Regulation of Electrocatalytic Activity by Local Microstructure: Focusing on the Catalytic Active Zone

Traditional regulation methods of active sites have successfully optimized the performance of electrocatalysts, but seem unable to achieve further breakthrough in the catalytic activity. Unlike the conventional viewpoint of focusing on single active site, the concept of local microstructure active zone is more comprehensive and new methods to regulate the reaction zone for electrocatalytic reactions are developed accordingly. The local microstructure active zone refers to the zone with high catalytic activity formed by the interaction between active atoms and neighboring coordination atoms as well as the surrounding environment. Instead of the traditional single active atom site, the active zone is more suitable for the actual electrochemical reaction process. According to this concept, the activity of electrocatalysts can be coordinated by multiple active atoms. This strategy is beneficial for understanding the relationship between material, structure, and catalysis, which realizes the design and synthesis of high-performance electrocatalysts. This review provides the research progress of this strategy for electrocatalytic reactions, with emphasis on their applications in oxygen evolution reaction, urea oxidation reaction, and carbon dioxide reduction.     

Nonmetal Doping as a Robust Route for Boosting the Hydrogen Evolution of Metal-Based Electrocatalysts

Recently, nonmetal doping has exhibited its great potential for boosting the hydrogen evolution reaction (HER) of transition-metal (TM)-based electrocatalysts. To this end, this work overviews the recent achievements made on the design and development of the nonmetal-doped TM-based electrocatalysts and their performance for the HER. It is also shown that by rationally doping nonmetal elements, the electronic structures of TM-based electrocatalysts can be effectively tuned and in turn the Gibbs free energy of the TM for adsorption of H* intermediates (ΔG_H*) optimized, consequently enhancing the intrinsic activity of TM-based electrocatalysts. Notably, we highlight that concurrently doping two nonmetal elements can continuously and precisely regulate the electronic structures of the TM, thereby maximizing the activity for HER. Moreover, nonmetal doping also accounts for enhancing the physical properties of the TM (i.e. surface area). Therefore, nonmetal doping is a robust strategy for simultaneous regulation of the chemical and physical features of the TM.     

Scalable Synthesis and Electrocatalytic Performance of Highly Fluorinated Covalent Organic Frameworks for Oxygen Reduction

In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of non-scalable solvothermal procedures. Our method allows for the room-temperature and scalable synthesis of a highly fluorinated DFTAPB-TFTA-COF, which exhibits intrinsic hydrophobicity. We used DFT-based calculations to elucidate the role of the fluorine atoms in enhancing the crystallinity of the material through corrugation effects, resulting in maximized interlayer interactions, as disclosed both from PXRD structural resolution and theoretical simulations. We further investigated the electrocatalytic properties of this material towards the oxygen reduction reaction (ORR). Our results show that the fluorinated COF produces hydrogen peroxide selectively with low overpotential (0.062 V) and high turnover frequency (0.0757 s⁻¹) without the addition of any conductive additives. These values are among the best reported for non-pyrolyzed and metal-free electrocatalysts. Finally, we employed DFT-based calculations to analyse the reaction mechanism, highlighting the crucial role of the fluorine atom in the active site assembly. Our findings shed light on the potential of fluorinated COFs as promising electrocatalysts for the ORR, as well as their potential applications in other fields.     

Interfacial Assembly of Nanocrystals on Nanofibers with Strong Interaction for Electrocatalytic Nitrate Reduction

One-dimensional fiber architecture serves as an excellent catalyst support. The orderly arrangement of active materials on such a fiber substrate can enhance catalytic performance by exposing more active sites and facilitating mass diffusion; however, this remains a challenge. We developed an interfacial assembly strategy for the orderly distribution of metal nanocrystals on different fiber substrates to optimize their electrocatalytic performance. Using electrochemical nitrate reduction reaction (NO₃⁻RR) as a representative reaction, the iron-based nanofibers (Fe/NFs) assembly structure achieved an excellent nitrate removal capacity of 2317 mg N/g Fe and N₂ selectivity up to 97.2 %. This strategy could promote the rational design and synthesis of fiber-based electrocatalysts.     

Oxidation reaction by xanthine oxidase: theoretical study of reaction mechanism

The oxidation process by molybdenum-containing enzyme, xanthine oxidase, is theoretically studied with a model complex representing the reaction center and a typical benchmark substrate, formamide. Comparisons were systematically made among reaction mechanisms proposed previously. In the concerted and stepwise mechanisms that were theoretically discussed previously, the oxidation reaction takes place with a moderate activation barrier. However, the product is less stable than the reactant complex, which indicates that these mechanisms are unlikely. Moreover, the product of the concerted mechanism is not consistent with the isotope experimental result. In addition to those mechanisms, another mechanism initiated by the deprotonation of the active site was newly investigated here. In the transition state of this reaction, the carbon atom of formamide interacts with the oxo ligand of the Mo center and the hydrogen atom is moving from the carbon atom to the thioxo ligand. This reaction takes place with a moderate activation barrier and considerably large exothermicity. Furthermore, the product by this mechanism is consistent with the isotope experimental result. Also, our computations clearly show that the deprotonation of the active site occurs with considerable exothermicity in the presence of glutamic acid and substrate. The intermediate of the stepwise mechanism could not be optimized in the case of the deprotonated active site. From all these results, it should be concluded that the one-step mechanism with the deprotonated active site is the most plausible.     

Molecular Mechanism of a Hotdog‐Fold Acyl‐CoA Thioesterase

Thioesterases are enzymes that hydrolyze thioester bonds between a carbonyl group and a sulfur atom. They catalyze key steps in fatty acid biosynthesis and metabolism, as well as polyketide biosynthesis. The reaction molecular mechanism of most hotdog‐fold acyl‐CoA thioesterases remains unknown, but several hypotheses have been put forward in structural and biochemical investigations. The reaction of a human thioesterase (hTHEM2), representing a thioesterase family with a hotdog fold where a coenzyme A moiety is cleaved, was simulated by quantum mechanics/molecular mechanics metadynamics techniques to elucidate atomic and electronic details of its mechanism, its transition‐state conformation, and the free energy landscape of the process. A single‐displacement acid‐base‐like mechanism, in which a nucleophilic water molecule is activated by an aspartate residue acting as a base, was found, confirming previous experimental proposals. The results provide unambiguous evidence of the formation of a tetrahedral‐like transition state. They also explain the roles of other conserved active‐site residues during the reaction, especially that of a nearby histidine/serine pair that protonates the thioester sulfur atom, the participation of which could not be elucidated from mutation analyses alone.     

Several Key Factors for Efficient Electrocatalytic Water Splitting: Active Site Coordination Environment,Morphology Changes and Intermediates Identification

Water-splitting has emerged as a promising alternative strategy to produce clean hydrogen fuel. However, current electrocatalytic water splitting suffers from sluggish kinetics, thus developing efficient electrocatalysts is crucial. Identifying reaction centers discloses the reaction mechanism and will undoubtedly facilitate the design and optimization of efficient water splitting electrocatalysts. This review summarizes several advances involving the identification of the actual active sites and intermediates capture on the catalytic surface. The morphology and valence states change on 2D materials are chose to illustrate how structural evolution affect catalytic activity. Specifically, in situ/ex situ electron microscopy techniques that used for the characterization of catalytic sites, and spectroscopy techniques that used to detect active intermediates at the molecular level are highlighted. In addition, several perspectives, such as the development of new in situ techniques and electrokinetic analysis methods, are emphasized to shed light on future research.     

A multisite molecular mechanism for Baeyer-Villiger oxidations on solid catalysts using environmentally friendly H2O2 as oxidant

The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO2(rutile). The tin active site has been modeled by means of a Sn(OSiH3)3OH cluster, which includes a defect in the framework that provides the flexibility necessary for the interaction between the adsorbates and the Lewis acid center. Two possible reaction pathways have been considered in the computational study, one of them involving the activation of the cyclohexanone carbonyl group by Sn (1) and the other one involving hydrogen peroxide being activated through the formation of a tin-hydroperoxo intermediate (2). Both the quantum-chemical results and the kinetic study indicate that the reaction follows mechanism 1, and that the catalyst active site consists of two centers: the Lewis acid Sn atom to which cyclohexanone has to coordinate, and the oxygen atom of the Sn-OH group that interacts with H2O2 forming a hydrogen bond.     

Optimal Configuration of N-Doped Carbon Defects in 2D Turbostratic Carbon Nanomesh for Advanced Oxygen Reduction Electrocatalysis

The charge redistribution strategy driven by heteroatom doping or defect engineering has been developed as an efficient method to endow inert carbon with significant oxygen reduction reaction (ORR) activity. The synergetic effect between the two approaches is thus expected to be more effective for manipulating the charge distribution of carbon materials for exceptional ORR performance. Herein we report a novel molecular design strategy to achieve a 2D porous turbostratic carbon nanomesh with abundant N-doped carbon defects (NDC). The molecular level integration of aromatic rings as the carbon source and urea units as the N source and sacrificial template into the novel precursor of polyurea (PU) promises the formation of abundant carbon edge defects and N doping sites. A special active site—a carbon edge defect doped with a graphitic valley N atom—was revealed to be responsible for the exceptional ORR performance of NDC material.     

Optimal Configuration of N‐Doped Carbon Defects in 2D Turbostratic Carbon Nanomesh for Advanced Oxygen Reduction Electrocatalysis

The charge redistribution strategy driven by heteroatom doping or defect engineering has been developed as an efficient method to endow inert carbon with significant oxygen reduction reaction (ORR) activity. The synergetic effect between the two approaches is thus expected to be more effective for manipulating the charge distribution of carbon materials for exceptional ORR performance. Herein we report a novel molecular design strategy to achieve a 2D porous turbostratic carbon nanomesh with abundant N‐doped carbon defects (NDC). The molecular level integration of aromatic rings as the carbon source and urea units as the N source and sacrificial template into the novel precursor of polyurea (PU) promises the formation of abundant carbon edge defects and N doping sites. A special active site—a carbon edge defect doped with a graphitic valley N atom—was revealed to be responsible for the exceptional ORR performance of NDC material.     

Nb掺杂调控CoSeS多级纳米结构用于增强析氢反应

电催化析氢(HER)是清洁制氢的一种有效途径,对于氢经济和氢能产业的发展具有重要意义.金属掺杂是提高电催化剂本征活性的有效方法,导电基底的采用也有利于电荷传输和催化性能的整体提高.尽管已有关于硒化物作为HER催化剂的相关报道,但是合成条件有限、导电性、本征活性的影响,其电催化性能仍有提升的空间.此外,在酸性电解液中的腐蚀和氧化极大限制了催化剂性能的发挥.基于此,本文以氮掺杂碳球为载体,采用金属Nb掺杂、非金属硫硒化物协同以及表面碳包覆的三重策略,将掺杂元素Nb和活性位中心元素Co封装到氮掺杂碳纳米球内并进行连续的硫硒化反应,成功构筑多级纳米结构(Nb-CoSeS@NC)以提高其电催化析氢性能.碳球可为活性位的生长和分散提供足够的空间,同时有效防止活性金属的腐蚀和分解,并阻止金属纳米颗粒的团聚.硫化过程实现了非金属硫元素的掺杂,对于提高硒化物的催化活性和导电性都有重要作用.通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)及电催化性能测试,详细研究了Nb-CoSeS@NC独特的纳米结构和电催化制氢性能,并分析了构效关系.XRD结果发现,引入Nb后Co9Se8和CoSe的特征峰移向更高的角度,表明其晶格体积的减小,有助于电荷传输.同时,氮掺杂碳球(NC)在26°可以观察到无定型碳的峰,而石墨碳的D带和G带强度比约为1.05,均表明NC中缺陷的存在,这可以进一步提高碳材料的导电性.SEM和TEM表征显示,催化剂为直径120 nm的均匀的纳米核壳结构,壳层约为30 nm,无明显的团聚和破碎,这是催化剂具有高稳定性的重要原因.表面的褶皱保证了大的活性比表面积,可以大大增加活性位点的数量.同时,催化剂与NC之间的紧密结合可以降低电子传输的阻抗进而改善其稳定性和析氢性能.分析高分辨率的TEM结果发现,Nb掺杂后,Nb-CoSeS@NC中Co₉Se₈的(222)晶面由0.301 nm减小至0.184 nm,与XRD结果相符.XPS表征揭示了引入Nb之后的电子效应.与CoSeS@NC相比,Nb的掺杂使Co 2p向更低的结合能移动,而Se 3d则移向高结合能移动,这是由于Nb导致了更强的电子相互作用.在0.5 M的H₂SO₄中测试催化剂的析氢性能,Nb-CoSeS@NC仅需115 mV的过电位便可以实现10 mA cm^-2的电流密度,Tafel斜率为43 mV dec^-1,优于CoSeS@NC等其他对比样品,且优于大多数掺杂型硒化物电催化剂.经过12 h稳定性测试,电流密度未见明显降低,表明该多级结构催化剂的优异稳定性.Nb-CoSeS@NC提高活性可归因为Nb的掺杂增强了催化剂的电子相互作用,有助于提高的其本征导电性.Nb、Co正离子可以形成氢化物-受体中心,可能会削弱S-H键和Se-H键,并促进H-H键的形成,因此,多元掺杂产生的协同效应可以有效促进HER过程.此外,坚固的氮掺杂纳米碳壳为活性位点的分散提供了足够的空间和优异的电荷传输性能,同时降低了金属活性位腐蚀的可能性.     

异原子配位结构碳基单原子电催化剂结构与性能相关性的研究进展

单原子催化剂是一类以相互孤立的单个金属原子作为催化活性中心的、 具有高原子经济性及高活性的负载型催化剂, 被广泛应用于能源电催化领域. 近年来, 通过使用两种或两种以上原子与活性中心金属原子配位, 构建具有异原子配位结构的单原子材料, 展现了优异的电催化性能. 研究发现, 这种不对称的配位结构有效调控了中心金属原子的电子结构, 优化了催化反应的吸附和脱附能量, 提高了电催化的性能. 本文综合评述了具有异原子配位结构碳基单原子电催化剂的合成策略、 表征技术与方法, 以及在前沿能源电催化应用中的催化剂性能与结构之间的构效关系, 并展望了异原子配位结构碳基单原子电催化剂的研究前景.     

基于非贵金属氧还原催化剂的质子交换膜燃料电池性能

质子交换膜燃料电池的成本和寿命问题是制约其商业化的主要瓶颈. 开发高效稳定的新型非铂氧还原催化剂是降低电池成本的重要途径. 过渡金属-氮-碳型非贵金属催化剂具有较高催化活性、资源丰富、价格低廉等优点, 被认为是未来最有希望替代铂的氧还原催化剂. 本综述从催化剂的设计构筑、催化层结构优化以及电池测试等方面, 对过渡金属-氮-碳型非贵金属催化剂的国内外最新研究进展进行了重点讨论, 并对未来其发展趋势提出展望.     

Hydrogen bonding pathways in human dihydroorotate dehydrogenase

Dihydroorotate dehydrogenase (DHOD) catalyzes the only redox reaction in the pathway for pyrimidine biosynthesis. In this reaction, a proton is transferred from a carbon atom of the substrate to a serine residue, and a hydride is transferred from another carbon atom of the substrate to a cofactor. The deprotonation of the substrate is postulated to involve a proton relay mechanism along a hydrogen bonding pathway in the active site. In this paper, molecular dynamics simulations are used to identify and characterize potential hydrogen bonding pathways that could facilitate the redox reaction catalyzed by human DHOD. The observed pathways involve hydrogen bonding of the active base serine to a water molecule, which is hydrogen bonded to the substrate carboxylate group or a threonine residue. The threonine residue is positioned to enable proton transfer to another water molecule leading to the bulk solvent. The impact of mutating the active base serine to cysteine is also investigated. This mutation is found to increase the average donor-acceptor distances for proton and hydride transfer and to disrupt the hydrogen bonding pathways observed for the wild-type enzyme. These effects could lead to a significant decrease in enzyme activity, as observed experimentally for the analogous mutant in Escherichia coli DHOD.     

Computational modeling of the catalytic mechanism of human placental alkaline phosphatase (PLAP)

Alkaline phosphatases (APs) catalyze the hydrolysis and transphosphorylation of phosphate monoesters. Quantum mechanical, molecular dynamics, and molecular docking techniques were applied to computationally model the catalytic mechanism of human placental AP (PLAP). Kinetic and thermodynamic evaluations were performed for each reaction step. The functional significances of the more important residues within the active site were analyzed. The role of the metal ion at the metal binding site M3 was also examined. The calculated activation and reaction energy and free energy values obtained suggested the nucleophilic attack of the Ser92 alkoxide on the phosphorus atom of the substrate would be the rate-limiting step of the catalytic hydrolysis of alkyl phosphate monoesters by PLAP. The reactivities of the wild-type M3-Mg enzyme and the M3-Zn protein were compared, and the main difference observed was a change in the coordination number of the M3 metal for the M3-Zn enzyme. This modification in the active site structure lowered the free energy profile for the second chemical step of the catalytic mechanism (hydrolysis of the covalent phosphoserine intermediate). Consequently, a greater stabilization of the phosphoseryl moiety resulted in a small increment in the activation free energy of the phosphoserine hydrolysis reaction. These computational results suggest that the activation of APs by magnesium at the M3 site is caused by the preference of Mg(2+) for octahedral coordination, which structurally stabilizes the active site into a catalytically most active conformation. The present theoretical results are in good agreement with previously reported experimental studies.     

Synergistic Effect of Boron Nitride and Carbon Domains in Boron Carbide Nitride Nanotube Supported Single-Atom Catalysts for Efficient Nitrogen Fixation

Developing the low-cost and efficient single-atom catalysts (SACs) for nitrogen reduction reaction (NRR) is of great importance while remains as a great challenge. The catalytic activity, selectivity and durability are all fundamentally related to the elaborate coordination environment of SACs. Using first-principles calculations, we investigated the SACs with single transition metal (TM) atom supported on defective boron carbide nitride nanotubes (BCNTs) as NRR electrocatalysts. Our results suggest that boron-vacancy defects on BCNTs can strongly immobilize TM atoms with large enough binding energy and high thermal/structural stability. Importantly, the synergistic effect of boron nitride (BN) and carbon domains comes up with the modifications of the charge polarization of single-TM-atom active site and the electronic properties of material, which has been proven to be the essential key to promote N₂ adsorption, activation, and reduction. Specifically, six SACs (namely V, Mn, Fe, Mo, Ru, and W atoms embedded into defective BCNTs) can be used as promising candidates for NRR electrocatalysts as their NRR activity is higher than the state-of-the art Ru(0001) catalyst. In particular, single Mo atom supported on defective BCNTs with large tube diameter possesses the highest NRR activity while suppressing the competitive hydrogen evolution reaction, with a low limiting potential of −0.62 V via associative distal path. This work suggests new opportunities for driving NH₃ production by carbon-based single-atom electrocatalysts under ambient conditions.     

Atomic Ensemble Effects in Electrocatalysis: The Site‐Knockout Strategy

During an electrocatalytic reaction bonds are broken and formed, and this requires that the reactants, the intermediates formed at the elementary reaction steps, and the products interact with a given number of surface atoms of the catalyst. Modifying the number of groups with an adequate number of surface atoms in a suitable geometric arrangement for a determined reaction step to proceed may affect the activity and/or selectivity of the catalyst. Although separating purely geometric atomic ensemble effects from electronic effects is not straightforward, the insights extracted from a detailed investigation of atomic ensemble effects can have a profound impact in the determination of electrocatalytic reaction mechanisms and in the design of more active and more selective electrocatalysts. This Minireview illustrates, using cyanide‐modified Pt(111) electrodes as an archetype, how eliminating only one kind of site from the surface (the site‐knockout strategy) by means of a regular array of inert adsorbates can be used to successfully study atomic ensemble effects in electrocatalysis. The possible consequences for the design of more efficient and more selective electrocatalysts are also commented on.     

Single-atom Iron Catalyst with Biomimetic Active Center to Accelerate Proton Spillover for Medical-level Electrosynthesis of H2O2 Disinfectant

Electrosynthesis of H₂O₂ has great potential for directly converting O₂ into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical-level H₂O₂ production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (Fe_SA-NS/C). The newly-developed Fe_SA-NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H₂O₂ at a high current of 100 mA cm⁻² with a record high H₂O₂ selectivity of 90 %. An accumulated H₂O₂ concentration of 5.8 wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally-designed catalytic active center with the atomic Fe site stabilized by three-coordinated nitrogen atoms and one-sulfur atom (Fe-N₃S-C). It was further found that the replacement of one N atom with S atom in the classical Fe-N₄-C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H₂O₂ electrosynthesis.     

Amidation‐Dominated Re‐Assembly Strategy for Single‐Atom Design/Nano‐Engineering: Constructing Ni/S/C Nanotubes with Fast and Stable K‐Storage

An amidation‐dominated re‐assembly strategy is developed to prepare uniform single atom Ni/S/C nanotubes. In this re‐assembly process, a single‐atom design and nano‐structured engineering are realized simultaneously. Both the NiO₅ single‐atom active centers and nanotube framework endow the Ni/S/C ternary composite with accelerated reaction kinetics for potassium‐ion storage. Theoretical calculations and electrochemical studies prove that the atomically dispersed Ni could enhance the convention kinetics and decrease the decomposition energy barrier of the chemically‐absorbed small‐molecule sulfur in Ni/S/C nanotubes, thus lowering the electrode reaction overpotential and resistance remarkably. The mechanically stable nanotube framework could well accommodate the volume variation during potassiation/depotassiation process. As a result, a high K‐storage capacity of 608 mAh g^?1 at 100 mA g^?1 and stable cycling capacity of 330.6 mAh g^?1 at 1000 mA g^?1 after 500 cycles are achieved.     

Universal Sub-Nanoreactor Strategy for Synthesis of Yolk-Shell MoS2 Supported Single Atom Electrocatalysts toward Robust Hydrogen Evolution Reaction

The coordination structure determines the electrocatalytic performances of single atom catalysts (SACs), while it remains a challenge to precisely regulate their spatial location and coordination environment. Herein, we report a universal sub-nanoreactor strategy for synthesis of yolk-shell MoS₂ supported single atom electrocatalysts with dual-anchored microenvironment of vacancy-enriched MoS₂ and intercalation carbon toward robust hydrogen-evolution reaction. Theoretical calculations reveal that the “E-Lock” and “E-Channel” are conducive to stabilize and activate metal single atoms. A group of SACs is subsequently produced with the assistance of sulfur vacancy and intercalation carbon in the yolk-shell sub-nanoreactor. The optimized C−Co−MoS₂ yields the lowest overpotential (η₁₀=17 mV) compared with previously reported MoS₂-based electrocatalysts to date, and also affords a 5–9 fold improvement in activity even comparing with those as-prepared single-anchored analogues. Theoretical results and in situ characterizations unveil its active center and durability. This work provides a universal pathway to design efficient catalysts for electro-refinery.