Preparation of single atom catalysts for high sensitive gas sensing

Single atom catalysts(SACs)have garnered significant attention in the field of catalysis over the past decade due to their exceptional atom utilization efficiency and distinct physical and chemical properties.For the semiconductor-based electrical gas sensor,the core is the catalysis process of target gas molecules on the sensitive materials.In this context,the SACs offer great potential for highly sensitive and selective gas sensing,however,only some of the bubbles come to the surface.To facilitate practical applications,we present a comprehensive review of the preparation strategies for SACs,with a focus on overcoming the challenges of aggregation and low loading.Extensive research efforts have been devoted to investigating the gas sensing mechanism,exploring sensitive materials,optimizing device structures,and refining signal post-processing techniques.Finally,the challenges and future perspectives on the SACs based gas sensing are presented.

Exploring the Roles of Single Atom in Hydrogen Peroxide Photosynthesis

This comprehensive review provides a deep exploration of the unique roles of single atom catalysts(SACs)in photocatalytic hydrogen peroxide(H_(2)O_(2))production.SACs offer multiple benefits over traditional catalysts such as improved efficiency,selectivity,and flexibility due to their distinct electronic structure and unique properties.The review discusses the critical elements in the design of SACs,including the choice of metal atom,host material,and coordination environment,and how these elements impact the catalytic activity.The role of single atoms in photocatalytic H_(2)O_(2)production is also analysed,focusing on enhancing light absorption and charge generation,improving the migration and separation of charge carriers,and lowering the energy barrier of adsorption and activation of reactants.Despite these advantages,several challenges,including H_(2)O_(2)decomposition,stability of SACs,unclear mechanism,and low selectivity,need to be overcome.Looking towards the future,the review suggests promising research directions such as direct utilization of H_(2)O_(2),high-throughput synthesis and screening,the creation of dual active sites,and employing density functional theory for investigating the mechanisms of SACs in H_(2)O_(2)photosynthesis.This review provides valuable insights into the potential of single atom catalysts for advancing the field of photocatalytic H_(2)O_(2)production.

Aqueous Zinc Batteries with Ultra‑Fast Redox Kinetics and High Iodine Utilization Enabled by Iron Single Atom Catalysts

Rechargeable aqueous zinc iodine(ZnǀǀI_(2))batteries have been promising energy storage technologies due to low-cost position and constitutional safety of zinc anode,iodine cathode and aqueous electrolytes.Whereas,on one hand,the low-fraction utilization of electrochemically inert host causes severe shuttle of soluble polyiodides,deficient iodine utilization and sluggish reaction kinetics.On the other hand,the usage of high mass polar electrocatalysts occupies mass and volume of electrode materials and sacrifices device-level energy density.Here,we propose a“confinement-catalysis”host composed of Fe single atom catalyst embedding inside ordered mesoporous carbon host,which can effectively confine and catalytically convert I_(2)/I^(−)couple and polyiodide intermediates.Consequently,the cathode enables the high capacity of 188.2 mAh g^(−1)at 0.3 A g^(−1),excellent rate capability with a capacity of 139.6 mAh g^(−1)delivered at high current density of 15 A g^(−1)and ultra-long cyclic stability over 50,000 cycles with 80.5%initial capacity retained under high iodine loading of 76.72 wt%.Furthermore,the electrocatalytic host can also accelerate the I^(+)↔I_(2)conversion.The greatly improved electrochemical performance originates from the modulation of physicochemical confinement and the decrease of energy barrier for reversible I−/I_(2)and I_(2)/I^(+)couples,and polyiodide intermediates conversions.

Improved Plasmonic Hot‑Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad‑Spectrum Photocatalytic H_(2)Evolution

ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.

Nickel single atom overcoordinated active sites to accelerate the electrochemical reaction kinetics for Li-S cathode

Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.

Recent advances in regulating the performance of acid oxygen reduction reaction on carbon-supported non-precious metal single atom catalysts

Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single atom catalysts(SACs)have been identified as potential catalysts in the field.Great advance has been obtained in constructing diverse active sites of SACs for improving the performance and understanding the fundamental principles of regulating acid ORR performance.However,the ORR performance of SACs is still unsatisfactory.Importantly,microenvironment adjustment of SACs offers chance to promote the performance of acid ORR.In this review,acid ORR mechanism,attenuation mechanism and performance improvement strategies of SACs are presented.The strategies for promoting ORR activity of SACs include the adjustment of center metal and its microenvironment.The relationship of ORR performance and structure is discussed with the help of advanced experimental investigations and theoretical calculations,which will offer helpful direction for designing advanced SACs for ORR.

Asymmetric N,O-Coordinated Single Atomic Co Sites for Stable Lithium Metal Anodes

Lithium metal has been considered one of the most promising anodes for next-generation rechargeable batteries,but its practical application is largely hindered by the uncontrollable dendrite growth and infinite volume change.Here,inspired by superior catalytic effects of single-atom catalysts,carbon-supported single atomic Co with asymmetric N,O-coordination(Co-N/O)is developed for Li metal battery.Experimental results and theoretical calculations indicate that single atomic Co atoms with asymmetric N,O-coordination present enhanced binding ability toward Li in comparison with N-coordinated atomic Co site and isolated O site,enabling uniform Li plating/stripping.Moreover,the asymmetric N,O-coordination around Co atoms induces co-activation effects,lowering the energy barriers toward Li^(+)to Li^(0)conversion and largely promoting the deposition kinetics.When used as a Li deposition host,the Co-N/O achieves a high average coulombic efficiency of 98.6%at a current density of 1 mA cm^(-2)and a capacity of 2 mAh cm^(-2),long cycling life of 2000 h in symmetrical cells,and excellent rate performance(voltage hysteresis of 23 mV at 8 mA cm^(-2)).This work provides a comprehensive understanding of single atomic metals with asymmetric heteroatom coordination in the design of Li metal anode.

High throughput screening of single atomic catalysts with optimized local structures for the electrochemical oxygen reduction by machine learning

Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.

Regulating local coordination environment of Mg-Co single atom catalyst for improved direct methanol fuel cell cathode

Fuel cells operated with a reformate fuel such as methanol are promising power systems for portable electronic devices due to their high safety,high energy density and low pollutant emissions.However,several critical issues including methanol crossover effect,CO-tolerance electrode and efficient oxygen reduction electrocatalyst with low or non-platinum usage have to be addressed before the direct methanol fuel cells(DMFCs)become commercially available for industrial application.Here,we report a highly active and selective Mg-Co dualsite oxygen reduction reaction(ORR)single atom catalyst(SAC)with porous N-doped carbon as the substrate.The catalyst exhibits a commercial Pt/C-comparable half-wave potential of 0.806 V(versus the reversible hydrogen electrode)in acid media with good stability.Furthermore,practical DMFCs test achieves a peak power density of over 200 m W cm^(-2)that far exceeds that of commercial Pt/C counterpart(82 m W cm^(-2)).Particularly,the Mg-Co DMFC system runs over 10 h with negligible current loss under 10 M concentration methanol work condition.Experimental results and theoretical calculations reveal that the N atom coordinated by Mg and Co atom exhibits an unconventional d-band-ditto localized p-band and can promote the dissociation of the key intermediate*OOH into*O and*OH,which accounts for the near unity selective 4e-ORR reaction pathway and enhanced ORR activity.In contrast,the N atom in SAC–Co remains inert in the absorption and desorption of*OOH and*OH.This local coordination environment regulation strategy around active sites may promote rational design of high-performance and durable fuel cell cathode electrocatalysts.

Single atoms transferring between a magneto-optical trap and a far-off-resonance optical dipole trap

Based on our work on single cesium atoms trapped in a large-magnetic-gradient vapour-cell magneto-optical trap （MOT）, the signal-to-noise ratio （SNR） is remarkably improved. Also a far-off-resonance optical dipole trap （FORT） formed by a strongly-focused 1064 nm single frequency Nd：YVO4 laser beam is introduced. One cesium atom is prepared in the MOT, and then it can transfer successfully between the MOT and the FORT which is overlapped with the MOT. Utilizing the effective transfer, the lifetime of single atoms trapped in the FORT is measured to be 6.9± 0.3 s. Thus we provide a system where the atomic qubit can be coherently manipulated.

Electrochemical Kinetic Modulators in Lithium–Sulfur Batteries:From Defect-Rich Catalysts to Single Atomic Catalysts

Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.

Pt-Co single atom alloy catalysts: Accelerated water dissociation and hydrogen evolution by strain regulation

The alkaline hydrogen evolution reaction(HER) on Pt-based catalysts is largely limited by the slow water dissociation kinetics. Pt-based single atom alloy catalysts(SAAC) with water dissociation sites have been demonstrated as excellent alkaline HER catalysts. However, the regulation of their activity and stability at the atomic scale is still a great challenge. Herein, the kinetic and stability issues are successfully resolved via engineering the electronic structure of Pt-Co SAAC by Au-induced tensile strain. The atomic dispersion of Co into the Pt shell was confirmed by extended X-ray absorption fine structure and the electronic structure and catalytic HER performance was modulated by the tensile strain induced by the Pt shell thickness. An inverse volcano-type relation between HER activity and surface strain was found.Density functional theory(DFT) calculations reveal that the Au-induced tensile strain on Pt-Co shell can not only boost the adsorption and dissociation kinetics of water at Co site by upshifting the dband and promoting the electron transfer, but also downshift the d-band center of Pt in Pt-Co shell, leading to optimized H* adsorption/desorption. The champion catalyst provides an overpotential of only 14 m V at the current density of 10 mA cm^(-2). This work not only provides an effective strategy for the construction of single-atom alloy electrocatalysts for high performance toward alkaline HER but also sheds light on the understanding of the reaction mechanism at the atomic level.

Extending a release-and-recapture scheme to single atom optical tweezer for effective temperature evaluation

By recording the fluorescence fraction of the cold atoms remaining in the magneto-optical trap （MOT） as a function of the release time, the release-and-recapture （R＆R） method is utilized to evaluate the effective temperature of the cold atomic ensemble. We prepare a single atom in a large-magnetic-gradient MOT and then transfer the trapped single atom into a 1064-nm microscopic optical tweezer. The energy of the single atom trapped in the tweezer is further reduced by polarization gradient cooling （PGC） and the effective temperature is evaluated by extending the R-R technique to a single atom tweezer. The typical effective temperature of a single atom in the tweezer is improved from about 105 μK to about 17 μK by applying the optimum PGC phase.

Identification of the Intrinsic Dielectric Properties of Metal Single Atoms for Electromagnetic Wave Absorption

Atomically dispersed metals on N-doped carbon supports(M-N_(xCs)) have great potential applications in various fields.However,a precise understanding of the definitive relationship between the configuration of metal single atoms and the dielectric loss properties of M-N_(xCs) at the atomic-level is still lacking.Herein,we report a general approach to synthesize a series of three-dimensional(3D)honeycomb-like M-N_xC(M=Mn,Fe,Co,Cu,or Ni) containing metal single atoms.Experimental results indicate that 3D M-N_(xCs) exhibit a greatly enhanced dielectric loss compared with that of the NC matrix.Theoretical calculations demonstrate that the density of states of the d orbitals near the Fermi level is significantly increased and additional electrical dipoles are induced due to the destruction of the symmetry of the local microstructure,which enhances conductive loss and dipolar polarization loss of 3D M-N_(xCs),respectively.Consequently,these 3D M-N_(xCs) exhibit excellent electromagnetic wave absorption properties,outperforming the most commonly reported absorbers.This study systematically explains the mechanism of dielectric loss at the atomic level for the first time and is of significance to the rational design of high-efficiency electromagnetic wave absorbing materials containing metal single atoms.

Low temperature surface oxygen activation in crystalline MnO_(2) triggered by lattice confined Pd single atoms

Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.

Research progress of precise structural regulation of single atom catalyst for accelerating electrocatalytic oxygen reduction reaction

The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.

Fe–N–C single atom catalysts for the electrochemical conversion of carbon,nitrogen and oxygen elements

Single atom catalysts(SACs)are constituted by isolated active metal centers,which are heterogenized on inert supports such as graphene,porous carbon,and amorphous carbon.The thermal stability,electronic properties,and catalytic activities of the metal center can be controlled via manipulating the neighboring heteroatoms such as nitrogen,oxygen,and sulfur.Due to the atomical dispersion of the active catalytic centers,the amount of metal required for catalysis can be decreased.Furthermore,new possibilities are offered to easily control the selectivity of a given transformation process as well as to improve turnover frequencies and turnover numbers of target reactions.Among them,Fe–N–C single atom catalysts own special electronic structure,and have been widely used in many fields of electrocatalysis.This review aims to summarize the synthesis of Fe–N–C based on anchoring individual iron atoms on carbon/graphene.The spin-related properties of Fe–N–C catalysts are described,including the relation between spin and electron structure of Fe–N x as well as the coupling between electronic structure of Fe–N x and electronic(orbit)of CO_(2),N_(2)and O_(2).Next,mechanistic investigations conducted to un-derstand the specific behavior of Fe–N–C catalysts are highlighted,including C,N,O electro-reduction.Finally,some issues related to the future developments of Fe–N–C are put forward and corresponding feasible solutions are offered.

Recent progress of electrochemical reduction of CO_(2)by single atom catalysts

Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.

In situ surface-confined fabrication of single atomic Fe-N_(4) on N-doped carbon nanoleaves for oxygen reduction reaction

Controllable fabrication of Fe-N-C based single-atom catalysts(SACs)for enhanced electrocatalytic performance is highly desirable but still challenging.Here,an in situ surface-confined strategy was demonstrated for the synthesis of single atomic Fe-N_(4))on N-doped carbon nanoleaves(L-FeNC).The in situ generated Zn3[Fe(CN)6]2 could not only serve as a protection layer against collapse of nanoleaves but also provide abundant Fe source for the formation of Fe-N moieties during pyrolysis,leading to high surface area and high graphitization degree of L-FeNC simultaneously.Benefiting from abundant Fe-N_(4))active sites,enhanced mass and charge transfer,the as-prepared L-FeNC manifested a half-wave potential of 0.89 V for oxygen reduction reaction(ORR)in 0.1 M KOH.A maximum power density of 140 m W cm^(-2)and stable discharge voltage even after operation for 50,000 s have been demonstrated when the L-FeNC was used as air cathode for Zn-air battery.This work not only provided a unique surfaceconfined strategy for the synthesis of two-dimensional nanocarbons,but also demonstrated the significant benefit from rational design and engineering of Fe-N-C SACs,thus offering great opportunities for fabrication of efficient energy conversion and storage devices.

Isolated Co single atoms in nitrogen-doped graphene for aluminum-sulfur batteries with enhanced kinetic response

Al-S batteries are promising next generation energy storage devices due to their high theoretical energy density(1340 Wh kg^(-1)),low cost,and safe operation.However,the electrochemical performance of Al-S batteries suffers poor reversibility owing to slow kinetic processes determined by the difficulty of reversible conversion between Al and S.Here,we proposed a single-atom catalysts comprising Co atoms embedded in a nitrogen-doped graphene(Co NG)as an electrochemical catalyst in the sulfur cathode that renders a reduced discharge-charge voltage hysteresis and improved sulfur utilization in the cathode.The structural and electrochemical analyses suggest that the Co NG facilitated both the formation and oxidation of Al S;during the electrochemical reactions of the sulfur species.Consequently,the Co NG-S composite can deliver a considerably reduced voltage hysteresis of 0.76 V and a reversible specific capacity of 1631 m Ah g^(-1) at 0.2 A g^(-1) with a sulfur utilization of more than 97%.