Current Status and Perspectives of Dual-Atom Catalysts Towards Sustainable Energy Utilization

The exploration of sustainable energy utilization requires the imple-mentation of advanced electrochemical devices for efficient energy conversion and storage,which are enabled by the usage of cost-effective,high-performance electro-catalysts.Currently,heterogeneous atomically dispersed catalysts are considered as potential candidates for a wide range of applications.Compared to conventional cata-lysts,atomically dispersed metal atoms in carbon-based catalysts have more unsatu-rated coordination sites,quantum size effect,and strong metal-support interactions,resulting in exceptional catalytic activity.Of these,dual-atomic catalysts(DACs)have attracted extensive attention due to the additional synergistic effect between two adja-cent metal atoms.DACs have the advantages of full active site exposure,high selectiv-ity,theoretical 100%atom utilization,and the ability to break the scaling relationship of adsorption free energy on active sites.In this review,we summarize recent research advancement of DACs,which includes(1)the comprehensive understanding of the synergy between atomic pairs;(2)the synthesis of DACs;(3)characterization meth-ods,especially aberration-corrected scanning transmission electron microscopy and synchrotron spectroscopy;and(4)electrochemical energy-related applications.The last part focuses on great potential for the electrochemical catalysis of energy-related small molecules,such as oxygen reduction reaction,CO_(2) reduction reaction,hydrogen evolution reaction,and N_(2) reduction reaction.The future research challenges and opportunities are also raised in prospective section.

Engineering of geometrical configurations in dual-atom catalysts for electrocatalytic applications

Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,but in-depth understanding the relationship between geometrical configurations and metal-metal interaction mechanisms for designing targeted DACs is still required.In this review,the recent progress in engineering of geometrical configurations of DACs is systematically summarized.Based on the polarity of geometrical configuration,DACs can be classified into two different types that are homonuclear and heteronuclear DACs.Furthermore,with regard to the geometrical configurations of the active sites,homonuclear DACs are identified into adjacent and bridged configurations,and heteronuclear DACs can be classified into adjacent,bridged,and separated configurations.Subsequently,metal-metal interactions in DACs with different geometrical configurations are introduced.Additionally,the applications of DACs in different electrocatalytic reactions are discussed,including the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and other catalysis.Finally,the future challenges and perspectives for advancements in DACs are high-lighted.This review aims to provide inspiration for the design of highly effcient DACs towards energy relatedapplications.

A post-modification strategy to precisely construct dual-atom sites for oxygen reduction electrocatalysis

Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.

Oxygen Reduction Reaction Activity of Fe-based Dual-Atom Catalysts with Different Local Configurations via Graph Neural Representation

The performance of proton exchange membrane fuel cells depends heavily on the oxygen reduction reaction(ORR)at the cathode,for which platinum-based catalysts are currently the standard.The high cost and limited availability of platinum have driven the search for alternative catalysts.While FeN4 single-atom catalysts have shown promising potential,their ORR activity needs to be further enhanced.In contrast,dual-atom catalysts(DACs)offer not only higher metal loading but also the ability to break the ORR scaling relations.However,the diverse local structures and tunable coordination environments of DACs create a vast chemical space,making large-scale computational screening challenging.In this study,we developed a graph neural network(GNN)-based framework to predict the ORR activity of Fe-based DACs,effectively addressing the challenges posed by variations in local catalyst structures.Our model,trained on a dataset of 180 catalysts,accurately predicted the Gibbs free energy of ORR intermediates and overpotentials,and identified 32 DACs with superior catalytic activity compared to FeN4 SAC.This approach not only advances the design of high-performance DACs,but also offers a powerful computational tool that can significantly reduce the time and cost of catalyst development,thereby accelerating the commercialization of fuel cell technologies.

MOF-assisted Synthesis of Dual-atom Palladium Catalysts for Acetylene Semi-hydrogenation

The selective removal of trace acetylene in ethylene feed gas is of great significance in the petrochemicalindustry;however, there are still challenges in designing and developing high-performance catalysts. Here, a MOFassistedencapsulation strategy was adopted for the precise synthesis of diatomic Pd2 sites on a ZnO support. When usedfor the acetylene semi-hydrogenation reaction, the dual-atom Pd2-ZnO catalyst exhibited improved catalytic performance,achieving complete conversion of acetylene at 125 °C with an 89% selectivity to ethene, as compared to Pd single-atom andnanoparticles. This enhancement was mainly attributed to the catalyst’s ability to dissociate H2 and facilitate the desorptionof intermediate C2H4. Moreover, the strong interaction between the support and the diatomic Pd sites was responsible for thecatalyst’s excellent stability during the long-term reaction.

Tuning dual-atom mediator toward high-rate bidirectional polysulfide conversion in Li-S batteries

An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric dispersion and sole electronic configuration limit the catalytic benefits and curtail the cell performance.Here,we propose a class of dual-atom catalytic moieties comprising hetero-or homo-atomic pairs anchored on N-doped graphene(NG)to unlock the liquid–solid redox puzzle of sulfur,readily realizing Li-S full cell under high-rate-charging conditions.As for Fe-Ni-NG,in-depth experimental and theoretical analysis reveal that the hetero-atomic orbital coupling leads to altered energy levels,unique electronic structures,and varied Fe oxidation states in comparison with homo-atomic structures(FeFe-NG or Ni-Ni-NG).This would weaken the bonding energy of polysulfide intermediates and thus enable facile electrochemical kinetics to gain rapid liquid-solid Li_(2)S_(4)?Li_(2)S conversion.Encouragingly,a Li-S battery based on the S@Fe-Ni-NG cathode demonstrates unprecedented fast-charging capability,documenting impressive rate performance(542.7 mA h g^(-1)at 10.0 C)and favorable cyclic stability(a capacity decay of 0.016%per cycle over 3000 cycles at 10.0 C).This finding offers insights to the rational design and application of dual-atom mediators for Li-S batteries.

1+1>2: Learning from the interfacial modulation on single-atom electrocatalysts to design dual-atom electrocatalysts for dinitrogen reduction

Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.

An interesting synergistic effect of heteronuclear dual-atom catalysts for hydrogen production:Offsetting or promoting

To elucidate the synergistic effect of dual-atom catalysts(DACs)at the microscopic level,we propose and construct a prototype heteronuclear system,CuNi/TiO_(2),in which the two elements of a pair have significantly different d electron-donating abilities,as a piece in the puzzle.Using density functional theory calculations,we investigate charge-dependent configurations of Cu-Ni dimers anchored on TiO_(2)by the mixing of individual constituent atoms.The d electron-donating ability determines deposition sequence and position of transition metal atoms on oxides,establishing dimer pattern and metal-support interactions.The interaction between Cu and Ni,beyond the coordination environment,predominately contributes to the synergistic effect.A complex adsorption-reduction behavior of H species on CuNi/TiO_(2)is observed.The reaction mechanism and catalytic activity of CuNi/TiO_(2)for hydrogen production are explored.At room temperature and high H coverages,CuNi/TiO_(2)shows better performance and efficiency than Ni1/TiO_(2).Our findings provide a new understanding of the synergistic effect on structure-activity relationships of supported dimers,which would be beneficial in the future design of various DACs or even atomically dispersed metal catalysts.

Theoretical screening of cooperative N-bridged dual-atom sites for efficient electrocatalytic nitrogen reduction with remolding insight

The electrocatalytic nitrogen reduction reaction(e-NRR)is a promising alternative method for the Haber–Bosch process.However,it still faces many challenges in searching for high activity,stability,and selectivity catalysts and ascertaining the catalytic mechanism with complete insight.Here,a series of graphene-based N-bridged dual-atom catalysts(M1-N-M2/NC)are systematically investigated via first-principle calculation and a high-throughput screening strategy.The result unveils that N_(2) adsorption on M1-N-M2/NC in bridge-on adsorption mode can effectively break the scaling relationship on single-atom catalysts(SACs).Moreover,V-N-Ru/NC and V-N-Os/NC are systematically screened out as promising e-NRR catalysts,with extremely low limiting potentials of-0.20 and-0.18 V,respectively.Furthermore,the adsorption site competition between*N_(2) and*H,as well as the competitive twin reactions of hydrogen evolution reaction(HER)on intermediates(N_(n)H_(m))during the e-NRR process,is systematically evaluated to form a remodeling insight for the reactions in mechanism,and the e-NRR of new proposed dual-atom catalysts(DACs)is strategically optimized for its high-efficiency performance potential via our remolding insight in e-NRR mechanism.This work provides new ideas and insights for the design and mechanism of e-NRR catalysts and an effective strategy for rapidly screening highly efficient e-NRR catalysts.

Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM2/NC, TM=Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir2/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM2/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.

Advanced dual-atom catalysts for rechargeable zinc-air batteries

Rechargeable zinc-air batteries(ZABs)have gained extensive research attention as a promising sustainable energy technology due to their considerable theoretical specific energy density,low toxicity,abundant availability,and robust safety features.However,the practical implementation of ZABs still faces challenges,primarily attributed to the sluggish kinetics of oxygen-involved reactions,including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)during the discharge and charge process.Therefore,searching for efficient bifunctional oxygen electrocatalysts is crucial to address these challenges.Dual-atom catalysts(DACs),an extension of singleatom catalysts(SACs),exhibit flexible architectures that allow for the combination of homogeneous and/or heterogeneous active sites,making them highly attractive for improving bifunctional activity.In this review,we first introduce the basic framework of ZABs and the structural characteristics of DACs.Subsequently,we organize the research progress on applying DACs in liquid and solid-state ZABs and elaborate on their unique catalytic mechanism.Finally,we highlight the challenges and future research directions for further innovation of DACs in ZABs.In summary,this review highlights the advantages of DACs compared with SACs used as bifunctional oxygen electrocatalysts and provides a reference for the broad applications of DACs in energy conversion and storage.

Dual-atom catalysts:controllable synthesis and electrocatalytic applications

Electrocatalysis,as the nexus for energy storage and environmental remediation,requires developing low-cost and highperforming heterogeneous catalysts.Compared with the single atom catalysts(SACs),dual-atom catalysts(DACs)are attracting ever-increasing interest due to their higher metal loading,more versatile active sites and unique reactivity.However,controlled synthesis of DACs remains a great challenge,and their electrocatalytic applications are still in infancy.This review first discusses the synthesis of DACs by highlighting several synthetic strategies.Subsequently,we exemplify the unique reactivities of DACs in electrocatalytic applications including water splitting,oxygen reduction,carbon dioxide reduction and nitrogen reduction.The structure-activity relations of DACs are specifically discussed in comparison with that of SACs,on the basis of experimental and theoretical studies.Finally,the opportunities and challenges of DACs are summarized in terms of rational design,controlled synthesis,characterization,and applications.

Rational design of graphyne-based dual-atom site catalysts for CO oxidation

There are increasing concerns about the environmental impact of rising atmospheric carbon monoxide concentrations,thus it is necessary to develop new catalysts for efficient CO oxidation.Based on first-principles calculations,the potential ofγ-graphyne(GY)as substrate for metals in the 4th and 5th periods under single-atom and dual-atoms concentration modes has been systematically investigated.It was found that single-atom Co,Ir,Rh,and Ru could effectively oxidate CO molecules,especially for single Rh.Furthermore,proper atoms concentration could boost the CO oxidation activity by supplying more reaction centers,such as Rh^(2)/GY.It was determined that two Rh atoms in Rh^(2)/GY act different roles in the catalytic reaction:one structural and another functional.Screening tests suggest that substituting the structural Rh atom in the center of acetylenic ring by Co or Cu atom is a possible way to maintain the reaction performance while reducing the noble metal cost.This systemic investigation will help in understanding the fundamental reaction mechanisms on GY-based substrates.We emphasize that properly exposed frontier orbital of functional metal atom is crucial in adsorption configuration as well as entire catalytic performance.This study constructs a workflow and provides valuable information for rational design of CO oxidation catalysts.

Regulating the Oxygen Affinity of Single Atom Catalysts by Dual-atom Design for Enhanced Oxygen Reduction Reaction Activity

This work chooses Cu/Fe single-atom catalysts(SACs)with weak/strong oxygen affinity to clarify the effect of dual-atom configuration on oxygen reduction reaction(ORR)performance based on density functional theory(DFT)calculations.The stability and ORR activity of single or dual Cu/Fe atomic sites anchored on nitrogen-doped graphene sheets(Cu-N4-C,Cu2-N_(6)-C,Fe-N4-C,and Fe_(2)-N_(6)-C)are investigated,and the results indicate the dual-atom catalysts(Cu2-N_(6)-C and Fe_(2)-N_(6)-C)are thermodynamically stable enough to avoid sintering and aggregation.Compared with single-atom active sites of Cu-N4-C,which show weak oxygen affinity and poor ORR performance with a limiting potential of 0.58 V,the dual-Cu active sites of Cu2-N_(6)-C exhibit enhanced ORR activity with a limiting potential up to 0.87 V due to strengthened oxygen affinity.Interestingly,for Fe SACs with strong oxygen affinity,the DFT results show that the dual-Fe sites stabilize the two OH*ligands structure[Fe_(2)(OH)2-N_(6)-C],which act as the active sites during ORR process,resulting in greatly improved ORR performance with a limiting potential of 0.90 V.This study suggests that the dual-atom design is a potential strategy to improve the ORR performance of SACs,in which the activity of the single atom active sites is limited with weak or strong oxygen affinity.

Spatial confinement of zeolitic imidazolate framework deposits by porous carbon nanospheres for dual-atom catalyst towards high-performance oxygen reduction reaction

Dual atom catalysts(DACs),are promising electrocatalysts for oxygen reduction reaction(ORR)on account of the potential dual-atom active sites for the optimized adsorption of catalytic intermediates and the lower reaction energy barriers.Herein,spatial confinement strategy to fabricate DACs with well-defined Fe,Co dual-atom active site is proposed by implanting zeolitic imidazolate frameworks inside the pores of highly porous carbon nanospheres(Fe/Co-SAs-Nx-PCNSs).The atomically dispersed dual-atom active sites facilitate the adsorption/desorption of intermediates.Furthermore,the spatial confinement effect protects metal atoms aggregating.Benefiting from the rich accessible dual-atom active sites and boosted mass transport,we achieve remarkable ORR performance with half-wave potential up to 0.91 and 0.8 V(vs.reversible hydrogen electrode(RHE)),and long-term stability up to 10 h in both alkaline and acidic electrolytes.The remarkably enhanced ORR catalytic property of our as-developed DACs is in the rank of excellence for 1%.The as-developed rechargeable Zn-air battery(ZAB)with Fe/Co-SAs-Nx-PCNSs air cathode delivers ultrahigh power density of 216 mW·cm^(−2),outstanding specific capacity of 813 mAh·g^(−1),and promising cycling operation durability over 160 h.The flexible Zn-air battery also exhibits excellent specific capacity,cycling stability,and flexibility performance.This work opens up a new pathway for the multiscale design of efficient electrocatalysts with atomically dispersed multiple active sites.

Synergy of heterogeneous Co/Ni dual atoms enabling selective C-O bond scission of lignin coupling with in-situ N-functionalization

Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.

双源CT电子密度/有效原子序数(Rho/Z)在孤立性肺结节中的诊断价值

目的:探讨双源CT(DSCT)双能量技术电子密度/有效原子序数(Rho/Z)在孤立性肺结节中良恶性的诊断价值。方法:回顾性收集130例双能量平扫及增强的孤立性肺结节患者,其中恶性组68例,良性组62例,利用Rho/Z应用程序对平扫及增强静脉期图像进行评估,记录参数Rho、Z和双能量指数(DEI)值,比较两组间的差异,对于有统计学差异的参数,将绘制受试者工作特性(ROC)曲线,以评估其诊断效能。结果:平扫时,恶性组Rho (31.1±22.33)HU明显高于良性组(24.69±20.91)HU,两组之间存在显著统计学差异(P=0.003<0.05),Z与DEI在两组间差异无统计学意义(P>0.05);增强静脉期,恶性组Rho (35.3±20.85)HU明显高于良性组(24.73±17.93)HU,两组之间可见显著统计学差异(P=0.001<0.05),Z与DEI在两组间差异均无统计学意义(P>0.05)。在两组的鉴别诊断中,平扫及增强静脉期Rho的ROC曲线下面积分别为0.652、0.696。结论:DSCT双能量技术Rho/Z有一定特征,有助于孤立性肺结节的诊断。

Dual‑Atom Nanozyme Eye Drops Attenuate Inflammation and Break the Vicious Cycle in Dry Eye Disease

Dry eye disease(DED)is a major ocular pathology worldwide,causing serious ocular discomfort and even visual impairment.The incidence of DED is gradually increasing with the highfrequency use of electronic products.Although inflammation is core cause of the DED vicious cycle,reactive oxygen species(ROS)play a pivotal role in the vicious cycle by regulating inflammation from upstream.Therefore,current therapies merely targeting inflammation show the failure of DED treatment.Here,a novel dual-atom nanozymes(DAN)-based eye drops are developed.The antioxidative DAN is successfully prepared by embedding Fe and Mn bimetallic single-atoms in N-doped carbon material and modifying it with a hydrophilic polymer.The in vitro and in vivo results demonstrate the DAN is endowed with superior biological activity in scavenging excessive ROS,inhibiting NLRP3 inflammasome activation,decreasing proinflammatory cytokines expression,and suppressing cell apoptosis.Consequently,the DAN effectively alleviate ocular inflammation,promote corneal epithelial repair,recover goblet cell density and tear secretion,thus breaking the DED vicious cycle.Our findings open an avenue to make the DAN as an intervention form to DED and ROSmediated inflammatory diseases.

双能量CT电子密度和有效原子序数测量的研究进展

在双能量CT多参数功能分析中,电子密度和有效原子序数的精确测量是实现精准影像诊断和辐射剂量估算的基础。本文综述不同双能量成像模式CT在测量电子密度和有效原子序数准确性方面的研究进展,旨在为影像诊断和治疗计划的研究和临床应用提供参考。

某双油路离心式喷嘴雾化性能分析

燃油喷嘴的雾化对于解决航空发动机燃烧室问题是至关重要的,为探究某双油路离心式喷嘴的雾化性能,运用两相界面追踪流体体积(Volume of Fluid,简称VOF)方法对该喷嘴的内外部流场进行数值仿真。以双油路离心喷嘴的雾化锥角、质量流率以及液膜厚度作为雾化性能指标,分别模拟出主油路单独供油、副油路单独供油以及主副油路同时供油三种不同工作模式在不同压差条件下喷嘴燃油流动的稳态情况,获得双油路离心喷嘴的雾化性能指标并对其影响规律进行研究。结果显示:数值仿真能较好地模拟出喷嘴的雾化特性,随着压差增大,扩口式主油路单独工作时的雾化锥角减小,平口式副油路单独工作时的雾化锥角增大。当主、副油路同时工作时,雾化锥角随压差的增大而增大且始终处于单路单独工作时的雾化锥角之间;质量流率随着压差的增大而增大且增幅逐渐减缓;液膜厚度在低压区随压差的增大而迅速减小,随后趋于稳定。