Single Layer of Polymeric Cobalt Phthalocyanine: Promising Low‐Cost and High‐Activity Nanocatalysts for CO Oxidation

The catalytic behavior of transition metals (Sc to Zn) combined in polymeric phthalocyanine (Pc) is investigated systematically by using first‐principles calculations. The results indicate that CoPc exhibits the highest catalytic activity for CO oxidation at room temperature with low energy barriers. By exploring the two well‐established mechanisms for CO oxidation with O₂, namely, the Langmuir–Hinshelwood (LH) and the Eley–Rideal (ER) mechanisms, it is found that the first step of CO oxidation catalyzed by CoPc is the LH mechanism (CO + O₂ → CO₂ + O) with energy barrier as low as 0.65 eV. The second step proceeds via both ER and LH mechanisms (CO + O → CO₂) with small energy barriers of 0.10 and 0.12 eV, respectively. The electronic resonance among Co‐3d, CO‐2π*, and O₂‐2π* orbitals is responsible for the high activity of CoPc. These results have significant implications for a novel avenue to fabricate organometallic sheet nanocatalysts for CO oxidation with low cost and high activity.     

Single-Atom Catalysts Supported by Crystalline Porous Materials: Views from the Inside

Single-atom catalysts (SACs) have recently emerged as an exciting system in heterogeneous catalysis showing outstanding performance in many catalytic reactions. Single-atom catalytic sites alone are not stable and thus require stabilization from substrates. Crystalline porous materials such as zeolites and metal-organic frameworks (MOFs) are excellent substrates for SACs, offering high stability with the potential to further enhance their performance due to synergistic effects. This review features recent work on the structure, electronic, and catalytic properties of zeolite and MOF-protected SACs, offering atomic-scale views from the “inside” thanks to the subatomic resolution of synchrotron X-ray absorption spectroscopy (XAS). The extended X-ray absorption fine structure and associated methods will be shown to be powerful tools in identifying the single-atom site and can provide details into the coordination environment and bonding disorder of SACs. The X-ray absorption near-edge structure will be demonstrated as a valuable method in probing the electronic properties of SACs by analyzing the white line intensity, absorption edge shift, and pre-/postedge features. Emphasis is also placed on in situ/operando XAS using state-of-the-art equipment, which can unveil the changes in structure and properties of SACs during the dynamic catalytic processes in a highly sensitive and time-resolved manner.     

Porous Carbon Membrane‐Supported Atomically Dispersed Pyrrole‐Type Fe?N4 as Active Sites for Electrochemical Hydrazine Oxidation Reaction

The rational design of catalytically active sites in porous materials is essential in electrocatalysis. Herein, atomically dispersed Fe‐N_x sites supported by hierarchically porous carbon membranes are designed to electrocatalyze the hydrazine oxidation reaction (HzOR), one of the key techniques in electrochemical nitrogen transformation. The high intrinsic catalytic activity of the Fe‐N_x single‐atom catalyst together with the uniquely mixed micro‐/macroporous membrane support positions such an electrode among the best‐known heteroatom‐based carbon anodes for hydrazine fuel cells. Combined with advanced characterization techniques, electrochemical probe experiments, and density functional theory calculation, the pyrrole‐type Fe? N₄ structure is identified as the real catalytic site in HzOR.     

En Route to High-Density Chiral Single-walled Carbon Nanotube Arrays using Solid Trojan Catalysts

Solid catalyst is widely recognized as an effective strategy to control the chirality of single-walled carbon nanotubes (SWNTs). However, it is still not compatible with high density in horizontal arrays. “Trojan” catalysts strategy is one of the most effective methods to realize SWNTs with high density and has great potential in chirality control. Here, the co-realization of high density and chirality controlling for SWNTs in a low-temperature growth process is reported based on the developed solid “Trojan” catalyst. High temperature “Trojan” catalyst formation process provides sufficient catalyst number to acquire high density. These liquid “Trojan” catalysts are cooled to solid state by adopting low growth temperature (540 °C), which can be good template to realize the chirality controlling of SWNTs with exposing six-fold symmetry face, (111). Finally, (9, 6) and (13, 1) SWNTs enriched horizontal array with the purity of ≈90% and density of 4 tubes µm⁻¹ is realized. The comparison between the distribution of initial catalysts and the density of as-grown tubes indicates no sacrificing on catalysts number to improve chirality selectivity. This work opens a new avenue on the catalyst's design and chirality controlling in SWNTs growth.     

Highly Exposed ?NH2 Edge on Fragmented g-C3N4 Framework with Integrated Molybdenum Atoms for Catalytic CO2 Cycloaddition: DFT and Techno-Economic Assessment

This study focuses on the applicability of single-atom Mo-doped graphitic carbon nitride (GCN) nanosheets which are specifically engineered with high surface area (exfoliated GCN),  NH₂ rich edges, and maximum utilization of isolated atomic Mo for propylene carbonate (PC) production through CO₂ cycloaddition of propylene oxide (PO). Various operational parameters are optimized, for example, temperature (130 °C), pressure (20 bar), catalyst (Mo₂GCN), and catalyst mass (0.1 g). Under optimal conditions, 2% Mo-doped GCN (Mo₂GCN) has the highest catalytic performance, especially the turnover frequency (TOF) obtained, 36.4 h⁻¹ is higher than most reported studies. DFT simulations prove the catalytic performance of Mo₂GCN significantly decreases the activation energy barrier for PO ring-opening from 50–60 to 4.903 kcal mol⁻¹. Coexistence of Lewis acid/base group improves the CO₂ cycloaddition performance by the formation of coordination bond between electron-deficient Mo atom with O atom of PO, while  NH₂ surface group disrupts the stability of CO₂ bond by donating electrons into its low-level empty orbital. Steady-state process simulation of the industrial-scale consumes 4.4 ton h⁻¹ of CO₂ with PC production of 10.2 ton h⁻¹. Techno-economic assessment profit from Mo₂GCN is estimated to be 60.39 million USD year⁻¹ at a catalyst loss rate of 0.01 wt% h⁻¹.     

Activating Single-Atom Ni Site via First-Shell Si Modulation Boosts Oxygen Reduction Reaction

Atomically dispersed nitrogen-coordinated 3d transition-metal site on carbon support (M-NC) are promising alternatives to Pt group metal-based catalysts toward oxygen reduction reaction (ORR). However, despite the excellent activities of most of M-NC catalysts, such as Fe-NC, Co-NC et al., their durability is far from satisfactory due to Fenton reaction. Herein, this work reports a novel Si-doped Ni-NC catalyst (Ni-SiNC) that possesses high activity and excellent stability. X-ray absorption fine structure and aberration-corrected transmission electron microscopy uncover that the single-atom Ni site is coordinated with one Si atom and three N atoms, constructing Ni-Si₁N₃ moiety. The Ni-SiNC catalyst exhibits a half-wave potential (E_1/2) of 0.866 V versus RHE, with a distinguished long-term durability in alkaline media of only 10 mV negative shift in E_1/2 after 35 000 cycles, which is also validated in Zn-air battery. Density functional theory calculations reveal that the Ni-Si₁N₃ moiety facilitates ORR kinetics through optimizing the adsorption of intermediates.     

Advances in Transition-Metal-Based Dual-Atom Oxygen Electrocatalysts

Oxygen electrocatalysis has aroused considerable interest over the past years because of the new energy technologies boom in hydrogen energy and metal–air battery. However, due to the sluggish kinetic of the four-electron transfer process in oxygen reduction reaction and oxygen evolution reaction, the electro-catalysts are urgently needed to accelerate the oxygen electrocatalysis. Benefit from the high atom utilization efficiency, unprecedentedly high catalytic activity, and selectivity, single-atom catalysts (SACs) are considered the most promising candidate to replace the traditional Pt-group-metal catalysts. Compared with SACs, the dual-atom catalysts (DACs) are attracting more attraction including higher metal loading, more versatile active sites, and excellent catalytic activity. Therefore, it is essential to explore the new universal methods approaching to the preparation, characterization, and to elucidate the catalytic mechanisms of the DACs. In this review, several general synthetic strategies and structural characterization methods of DACs are introduced and the involved oxygen catalytic mechanisms are discussed. Moreover, the state-of-the-art electrocatalytic applications including fuel cells, metal–air batteries, and water splitting have been sorted out at present. The authors hope this review has given some insights and inspiration to the researches about DACs in electro-catalysis.     

Electronic Modulation of Metal-Organic Frameworks Caused by Atomically Dispersed Ru for Efficient Hydrogen Evolution

Designing excellent electrocatalysts for the hydrogen evolution reaction (HER) is extremely significant in producing clean and sustainable hydrogen fuel. Herein, a rational strategy is developed to fabricate a promising electrocatalyst by introducing atomically dispersed Ru into a cobalt-based metal-organic framework (MOF), Co-BPDC (Co(bpdc)(H₂O)₂, BPDC: 4,4'-Biphenyldicarboxylic acid). The obtained CoRu-BPDC nanosheet arrays exhibit remarkable HER performance with an overpotential of 37 mV at a current density of 10 mA cm⁻² in alkaline media, which is superior to most of the MOF-based electrocatalysts and comparable to the commercial Pt/C. Synchrotron radiation-based X-ray absorption fine structure (XAFS) spectroscopy studies verify that the isolated Ru atoms are dispersed in Co-BPDC nanosheets with the formation of five-coordinated Ru-O₅ species. XAFS spectroscopy combined with density functional theory (DFT) calculations unravels that atomically dispersed Ru can modulate the electronic structure of the as-obtained Co-BPDC, contributing to the optimization of binding strength for H* and the enhancement of HER performance. This work opens a new avenue to rationally design highly-active single-atom modified MOF-based HER electrocatalysts via modulating electronic structures of MOF.     

Graphene-Encapsulated Bifunctional Catalysts with High Activity and Durability for Zn–Air Battery

Carbon-based electrocatalysts with both high activity and high stability are desirable for use in Zn–air batteries. However, the carbon corrosion reaction (CCR) is a critical obstacle in rechargeable Zn–air batteries. In this study, a cost-effective carbon-based novel material is reported with a high catalytic effect and good durability for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), prepared via a simple graphitization process. In situ growth of graphene is utilized in a 3D-metal-coordinated hydrogel by introducing a catalytic lattice of transition metal alloys. Due to the direct growth of few-layer graphene on the metal alloy decorated 3d-carbon network, greatly reduced CCR is observed in a repetitive OER test. As a result, an efficient bifunctional electrocatalytic performance is achieved with a low ΔE value of 0.63 V and good electrochemical durability for 83 h at a current density of 10 mA cm⁻² in an alkaline media. Moreover, graphene-encapsulated transition metal alloys on the nitrogen-doped carbon supporter exhibit an excellent catalytic effect and good durability in a Zn–air battery system. This study suggests a straightforward way to overcome the CCR of carbon-based materials for an electrochemical catalyst with wide application in energy conversion and energy storage devices.     

Single-Atom Catalysts in Catalytic Biomedicine

The intrinsic deficiencies of nanoparticle-initiated catalysis for biomedical applications promote the fast development of alternative versatile theranostic modalities. The catalytic performance and selectivity are the critical issues that are challenging to be augmented and optimized in biological conditions. Single-atom catalysts (SACs) featuring atomically dispersed single metal atoms have emerged as one of the most explored catalysts in biomedicine recently due to their preeminent catalytic activity and superior selectivity distinct from their nanosized counterparts. Herein, an overview of the pivotal significance of SACs and some underlying critical issues that need to be addressed is provided, with a specific focus on their versatile biomedical applications. Their fabrication strategies, surface engineering, and structural characterizations are discussed briefly. In particular, the catalytic performance of SACs in triggering some representative catalytic reactions for providing the fundamentals of biomedical use is discussed. A sequence of representative paradigms is summarized on the successful construction of SACs for varied biomedical applications (e.g., cancer treatment, wound disinfection, biosensing, and oxidative-stress cytoprotection) with an emphasis on uncovering the intrinsic catalytic mechanisms and understanding the underlying structure–performance relationships. Finally, opportunities and challenges faced in the future development of SACs-triggered catalysis for biomedical use are discussed and outlooked.