The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing mul...The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site−1 at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.展开更多
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 ...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.展开更多
Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are...Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates,which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts.In this work,Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)_(2)nanosheet arrays.Based on the X-ray absorption fine structure analysis and first-principles calculations,Pt SA was bonded with Ni sites of amorphous Ni(OH)_(2),rather than conventional O sites,resulting in negatively charged Pt^(δ-).In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms,which were the essential intermediate for alkaline hydrogen evolution reaction.The hydrogen spillover process was revealed from amorphous Ni(OH)_(2)that effectively cleave the H-O-H bond of H_(2)O and produce H atom to the Pt SA sites,leading to a low overpotential of 48 mV in alkaline electrolyte at-1000 mA cm^(-2)mg^(-1)_(Pt),evidently better than commercial Pt/C catalysts.This work provided new strategy for the control-lable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.展开更多
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...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.展开更多
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 ...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.展开更多
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,b...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.展开更多
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 a...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.展开更多
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 ato...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 utiliza...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.展开更多
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...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.展开更多
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,su...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.展开更多
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 demons...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.展开更多
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...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.展开更多
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 s...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.展开更多
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 suppor...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.展开更多
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 ene...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.展开更多
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...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.展开更多
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 va...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.展开更多
基金supported in China by the Natural Science Funds for Distinguished Young Scholar of Heilongjiang Province(No.JC2018004).
文摘The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site−1 at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.
基金supported by the National Key Research and Development Program of China(2022YFB3204700)the National Natural Science Foundation of China(52122513)+2 种基金the Natural Science Foundation of Heilongjiang Province(YQ2021E022)the Natural Science Foundation of Chongqing(2023NSCQ-MSX2286)the Fundamental Research Funds for the Central Universities(HIT.BRET.2021010)。
文摘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.
基金supported by National Natural Science Foundation of China(52373221,U1910208,52250119)the National Key R&D Program of China(2020YFA0710403)the Scientific Research Fund of Hunan Provincial Education Department(NO.23B0114).
文摘Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates,which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts.In this work,Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)_(2)nanosheet arrays.Based on the X-ray absorption fine structure analysis and first-principles calculations,Pt SA was bonded with Ni sites of amorphous Ni(OH)_(2),rather than conventional O sites,resulting in negatively charged Pt^(δ-).In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms,which were the essential intermediate for alkaline hydrogen evolution reaction.The hydrogen spillover process was revealed from amorphous Ni(OH)_(2)that effectively cleave the H-O-H bond of H_(2)O and produce H atom to the Pt SA sites,leading to a low overpotential of 48 mV in alkaline electrolyte at-1000 mA cm^(-2)mg^(-1)_(Pt),evidently better than commercial Pt/C catalysts.This work provided new strategy for the control-lable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.
基金This work was financially supported by the Guangdong Basic and Applied Basic Research Foundation(2020A1515010982)the National Natural Science Foundation of China(21805191)+2 种基金Shenzhen Science and Technology Program(JCYJ20210324094000001,20190808142001745,20200812122947002)Shenzhen Peacock Plan(20210802524B and 20180921273B)the Australian Research Council(FT200100015)。
文摘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.
基金supported by the National Key Research and Development Project(2020YFC1521900 and 2020YFC1521904)the Shaanxi Provincial Science Foundation(2021GXLH-01-11)+1 种基金We would also like to thank National Natural Science Foundation of China(52202299)Analytical&Testing Center of Northwestern Polytechnical University(2022T006).
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.51871078 and 52071119)Interdisciplinary Research Foundation of HIT(Grant No.IR2021208)+1 种基金State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS38)Heilongjiang Science Foundation(No.LH2020B006).
文摘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.
基金financial support from the National Natural Science Foundation of China(21878270,21878267,21922811,21978258 and 21961160742)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)+3 种基金the Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Fundamental Research Funds for the Central Universities(2020XZZX002-09)the Startup Foundation for Hundred-Talent Program of Zhejiang Universitythe Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10)。
文摘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.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U20A20280)the Postgraduate Scientific Research Innovation Project of Hunan Province(CX20210171)。
文摘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.
基金the funding support from the National Natural Science Fund for Distinguished Young Scholars(52125103)the National Natural Science Foundation of China(52071041,12074048 and 12147102)+2 种基金Chongqing Natural Science Foundation(cstc2020jcyj-msxm X0777 and cstc2020jcyj-msxm X0796)Science Foundation of Donghai Laboratory(DH-2022KF0307)the Fundamental Research Funds for the Central Universities(106112016CDJZR308808)。
文摘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.
基金supported by the Ministry of Education,Singapore,under its MOE tier2 grant MOE2019-T2-1-181.
文摘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.
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the Beijing Natural Science Foundation (Z210016)the National Natural Science Foundation of China (21935001)。
文摘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.
基金supported by the National Natural Science Foundation of China (Grant Nos 60578018 and 10434080)the project for excellent research team from the National Natural Science Foundation of China (Grant No 60821004)+4 种基金the Program for New Century Excellent Talents of the Education Ministry of China (Grant No NCET-07-0524)the State Basic Key Research Program of China (Grant No 2006CB921102)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No 20070108003)the Natural Science Foundation of Shanxi Province,China (Grant No 2007011003)the Scientific Research Funds for Returned Scholars Abroad of Shanxi Province,China
文摘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.
基金fellowship funding supported by the Alexander von Humboldt Foundationfinancial funding support from the Natural Science Foundation of Jiangsu Province(BK.20210636)Natural Science Foundation of China(21773294 and 21972164)。
文摘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.
基金supported by the National Natural Science Foundation of China (U2032151)the National Key R&D Program of China (2018YFB1502600)+1 种基金the Basic Research and Applied Basic Research Foundation of Guangzhou (B3210580)the Natural Science Foundation of Guangdong Province (B6211050)。
文摘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.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.60978017,61078051 and 10974125)the Science Fund for Creative Research Groups of the National Natural Science Foundation of China (Grant No.60821004)the Program for New Century Excellent Talents of Ministry of Education of China (Grant No.NCET-07-0524)
文摘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.
基金financial supports from the NNSF of China(Grant No.51972077)the Fundamental Research Funds for the Central Universities(Grant No.3072020CF2518,3072020CFT2505+1 种基金3072021CFT2506,3072021CF2523 and 3072021CF2524)Heilongjiang Touyan Innovation Team Program.
文摘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.
基金X.Liao gratefully thanks the support from the National Natural Science Foundation of China(No.21706216)the Sichuan Science and Technology Program(2020YFG0162)+3 种基金the Young Scholar Project in Xihua University.X.Li acknowledges the support from the National Natural Science Foundation of China(No.21972163)the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program,and the Development Fund for Shanghai Talents.Z.Jiang acknowledges financial support from the Joint Fund U1732267.M.Y.thanks the JSPS KAKENHI(No.JP 18H05517)JST-CREST for financial supports,and Riken SPring-8 for the approval of the SRXRD measurement(20190028)EXAFS studies were carried out at the BL14W1 beamline in the Shanghai Synchrotron Radiation Facility[63],Shanghai Institute of Applied Physics,China(16ssr-f00787).X.Liao gratefully thanks the useful discussion with Ya Wang and Yanmin Liu.
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.22108306)the Taishan Scholars Program of Shandong Province(Grant No.tsqn201909065)the Shandong Provincial Natural Science Foundation(Grant Nos.ZR2021YQ15,ZR2020QB174)。
文摘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.
基金We are grateful for the financial support from National Natural Sci-ence Foundation of China(No.21974103)and the start-up funds of Wuhan University.
文摘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.
文摘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.