Surface Science最新文献

{"title":"One century of evolution of surface science, a personal perspective","authors":"Miquel B. Salmeron,&nbsp;Xiao Zhao","doi":"10.1016/j.susc.2024.122636","DOIUrl":"10.1016/j.susc.2024.122636","url":null,"abstract":"<div><div>Compared to the bulk, surfaces of materials usually exhibit unique chemical, structural and electronic properties due to their distinct interactions with the external phase, such as vacuum, gas, liquid or another solid. Breakthroughs in this field are typically driven by significant instrumental development. In this review we will highlight a few developments in surface science in the last 40 years, as well as the discoveries they brought to the scientific and engineering communities. These findings, together with relevant technical developments, enable a deeper understanding of phenomena critical to catalysis, energy conversion, and nanotechnology.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122636"},"PeriodicalIF":2.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel MoS2/Pd5 nanocluster heterojunction system with improved surface reactivity for efficient gas sensing: A DFT study","authors":"Khalid Mujasam Batoo ,&nbsp;Iman Samir Alalaq ,&nbsp;Rekha MM ,&nbsp;Anurag Mishra ,&nbsp;Shilpa Sharma ,&nbsp;G.V. Siva Prasad ,&nbsp;Muhammad Farzik Ijaz ,&nbsp;Salima B. Alsaadi ,&nbsp;Ahmed Ali Mtasher ,&nbsp;Fadeel F. Seed","doi":"10.1016/j.susc.2024.122648","DOIUrl":"10.1016/j.susc.2024.122648","url":null,"abstract":"<div><div>Our work has reflected considerable interest in unique Pd nanocluster/MoS₂ heterojunction systems due to their potential applications in materials science, chemistry and physics. We focused on exploiting Pd₅/MoS₂ nanocluster system, a novel heterojunction material for gas sensing applications. In addition, we exploited the electronic properties of Pd dopant on the MoS₂ surface to make a comparative study. Our DFT calculations indicate that the Pd₅/MoS₂ heterojunction structure exhibits a higher affinity for adsorbing gas molecules such as CO, NH₃, NO, and NO₂, while the perfect MoS₂ shows weak gas adsorption capacity. Pd₅/MoS₂ heterojunction exhibits semiconducting feature with a weakened and narrower band gap, making it more suitable for gas sensing due to its higher conductivity. We analyzed important factors like adsorption distance/energies, density of states, band structure and difference of electron density concerning adsorbed gases on the heterojunction surface. Based on the electron density difference maps, we can see the giant growth of charges over the adsorbed molecules, as well as between the adsorbing atoms. Based on our findings, the conductivity of the nanomaterial undergoes a remarkable change, which helps reinforce the applicability of the Pd₅/MoS₂ heterojunction nanosystem in sensing and adsorbing gas molecules.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122648"},"PeriodicalIF":2.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A study of Cl adsorption on Pt(111) and Pt(100) using Ab Initio Grand-canonical Monte Carlo","authors":"Eun Mi Kim,&nbsp;Junseok Kim,&nbsp;Kristen A. Fichthorn","doi":"10.1016/j.susc.2024.122647","DOIUrl":"10.1016/j.susc.2024.122647","url":null,"abstract":"<div><div>We used <em>ab initio</em> grand-canonical Monte Carlo (AIGCMC) simulations based on plane-wave density-functional theory to probe the structures and surface energies of Pt(100) and Pt(111) with adsorbed chlorine. For Pt(100), we considered both the (1 × 1) surface and a (5 × 1) reconstruction, as a model for the experimentally observed “hex” reconstruction of Pt(100). We constructed phase diagrams of the surface energies as function of the Cl chemical potential and identified the most relevant surfaces. For Pt(100), we find the hex reconstruction is favored at low Cl chemical potentials and that Cl adsorption lifts the reconstruction. The progression of ordered structures predicted for this surface is: bare (5 × 1) Pt(100), Θ = 1/2 (1 × 1) Pt(100), and Θ = 2/3 (1 × 1) Pt(100), where Θ is the fractional surface coverage of Cl. All these structures are seen experimentally. We also observe a structure with Θ = 3/4 and intermixing between Pt and Cl on Pt(100) that is related to the structure at Θ = 2/3. For Pt(111), we find a progression of (3 × 3) unit cells at Θ = 1/9, 1/3, 4/9, 5/9, and 2/3. The structures at Θ = 1/3 and 4/9 have been proposed experimentally and most experiments predict a series of (3 × 3) unit cells with increasing Cl coverage. If intermixing between Cl and Pt does not occur in experiment, then we find a (4 × 2) Cl structure at Θ = 1/2 is energetically favored, as is observed in experiment. A strength of AIGCMC is the capability to identify relevant structures, including disordered structures, without predefined input. This increases the chance of having high fidelity to experiment and identifying relevant substrates for applications.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122647"},"PeriodicalIF":2.1,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Abnormal adsorption of lithium on the graphene surface of graphene/dT(H)-MoS2 heterostructures","authors":"Rui Yang,&nbsp;Xiao-Huan Lv,&nbsp;Ke-Xin Hou,&nbsp;Xing-Qiang Shi,&nbsp;Jiang-Long Wang","doi":"10.1016/j.susc.2024.122646","DOIUrl":"10.1016/j.susc.2024.122646","url":null,"abstract":"<div><div>The graphene/MoS₂ heterostructures (Gr/MoS₂) exhibit excellent performance for ion batteries, such as superior stability and cyclicity for ion battery storage, and have great potentials for other applications. Lithium (Li) adsorption on/in Gr/MoS₂ heterostructures exhibits advanced properties and interesting phenomena, as well as the phase engineering of MoS₂. However, unified understanding for the different adsorption behaviors remains lacking, although fully understanding to the adsorption behaviors is of vital importance for their applications. In the current work, the Li adsorptions on the Gr surface of Gr/dT(H)-MoS₂ heterostructures are systematically analyzed based on density functional theory calculations, and highlight the differences between Gr/H-MoS₂ and Gr/dT-MoS₂ for Li adsorption. To fully understand the adsorption behaviors, we perform detailed analyses from four interrelated aspects: 1) Electrostatic interactions from detailed Bader charge analysis, 2) charge density difference Δρ(<em>z</em>), 3) energy-level alignment between Li and the band edges of Gr, dT-, and H-MoS₂, and 4) the resulted interface dipoles. We find that partial electrons in Li can pass through Gr to H-MoS₂ and the origin is attributed to the weak electronic-shielding of Gr (even weaker than H-MoS₂). All of the above extended analysis not only enables us to understand the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS₂ heterostructures, but also helps guide the selection of ion battery materials. Moreover, we extend the discussion of Li adsorption to other alkali metal atoms with smaller work functions (such as: Na and K). Our work not only provides understanding to the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS₂ heterostructures, but also helps guide the selection of ion battery materials. So, the insights from this study are important for their related applications. This paper reveals and explains an interesting abnormal adsorption phenomenon of lithium on van der Waals heterostructures of graphene and different phases of MoS₂.The conclusion and insights from this work is not limited to Li (applicable at least to Na and K, also), and hence our work is helpful for establishing the surface-adsorption mechanisms of ion batteries.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122646"},"PeriodicalIF":2.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142592995","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Time-resolved photoelectron spectroscopy at surfaces","authors":"Martin Aeschlimann ,&nbsp;Jan Philipp Bange ,&nbsp;Michael Bauer ,&nbsp;Uwe Bovensiepen ,&nbsp;Hans-Joachim Elmers ,&nbsp;Thomas Fauster ,&nbsp;Lukas Gierster ,&nbsp;Ulrich Höfer ,&nbsp;Rupert Huber ,&nbsp;Andi Li ,&nbsp;Xintong Li ,&nbsp;Stefan Mathias ,&nbsp;Karina Morgenstern ,&nbsp;Hrvoje Petek ,&nbsp;Marcel Reutzel ,&nbsp;Kai Rossnagel ,&nbsp;Gerd Schönhense ,&nbsp;Markus Scholz ,&nbsp;Benjamin Stadtmüller ,&nbsp;Julia Stähler ,&nbsp;Martin Weinelt","doi":"10.1016/j.susc.2024.122631","DOIUrl":"10.1016/j.susc.2024.122631","url":null,"abstract":"<div><div>Light is a preeminent spectroscopic tool for investigating the electronic structure of surfaces. Time-resolved photoelectron spectroscopy has mainly been developed in the last 30 years. It is therefore not surprising that the topic was hardly mentioned in the issue on “The first thirty years” of surface science. In the second thirty years, however, we have seen tremendous progress in the development of time-resolved photoelectron spectroscopy on surfaces. Femtosecond light pulses and advanced photoelectron detection schemes are increasingly being used to study the electronic structure and dynamics of occupied and unoccupied electronic states and dynamic processes such as the energy and momentum relaxation of electrons, charge transfer at interfaces and collective processes such as plasmonic excitation and optical field screening. Using spin- and time-resolved photoelectron spectroscopy, we were able to study ultrafast spin dynamics, electron–magnon scattering and spin structures in magnetic and topological materials. Light also provides photon energy as well as electric and magnetic fields that can influence molecular surface processes to steer surface photochemistry and hot-electron-driven catalysis. In addition, we can consider light as a chemical reagent that can alter the properties of matter by creating non-equilibrium states and ultrafast phase transitions in correlated materials through the coupling of electrons, phonons and spins. Electric fields have also been used to temporarily change the electronic structure. This opened up new methods and areas such as high harmonic generation, light wave electronics and attosecond physics. This overview certainly cannot cover all these interesting topics. But also as a testimony to the cohesion and constructive exchange in our ultrafast community, a number of colleagues have come together to share their expertise and views on the very vital field of dynamics at surfaces. Following the introduction, the interested reader will find a list of contributions and a brief summary in Section <span><span>1.3</span></span>.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122631"},"PeriodicalIF":2.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142722421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"X-ray and photoelectron spectroscopy of surface chemistry; from bonding via femtosecond to operando","authors":"Anders Nilsson","doi":"10.1016/j.susc.2024.122637","DOIUrl":"10.1016/j.susc.2024.122637","url":null,"abstract":"<div><div>For the 60th anniversary of Surface Science, I present here a personal account of some of the most significant contributions I have made to the field over the past three decades. The utilisation of X-rays serves as the foundation for these studies, encompassing X-ray spectroscopy for the mapping of surface chemical bonds, probing of surface reactions on ultrafast timescales, and X-ray photoelectron spectroscopy under operando conditions. The direct projection of electronic states onto the adsorbed atom allowed the detection of bonding and anti-bonding states within the d-band model. The selective probing of orbitals of different symmetries on the two atoms in adsorbed N₂ provided a fundamental understanding of the nature of diatomic bonding to surfaces. Ultrafast optical pumping and X-ray laser techniques allowed the study of CO undergoing desorption leading to the observation of the precursor state. Pump-probed studies of co-adsorbed CO and O on Ru enabled the means to detect transition state species during catalytic CO oxidation. The use of operando X-ray photoelectron spectroscopy at near-atmospheric pressures opened the door to probe the surface chemistry and gain insight into the reaction mechanism during hydrogenation reactions to produce ammonia, hydrocarbons, methanol and ethanol. By inserting an electrochemical cell into the spectroscopic chamber, both fuel cell and water splitting electrocatalysis could be studied giving insight about the reaction mechanism.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122637"},"PeriodicalIF":2.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Adsorption and sensing performances of transition metal doped ZnO monolayer for CO and NO: A DFT study","authors":"Hongliang Tang ,&nbsp;Ying Duan ,&nbsp;Xu Yang ,&nbsp;Jing Wang ,&nbsp;Yuyang Wang","doi":"10.1016/j.susc.2024.122635","DOIUrl":"10.1016/j.susc.2024.122635","url":null,"abstract":"<div><div>In this study, theoretically, density functional theory was employed to explore the adsorption behavior of CO and NO prevalent hazardouss gases, on transition metal (TM = Fe, Co, Ni, and Cu) doped ZnO monolayer. The multifaceted analysis encompasses an array of critical aspects, including the adsorption structure, adsorption energy, density of states (DOS) and electron transfer to unravel the adsorption behavior. Our calculations show that TM atom doped ZnO monolayer exhibit high stability. TM doped can significantly enhance the interaction between the gas molecules (CO and NO) and the ZnO monolayer. Analysis of the recovery time and electrical conductivity of the adsorbed systems suggests that the Co-ZnO could be a suitable material for CO sensing,while the Cu-ZnO and Ni-ZnO can be used for NO sensing. These results suggest that transition metal doped can be a promising sensor candidate for toxic gas molecules adsorption and detection.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122635"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142553518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fabrication of B-C-N nanosheets on Rh(111) from benzene – borazine mixtures","authors":"László Óvári ,&nbsp;Gábor Vári ,&nbsp;Máté Farkas ,&nbsp;Gyula Halasi ,&nbsp;Nikolett Oláh ,&nbsp;Csaba Vass ,&nbsp;Arnold P. Farkas ,&nbsp;András Berkó ,&nbsp;János Kiss ,&nbsp;Zoltán Kónya","doi":"10.1016/j.susc.2024.122633","DOIUrl":"10.1016/j.susc.2024.122633","url":null,"abstract":"<div><div>Atomic level studies of solid state surfaces performed in ultra-high vacuum (UHV) had already an energetic 15–20 years past when our research group in Szeged started working in this field in mid 1970s. Till then several very important methods had been developed, like UHV technology, commercially available electron and photoelectron spectroscopy techniques, etc. Characterization of metal and semiconductor (oxide) surfaces and their adsorption properties had already been widely studied. In any case, the last 40–50 years also witnessed great discoveries and exciting new techniques. Considering only the activity related to heterogeneous catalysis, the main focus of our research group, new breakthrough methods emerged like HREELS, RAIRS, SPM, NAPXPS, EXAFS, NEXAFS. Along this path, new experimental and theoretical approaches appeared like planar model catalysts and inverse catalysts, atomic level investigation and understanding of surface diffusion-controlled phenomena (particle growth and disruption, strong metal-support interaction (SMSI), decoration, spillover), atomic level identification of active sites, self-organized nano-systems, surface alloys and nanotemplates. It was great to participate in this magical activity for more than 50 years. Both internationally and locally in Szeged, in the last two decades, surface science has opened to the wide world of 2D materials like the semimetal graphene and the insulator hexagonal boron nitride. However, the formation of a mixed layer of C, B and N proved to be a difficult task due to the primary tendency for phase separation. In the present work, we report on a preparation method of honeycomb “BCN” materials on Rh(111) by using benzene/borazine mixtures as precursors. It was demonstrated that by a suitable choice of the growth parameters, the formation of large, separated graphene and h-BN islands can be avoided.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122633"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the atomic-scale dynamics of Fe3O4(001) at catalytically relevant temperatures using FastSTM","authors":"Johanna Reich ,&nbsp;Sebastian Kaiser ,&nbsp;Alexander Bourgund ,&nbsp;Matthias Krinninger ,&nbsp;Ueli Heiz ,&nbsp;Friedrich Esch ,&nbsp;Barbara A.J. Lechner","doi":"10.1016/j.susc.2024.122634","DOIUrl":"10.1016/j.susc.2024.122634","url":null,"abstract":"<div><div>Surfaces and interfaces of functional nanoscale materials are typically highly dynamic when employed at elevated temperatures. Both, lateral surface and vertical bulk exchange diffusion processes set in, which can be relevant for applications such as heterogeneous catalysis. Time-resolved scanning tunneling microscopy (STM) is being pushed to ever faster measurement modes to follow such dynamic phenomena in situ. Here, we present FastSTM movies monitoring a range of atomic-scale dynamics of a prototypical reducible oxide catalyst support, Fe₃O₄(001), at elevated temperatures. Antiphase domain boundaries between two domains of the reconstructed surface exhibit local mobility from around 350 K, while Fe-rich point defects, in a stable equilibrium with the bulk, appear to diffuse in a peculiar zigzag pattern above 500 K. Finally, exploiting the diffusivity of Fe interstitials, we follow the propagation of step edges in the topmost atomic layer of the Fe₃O₄(001) surface in an oxygen atmosphere.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122634"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142592996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Growth and electronic structure of the nodal line semimetal in monolayer Cu2Si on Cu(111)","authors":"Jinfeng Xu ,&nbsp;Chen Liu ,&nbsp;Yuxuan Guo ,&nbsp;Guikai Zhang ,&nbsp;Kun Liu ,&nbsp;Haijie Qian ,&nbsp;Kaiqi Nie ,&nbsp;Zhenyu Wang ,&nbsp;Jiaou Wang","doi":"10.1016/j.susc.2024.122632","DOIUrl":"10.1016/j.susc.2024.122632","url":null,"abstract":"<div><div>Cu₂Si, a single-layer two-dimensional material with a honeycomb structure, has been proposed to have Dirac nodal line fermions. In this study, the synchrotron radiation X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (SR-XPS, SR-UPS, and SR-ARPES) techniques were used to investigate the dynamic process of in situ deposition of single-layer Cu₂Si on a Cu(111) crystal surface via molecular beam epitaxy (MBE). Cu₂Si existed as a monolayer (ML) alloy, and there were competing mechanisms of distinct chemical states of silicon in different growth periods, according to a detailed examination of the experimental SR-XPS and SR-UPS spectra. Additionally, a weak interaction between the Cu₂Si ML and Cu(111) was demonstrated via SR-ARPES and first-principles computations. The unique electronic structure of the Cu₂Si ML was not destroyed by either this weak interaction or the disordered silicon produced on the surface during the growth process. The study of the Cu₂Si growth kinetics provides a guarantee and a basis for the future exploration of the exotic properties of Cu₂Si.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122632"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142553519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}