highly efficient hydrogen evolution.