Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Methanol steam reforming for hydrogen production driven by an atomically precise Cu catalyst

Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Atomically self-healing of structural defects in monolayer WSe_(2)

Minimizing disorder and defects is crucial for realizing the full potential of two-dimensional transition metal dichalcogenides(TMDs) materials and improving device performance to desired properties. However, the methods in defect controlcurrently face challenges with overly large operational areas and a lack of precision in targeting specific defects. Therefore,we propose a new method for the precise and universal defect healing of TMD materials, integrating real-time imaging withscanning transmission electron microscopy (STEM). This method employs electron beam irradiation to stimulate the diffusionmigration of surface-adsorbed adatoms on TMD materials grown by low-temperature molecular beam epitaxy (MBE),and heal defects within the diffusion range. This approach covers defect repairs ranging from zero-dimensional vacancydefects to two-dimensional grain orientation alignment, demonstrating its universality in terms of the types of samples anddefects. These findings offer insights into the use of atomic-level focused electron beams at appropriate voltages in STEMfor defect healing, providing valuable experience for achieving atomic-level precise fabrication of TMD materials.

Atomically dispersed Fe sites on hierarchically porous carbon nanoplates for oxygen reduction reaction

Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.

Atomically dispersed Ni electrocatalyst for superior urea-assisted water splitting

Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.

Atomically Dispersed Dual‑Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis

The real structure and in situ evolution of catalysts under working conditions are of paramount importance,especially for bifunctional electrocatalysis.Here,we report asymmetric structural evolution and dynamic hydrogen-bonding promotion mechanism of an atomically dispersed electrocatalyst.Pyrolysis of Co/Ni-doped MAF-4/ZIF-8 yielded nitrogen-doped porous carbons functionalized by atomically dispersed Co–Ni dual-metal sites with an unprecedented N8V4 structure,which can serve as an efficient bifunctional electrocatalyst for overall water splitting.More importantly,the electrocatalyst showed remarkable activation behavior due to the in situ oxidation of the carbon substrate to form C–OH groups.Density functional theory calculations suggested that the flexible C–OH groups can form reversible hydrogen bonds with the oxygen evolution reaction intermediates,giving a bridge between elementary reactions to break the conventional scaling relationship.

Atomically precise gold nanoclusters for healthcare applications

The potential application of gold nanoparticles(GNPs)in biomedicine has been extensively reported.However,there is still too much puzzle about their real face and potential health risks in comparison with the commercial drug molecules.The emergence of atomically precise gold nanoclusters(APGNCs)provides the opportunity to address the puzzle due to their ultrasmall size,defined molecular formula,editable surface engineering,available structures and unique physicochemical properties including excellent biocompatibility,strong luminescence,enzyme-like activity and efficient renal clearance,et al.Recently,these advantages of APGNCs also endow them promising performances in healthcare such as bioimaging,drug delivery,antibacterial and cancer therapy.Especially,their clear composition and structures like the commercial drug molecules facilitate the study of their functions and the structure-activity relationship in healthcare,which is essential for the guided design of APGNC nanomedicine.Therefore,this review will focus the advantages and recent progress of APGNCs in health care and envision their prospects for the future.

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase‑Like Activity for Sensitive Biosensing

Although nanozymes have been widely developed,accurate design of highly active sites at the atomic level to mimic the electronic and geometrical structure of enzymes and the exploration of underlying mechanisms still face significant challenges.Herein,two functional groups with opposite electron modulation abilities(nitro and amino)were introduced into the metal–organic frameworks(MIL-101(Fe))to tune the atomically dispersed metal sites and thus regulate the enzymelike activity.Notably,the functionalization of nitro can enhance the peroxidase(POD)-like activity of MIL-101(Fe),while the amino is poles apart.Theoretical calculations demonstrate that the introduction of nitro can not only regulate the geometry of adsorbed intermediates but also improve the electronic structure of metal active sites.Benefiting from both geometric and electronic effects,the nitro-functionalized MIL-101(Fe)with a low reaction energy barrier for the HO*formation exhibits a superior POD-like activity.As a concept of the application,a nitro-functionalized MIL-101(Fe)-based biosensor was elaborately applied for the sensitive detection of acetylcholinesterase activity in the range of 0.2–50 mU mL−1 with a limit of detection of 0.14 mU mL−1.Moreover,the detection of organophosphorus pesticides was also achieved.This work not only opens up new prospects for the rational design of highly active nanozymes at the atomic scale but also enhances the performance of nanozyme-based biosensors.

Atomically Dispersed Transition Metal-Nitrogen-Carbon Bifunctional Oxygen Electrocatalysts for Zinc-Air Batteries:Recent Advances and Future Perspectives

Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

A facile sulfur-assisted method to synthesize porous alveolate Fe/g-C3N4 catalysts with ultra-small cluster and atomically dispersed Fe sites

Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.

Cation-vacancy induced Li+ intercalation pseudocapacitance at atomically thin heterointerface for high capacity and high power lithium-ion batteries

It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully create Co vacancies at the interface of atomically thin Co_(3−x)O_(4)/graphene@CNT heterostructure for high-energy/power lithium storage. The creation of Co-vacancies in the sample was confirmed by high-resolution scanning transmission electron microscope (HRSTEM), X-ray photoelectron spectroscopy (XPS) and electron energy loss near-edge structures (ELNES). The obtained Co_(3−x)O_(4)/graphene@CNT delivers an ultra-high capacity of 1688.2 mAh g^(−1) at 0.2 C, excellent rate capability of 83.7% capacity retention at 1 C, and an ultralong life up to 1500 cycles with a reversible capacity of 1066.3 mAh g^(−1). Reaction kinetic study suggests a significant contribution from pseudocapacitive storage induced by the Co-vacancies at the Co_(3−x)O_(4)/graphene@CNT interface. Density functional theory confirms that the Co-vacancies could dramatically enhance the Li adsorption and provide an additional pathway with a lower energy barrier for Li diffusion, which results in an intercalation pseudocapacitive behavior and high-capacity/rate energy storage.

Band gap engineering of atomically thin two-dimensional semiconductors

Atomically thin two-dimensional （2D） layered materials have potential applications in nanoelectronics, nanophoton- ics, and integrated optoelectronics. Band gap engineering of these 2D semiconductors is critical for their broad applications in high-performance integrated devices, such as broad-band photodetectors, multi-color light emitting diodes （LEDs）, and high-efficiency photovoltaic devices. In this review, we will summarize the recent progress on the controlled growth of composition modulated atomically thin 2D semiconductor alloys with band gaps tuned in a wide range, as well as their induced applications in broadly tunable optoelectronic components. The band gap engineered 2D semiconductors could open up an exciting opportunity for probing their fundamental physical properties in 2D systems and may find diverse applications in functional electronic/optoelectronic devices.

Atomically flat surface preparation for surface-sensitive technologies

Surface-sensitive measurements are crucial to many types of researches in condensed matter physics.However,it is difficult to obtain atomically flat surfaces of many single crystals by the commonly used mechanical cleavage.We demonstrate that the grind-polish-sputter-anneal method can be used to obtain atomically flat surfaces on topological materials.Three types of surface-sensitive measurements are performed on CoSi(001)surface with dramatically improved quality of data.This method extends the research area of surface-sensitive measurements to hard-to-cleave alloys,and can be applied to irregular single crystals with selective crystalline planes.It may become a routine process of preparing atomically flat surfaces for surface-sensitive technologies.

Atomically dispersed Fe atoms anchored on N-doped carbon hollow nanospheres boost the electrocatalytic performance for oxygen reduction reaction

Oxygen reduction reaction(ORR)is the key reaction at the cathode of proton exchange membrane fuel cells(PEMFCs)and metal-air batteries(1)To address the challenges associated with Pt-based electrocatalysts having prominent activity for ORR,e.g.scarce abundance,prohibitive cost,poor stability,and vulnerability to reaction intermediates,it is necessary to explore other cost-effective ORR electrocatalysts with competitive or even superior performance to promote the commercialization of the energy conversion devices.

Enhancing sintering resistance of atomically dispersed catalysts in reducing environments with organic monolayers

Atomically dispersed precious metal catalysts maximize atom efficiency and exhibit unique reactivity.However,they are susceptible to sintering.Catalytic reactions occurring in reducing environments tend to result in atomically dispersed metals sintering at lower temperatures than in oxidative or inert atmospheres due to the formation of mobile metal-H or metal-CO complexes.Here,we develop a new approach to mitigate sintering of oxide supported atomically dispersed metals in a reducing atmosphere using organophosphonate self-assembled monolayers(SAMs).We demonstrate this for the case of atomically dispersed Rh on Al_(2)O_(3) and TiO_(2) using a combination of CO probe molecule FTIR,temperature programmed desorption,and alkene hydrogenation rate measurements.Evidence suggests that SAM functionalization of the oxide provides physical diffusion barriers for the metal and weakens the interactions between the reducing gas and metal,thereby discouraging the adsorbate-promoted diffusion of metal atoms on oxide supports.Our results show that support functionalization by organic species can provide improved resistance to sintering of atomically dispersed metals with maintained catalytic reactivity.

Activating Inert Sites in Cobalt Silicate Hydroxides for Oxygen Evolution through Atomically Doping

Metal silicate hydroxides have been recognized as efficient oxygen evolution reaction(OER)electrocatalysts,yet tailoring of their intrinsic activity remains confused.Herein,Fe had been incorporated into cobalt silicate hydroxide nanosheets and the resulted material achieves a competitive OER catalytic activity.It is found that the doping state obviously affects the electrical transport property.Specifically,highly dispersed Fe atoms(low-concentration Fe doping)trigger slight electron transfer to Co atoms while serried Fe(highconcentration Fe doping)attract vast electrons.By introducing 6 at.%Fe doping,partial relatively inert Co sites are activated by atomically dispersed Fe,bearing an optimal metal 3d electronic occupation and adsorption capacity to oxygen intermediate.The introduced Co-O-Fe unit trigger the p-donation effect and decrease the number of electrons in p*-antibonding orbitals,which enhance the Fe-O covalency and the structural stability.As a result,the sample delivers a low overpotential of 293 mV to achieve a current density of 10 mA cm^(-2).This work clarifies the superiority of atomically dispersed doping state,which is of fundamental interest to the design of doped catalyst.

Atomically precise metal nanoclusters for(photo)electroreduction of CO_(2): Recent advances, challenges and opportunities

To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO_(2) RR) is involved with multiple electrons and multiple products,plus the complexity of the surface chemical environment of the catalyst,it is extremely challenging to establish the structure/function relationship.Atomically precise metal nanoclusters(NCs),with crystallographically resolved structure,molecule-like characters and strong quantum confinement effects,have been emerging as a new type of catalyst for CO_(2) RR,and more importantly,they can provide an ideal platform to unravel the comprehensive mechanistic insights and establish the structure/function relationship eventually.In this review,the recent advances regarding employing molecular metal NCs with well-defined structure including Au NCs,Au-based alloy NCs,Ag NCs,Cu NCs for CO_(2) RR and relevant mechanistic studies are discussed,and the opportunities and challenges are proposed at the end for paving the development of CO_(2) RR by using atomically precise metal NCs.