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.

Atomic interface regulation is thought to be an efficient method to adjust the performance of single atom catalysts. Herein, a practical strategy was reported to rationally design single copper atoms coordinated with both sulfur and nitrogen atoms in metal-organic framework derived hierarchically porous carbon (S-Cu-ISA/SNC). The atomic interface configuration of the copper site in S-Cu-ISA/SNC is detected to be an unsymmetrically arranged Cu-S1N3 moiety. The catalyst exhibits excellent oxygen reduction reaction activity with a half-wave potential of 0.918 V vs. RHE. Additionally, through in situ X-ray absorption fine structure tests, we discover that the low-valent Cuprous-S1N3 moiety acts as an active center during the oxygen reduction process. Our discovery provides a universal scheme for the controllable synthesis and performance regulation of single metal atom catalysts toward energy applications. Engineering the coordination environment of single atom catalysts offers to opportunity to optimize electrocatalytic activity. In this work, the authors prepare an unsymmetrical Cu-S1N3 single atom site on porous carbon with high performance in the oxygen reduction reaction.

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Engineering unsymmetrically coordinated Cu-S 1 N 3 single atom sites with enhanced oxygen reduction activity

Emerging single atom catalysts (SACs), especially carbon-based SACs are appealing materials in environmental catalysis because of their ultrahigh performances, environmental friendliness, structural/chemical robustness, and the maximum utilization of active metal sites. The metal centres, carbon matrixes, and coordination characteristics collectively determine the electronic features of carbon-based SACs, and their behaviours in catalysing peroxide activation and efficiencies in advanced oxidation processes (AOPs). However, there is lack of a comprehensive and critical review reporting the successful marriage of carbon-based SACs in AOP-based remediation technologies. It is particularly necessary to systematically compare and reveal the catalytic sites and the associated mechanisms of carbon-based SACs in diverse AOP systems. In this review, we highlight the synthetic strategies, characterisation, and computation of carbon-based SACs, and for the first time, showcase their innovative applications in AOP technologies. We unveil the origins of versatile catalytic oxidation pathways in different AOP systems and the mechanisms of micropollutant degradation over carbon-based SACs, distinguished from the upsized counterparts (metals/oxides and carbon substrates). We also provide directions to the rational design of on-demand SACs for green chemistry and environmental sustainability. Also, we suggest a designated and integrated experimental/theoretical protocol for revealing the structure-catalysis relations of SACs in AOP applications, and propose the prospects for future opportunities and challenges.

Single-atom catalysis in advanced oxidation processes for environmental remediation.

Demonstrated here is the correlation between atomic configuration induced electronic density of single-atom Co active sites and oxygen reduction reaction (ORR) performance by combining density-functional theory (DFT) calculations and electrochemical analysis. Guided by DFT calculations, a MOF-derived Co single-atom catalyst with the optimal Co1 -N3 PS active moiety incorporated in a hollow carbon polyhedron (Co1 -N3 PS/HC) was designed and synthesized. Co1 -N3 PS/HC exhibits outstanding alkaline ORR activity with a half-wave potential of 0.920 V and superior ORR kinetics with record-level kinetic current density and an ultralow Tafel slope of 31 mV dec-1 , exceeding that of Pt/C and almost all non-precious ORR electrocatalysts. In acidic media the ORR kinetics of Co1 -N3 PS/HC still surpasses that of Pt/C. This work offers atomic-level insight into the relationship between electronic density of the active site and catalytic properties, promoting rational design of efficient catalysts.

Atomic-Level Modulation of Electronic Density at Cobalt Single-Atom Sites Derived from Metal-Organic Frameworks: Enhanced Oxygen Reduction Performance.

The electronic metal-support interaction (EMSI), which acts as a bridge between theoretical electronic study and the design of heterogenous catalysts, has attracted much attention. Utilizing the interaction between the metal and the support is one of the most essential strategies to enhance electrocatalytic efficiency due to structural and synergetic promotion. To date, as the ideal model for realizing EMSI, many types of single-atom catalysts (SACs) have been developed. The understanding of the electronic interaction on SACs has also been pushed to a higher level. However, systematic theories and operando experiments are seldom reported, and will be necessary to put forward and be carried out, respectively. Herein, the types, characterization, mechanism, and electrocatalytic applications of EMSI are comprehensively summarized and discussed. In addition to the basic information above, the challenges, opportunities, and future development of the EMSI on SACs are also proposed to present an overall view and reference to the later research.

Electronic Metal–Support Interaction of Single-Atom Catalysts and Applications in Electrocatalysis

Atomically dispersed transition metal active sites have emerged as one of the most important fields of study because they display promising performance in catalysis and have the potential to serve as ideal models for fundamental understanding. However, both the preparation and determination of such active sites remain a challenge. The structural engineering of carbon- and nitrogen-coordinated metal sites (M-N-C, M = Fe, Co, Ni, Mn, Cu, etc.) via employing new heteroatoms, e.g., P and S, remains challenging. In this study, carbon nanosheets embedded with nitrogen and phosphorus dual-coordinated iron active sites (denoted as Fe-N/P-C) were developed and determined using cutting edge techniques. Both experimental and theoretical results suggested that the N and P dual-coordinated iron sites were favorable for oxygen intermediate adsorption/desorption, resulting in accelerated reaction kinetics and promising catalytic oxygen reduction activity. This work not only provides efficient way to prepare well-defined single-atom active sites to boost catalytic performance but also paves the way to identify the dual-coordinated single metal atom sites.

Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination

Oxygen-bearing copper (OBC) has been widely studied for enabling the C-C coupling of the electrocatalytic CO2 reduction reaction (CO2RR) since this is a distinctive hallmark of strongly correlated OBC systems and may benefit many other Cu-based catalytic processes. Unresolved problems, however, include the instability of and limited knowledge regarding OBC under realistic operating conditions, raising doubts about its role in CO2RR. Here, an atypical and stable OBC catalyst with a hierarchical pore and nanograin-boundary structure was constructed and was found to exhibit efficient CO2RR for the production of ethylene with a Faradaic efficiency of 45% at a partial current density of 44.7 mA cm-2 in neutral media, and the ethylene partial current density is nearly 26 and 116 times that of oxygen-free copper (OFC) and commercial Cu foam, respectively. More importantly, the structure-activity relationship in CO2RR was explored through a comprehensive analysis of experimental data and computational techniques, thus increasing the fundamental understanding of CO2RR. A systematic characterization analysis suggests that atypical OBC (Cu4O) was formed and that it is stable even at -1.00 V [(vs the reversible hydrogen electrode (RHE)]. Density functional theory calculations show that the atypical OBC enables control over CO adsorption and dimerization, making it possible to implement a preference for the electrosynthesis of ethylene (C2) products. These results provide insight into the synthesis and structural characteristics of OBC as well as its interplay with ethylene selectivity.

Atypical Oxygen-Bearing Copper Boosts Ethylene Selectivity toward Electrocatalytic CO2 Reduction.

Visible-light driven CO2 reduction coupled with water oxidation on Cl-doped Cu2O nanorods

Many organic molecules have unique magnetic properties and can potentially serve as excellent molecular spin devices, which is worth exploring deeply. Here, the spin transport properties of Mn, Fe, Co and Cu porphyrin dimer devices are investigated based on the first principles method. The spin filtering efficiencies of these molecular devices are maintained at 100% within certain applied voltage ranges and magnetoresistance ratios are higher than 108% which increase as the voltage increases. To explain the excellent spin-filtering and giant magnetoresistance effects, analysis of spin electron densities and transmission spectra indicates that magnetic properties are mainly contributed by the metal atoms and their neighbouring N atoms. From the transmission pathway studies, spin electrons come mainly through the π-conjugated structure of the metal porphyrin ring. Interestingly, in the Cu porphyrin dimer device, magnetic moments of the Cu-N structure in the Cu porphyrin dimer device show spin behaviors different from those of Mn, Fe and Co porphyrin dimer devices.

Ling Shuai

Papers

Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination

Atypical Oxygen-Bearing Copper Boosts Ethylene Selectivity toward Electrocatalytic CO2 Reduction.

Visible-light driven CO2 reduction coupled with water oxidation on Cl-doped Cu2O nanorods

Designing bifuncitonal molecular devices with a metalloporphyrin dimer.