Research Interests

Quantum Chemical Modeling of Adsorption and the Relevant Processes on Solid Surfaces, Nanoparticles and Carbon Nanotubes

X.L.acknowledges the financial support from the Natural Science Foundation of China, the Ministry of Education, Fok Ying-Dung Educational Foundation, Natural Science Foundation of Fujian Province and Xiamen University.

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Fundings and Projects

    As a PI, I am running the following projects,
  1. A Theoretical investigation on the chemical and phyical properties of narrow-energy gap molecules and related materials, NSFC (Jan. 2010-Dec. 2012, Grant No. 20973137).
  2. Quantum Chemical Modeling of Nanostructural Systems, National Science Fund for Distinguished Young Scholars (Jan. 2005-Dec. 2008, Grant No. 20425312), Natural Science Foundation of China(NSFC).
  3. Theoretical Investigations on the Structures and Chemical Properties of Endohedral Metallofullerenes, NSFC (Jan. 07 - Dec. 09, Grant No. 20673088).
  4. Theoretical Investigations on the Chemical Modification of Carbon Nanotubes, NSFC (Jan. 03 - Dec. 05, Grant No. 20203013).
  5. Theoretical Investigations on Chemical Modification and CVD processes on the Surfaces of Group IVA Semiconductors, Fok Ying-Tung Young Faculty Fellowship(02-05, Grant No.81011 ), Fok Ying-Tung Education Foundation & The Ministry of Education, China.
  6. Quantum Chemical Study on the Sidewall-Functionalization of Single-Walled Carbon Nanotubes, (02-04, Grant No. E0210001), Natural Science Foundation of Fujian Province.
  7. The Ph.D. Programs Foundation of Ministry of Education of China (02-04, Grant No. 20010384005), The Ministry of Education of China

    As a collaborator, I have been involved in the following projects,
  1. 973 Project(Jan. 2011-Dec. 2013, Grant No.2011CB808504), Minitry of Sicence and Technology, Prof. Weihai Fang (PI),
  2. 973 Project(Jan. 2008-Dec. 2012, Grant No.2007CB815307), Minitry of Sicence and Technology, Prof. Lansun Zheng (PI),
  3. (Jan. 2011-Dec. 2014, Key project, Grant No. 21031004), Natural Science Foundation of China(NSFC), Prof. Suyuan Xie (PI),
  4. Inorganic Cluster Science,National Science Fund for Innovative Research Group (Jan. 2008-Dec. 2011, Grant No. 20721001), Natural Science Foundation of China(NSFC), Prof. Lansun Zheng (PI).
  5. Physical Chemistry for Solid Surfaces and the Related Nanostructural Sytems,National Science Fund for Innovative Research Group (Sept. 2000-Aug. 2006, Grant No. 20021002), Natural Science Foundation of China(NSFC), Profs. Zhongqun Tian, Shigang Sun and Lansun Zheng (PIs).
  6. (Jan. 2003-Dec. 2005, Grant No. 90206038), Natural Science Foundation of China(NSFC), Prof. Qianer Zhang (PI),
  7. (Jan. 2004-Dec. 2006, Grant No.2002F010), Natural Science Foundation of Fujian Province, Prof. Qianer Zhang (PI).
  8. (Sept. 2002-Aug. 2005, Grant No. 2002CCA01600), Ministry of Science and Technology, China; Prof. Lansun Zheng (PI)


A. Cluster-Surface Analogy:

A1. Cluster Modeling of Adsorption and Processes on Metal Oxides.

   In the recent years, the use of cluster model to study adsorption and the relevant process on solid surfaces has become popular and many successful applications of the method have been made. In the framework of cluster-surface analogy, a bulk solid could be regarded as a sum of two fragments. One is a cutout cluster to be explicitly treated in quantum chemical calculations, the other is the surrounding of the cutout cluster. Accordingly, in order to establish a reasonable cluster model, one has to answer two questions: (i) how to cut out a cluster; and (ii) how to suitably account for the cluster-lattice interaction. The answers to the questions above vary with and depend on the nature of the solid to be simulated.
   For the modeling of metal oxides, we have proposed, in regard to th e first question, three principles, namely, neutrality principle, stoichiometrical principle and coordination principle, according to which a neutral, stoichiometrical cutout cluster with the minimal amount of dangling bonds is preferred. Case studies on ZnO and MgO demonstrated a good correlation of the topologic parameters Nd(the total amount of dangling bonds of a cutout cluster) and Beta(the average dangling bonds on each in-cluster atom) with the stability of clusters, which not only provides an efficient way to set up a good cluster model of a given size without paying for the high cost of detailed preliminary calculations, but also ensures a good convergence from the cluster to the surface. For the second question, some sophisticated embedding schemes have been developed recently. In the modeling of ionic metal oxide, the most common, yet effective way is to simulate the influence of the surrounding with a point charge (PC) array that adopts the lattice position of bulk solid. In our recent investigations, we have found the calculated electronic properties of the substrate clusters and the adsorption properties vary with the ways (magnitude and shape of PCs, shape and size of the embedding PC array) to describe the surrounding. Accordingly, we have proposed the SPC embedded cluster model method. The main points of the so-called SPC cluster model can be summarized as follows: a Stoichiometric cutout cluster with the least dangling bonds embedded in a Symmetric PCC (point charge cluster), and a Spherically expanded point charge (or point charges augmented with ECP (effective core potential)) surrounding with charges being Self-consistently determ ined. Case studies of chemisorptions or reactions on the metal oxides of different degree of ionicity, e.g., CO/Mg O , H2/ZnO, N2O/MgO, NO/MgO and H2/TiO2, demonstrated the efficiency of the SPC embedded cluster model .
 
    Some Relevant Papers:
  1. "Cluster Modeling of Metal Oxides: How to cut out cluster?", X. Lu, X. Xu, N. Wang, Q. Zhang, M. Ehara, and H. Nakatsuji, Chem. Phys. Lett., 291 (1998) 457.
     
     
  2. "Cluster Modeling of Metal Oxides: the Influence of the Surrounding Point Charges on the Embedded Cluster", X. Xu, H. Nakatsuji, M. Ehara, X. Lu, N. Wang, Q. Zhang, Chem. Phys. Lett.,292(1998), 282.
     
  3. "On the Cluster modeling of metal oxides: Case study of MgO and CO/MgO adsorption system", X. Xu, H. Nakatsuji, X. Lu, M. Ehara, N. Wang, Q. Zhang, Theoretical Chemistry Accounts, 102(1999) 170.
     
  4. "Heterolytic Adsorption of H2 on ZnO(10-10) Surface: An Ab Initio SPC Cluster Model Study", X. Lu, X. Xu, N. Wang, Q. Zhang, H. Nakatsuji, M. Ehara, J. Phys. Chem. B 103 (1999) 2689.
     
     
  5. "N2O Decomposition on MgO and Li/MgO Catalysts: An Ab Initio Study", X. Lu, X. Xu, N. Wang, Q. Zhang, J. Phys. Chem. B 103 (1999), 3373.
     
     
  6. "A quantum chemical study of NO/MgO chemisorption system: Hybrid B3LYP calculations on NO/(MgO)n (n=4,6,8) model systems", X. Lu, X. Xu, N. Wang, Q. Zhang, Chem. Phys. Lett., 300 (1999) 109.
     
  7. "NO Adsorption and Decomposition on MgO Catalyst: A Quantum Chemical Study", X. Lu, X. Xu, N. Wang, Q. Zhang, J. Phys. Chem. B 103 (1999), 5657.
     
  8. "Convergence from Clusters to the Bulk Solid: Ab Initio Calculations of (MgO)x (X=2-16) Clusters", X. Lu, X. Xu, N. Wang, Q. Zhang, Int. J. Quant. Chem. , 73(1999), 377.

     
  9. "Chemisorption of CO at Strongly Basic Sites of MgO Solid: A Theoretical Study", X. Lu, X. Xu, N. Wang, Q. Zhang, J. Phys. Chem. B, 104 (2000), 10024.
     

A2. Cluster Modeling of Adsorption and Processes on the Surfaces of Semiconductors.

This project is supported by the Fok Ying-Tung Educational Foundation and the Natural Science Foundation of China.

    We employ ab initio methods to explore the reaction mechanisms of various molecules (either inorganic or organic) on the surfaces of group IV semiconductors (Diamond, Silicon and Germanium) and to predict novel reactions for the functionalization of these solid surfaces.
    Some Relevant papers:
     
  1. "Diradical Mechanisms for the Cycloaddition Reactions of 1,3-butadiene, benzene, thiophene, ethylene and acetylene on Si(111)-7x7 Surface", X. Lu, X. Wang, Q. Yuan, Q. Zhang, J. Am. Chem. Soc. , 125 (2003) 7923-7929.
     
  2. "Chemisorption of NO on Si(111)-7x7 Surface: A DFT Study", Z. Su, X. Lu, Q. Zhang, Chem. Phys. Lett. , 375 (2003) 106-112.
     
  3. "Hydroboration of C(100) Surface, Fullerene, and the Sidewalls of Single-wall Carbon Nanotubes with Borane", L. Long, X. Lu, F. Tian, Q. Zhang, J. Org. Chem. , 68 (2003) 4495-4498.
     
  4. "Diradical Mechanism for the [2+2] Cycloaddition of Ethylene on Si(100) Surface", X. Lu, J. Am. Chem. Soc. , 125 (2003) 6384-6385.
     
  5. "The Chemistry of HN3 on Ge(100)-2x1: A Theoretical Study", X. Lu, Z. Su, X. Xu, N. Wang, Q. Zhang, Chem. Phys. Lett. , 371 (2003) 172-177.
     
  6. "High Charge Flexibility of the Surface Dangling Bond States on the Si(111)-7x7 Surface and NH3 Chemisorption: A DFT Study", X. Lu, X. Xu, N. Wang, Q. Zhang, M.C. Lin, Chem. Phys. Lett. , 355 (2002) 365-370.
     
  7. "Chemisorption of Acetonitrile, Pyridine and Pyrazine on the Si(100)-2x1 Surface: Theoretical Predictions", X. Lu, X. Xu, N. Wang, Q. Zhang, New J. Chem., 26(2002) 160-164.
     
  8. "A DFT Study of the 1,3-Dipolar Cycloadditions on the C(100)-2x1 Surface" X. Lu, X. Xu, N. Wang, Q. Zhang, J. Org. Chem. , 67 (2002) 515-520.
     
  9. "Reactions of Some [C,N,O]-Containing Molecules with Silicon Surfaces: Experimental and Theoretical Studies" (Review) X. Lu, M.C. Lin, Int. Rev. Phys. Chem., 21 (2002), 137-184.
     
  10. "Chemisorption and Decomposition of Thiophene and Furan on the Si(100)-2x1 Surface: A Theoretical Study.", X. Lu, X. Xu, N. Wang, Q. Zhang, M.C. Lin, J. Phys. Chem. B, 105(2001) 10069.
     
  11. "A Theoretical Study of HN3 reaction with the C(100)-2x1 surface", X. Lu, X. Xu, N. Wang, Q. Zhang, M.C. Lin, Chem. Phys. Lett., 343 (2001) 212.
     
  12. "Theoretical Study of the [4+2] Cycloadditions of some 6- and 5-member Ring Aromatic Compounds on the on the Si(100)-2x1 Surface: Correlation between Binding Energy and Resonance Energy", X. Lu, M.-C. Lin, X. Xu, N. Wang, Q. Zhang, PhysChemComm, 13 (2001) 1.
     
  13. "Adsorptions of Methanol,Formaldehyde and Formic Acid on the Si(100)-2x1 Surface: A Theoretical Study", X. Lu, Q. Zhang, M.C. Lin, Phys. Chem. Chem. Phys., 3(2001) 2156.
     
  14. "Adsorption and Reactions of HCN on the Si(100)-2x1 Surface: A Density Functional Study." F. Bacalzo-Gladden, X. Lu, M.C. Lin, J. Phys. Chem. B, 105 (2001) 4368.
     
  15. "Bonding Configurations of C2H2 Chemisorption on the Si(100)-2x1 Surface Predicted by Density Functional Cluster Model Calculations." X. Lu, M.C. Lin, Phys. Chem. Chem. Phys., 2 (2000) 4213.
     

A3. Cluster Modeling of Adsorption and Processes on Metal Surfaces.

    Some Relevant papers:
     
  1. "Ab Initio Studies on Metallic Ni-CO Cluster", X. Xu, N. Wang, X. Lu and Q. Zhang, J. Xiamen Univ. (Natur. Sci.), (in Chinese) 33 (1994), 823-826.
     
  2. "Surface-Cluster Analogy: Ab Initio Studies of Pdn (n=1-7) Clusters", X. Xu, N.Q. Wang, X. Lu, Q.E. Zhang, Science in China,(in Chinese), B25 (1995) 573-578.
     
  3. "Ab Initio Studies on Pdn-CO(n=1-7) Cluster Models", X. Xu, N.Q. Wang, X. Lu, Q.E. Zhang, Acta Chimica Sinica, (in Chinese) 53 (1995) 670.
     
  4. "Cyanide Adsorbed on Coinage Metal Electrodes: A Relativistic Density Functional Investigation", M. Liao, X. Lu, Q. Zhang; Int. J. Quant. Chem., 67 (1998), 175.

     
  5. "The Adsorption of NO2 on Au(111) Surface: An Ab Initio Study", X. LU, X. Xu, D. Wu, N. Wang, Q. Zhang, J. Phys. Chem. A, 103 (1999) 10969.
     

B.Theoretical Study on Nano-Chemistry:

B1. Chemistry of Carbon Nanotubes

We are using ONIOM approach (QM/QM and QM/MM) to predict chemical reactions on the sidewalls of carbon nanotubes that would lead to functionalized nanotubes. Also, some hypothetical reactions inside the nanotubes will be checked to see in what manner the confinement of the tube wall would affect the reactions' kinetics.
This project is supported by the Ministry of Education (CHINA), Natural Science Foundation of China, and Natural Science Foundation of Fujian Province.
    Relevant publications are:
  1. "Are the Stone-Wales Defects Always More Reactive than Perfect Sites in the Sidewalls of Single-Wall Carbon Nanotubes", X. Lu*, Zhongfang Chen, Paul v. R. Schleyer, J. Am. Chem. Soc., 126(2004), in press.
  2. "A Theoretical Exploration of the 1,3-Dipolar Cycloadditions onto the Sidewalls of (n,n) Armchair Single-Wall Carbon Nanotubes", X. Lu, F. Tian, X. Xu, N. Wang, Q. Zhang, J. Am. Chem. Soc , 125 (2003) 10459-10464
     
  3. "The [2+1] Cycloadditions of dichlorocarbene, Silylene, Germylene and Oxycarbonylnitrene onto the Sidewall of Armchair (5,5) Single-Wall Carbon Nanotube", X. Lu, F. Tian, Q. Zhang, J. Phys. Chem. B , 107 (2003) in press.
     
  4. "Hydroboration of C(100) Surface, Fullerene, and the Sidewalls of Single-wall Carbon Nanotubes with Borane", L. Long, X. Lu, F. Tian, Q. Zhang, J. Org. Chem. , 68 (2003) 4495-4498.
     
  5. "Organic Functionalization of the Sidewalls of Single-Wall Carbon Nanotubes by Diels-Alder Reactions: A Theoretical Prediction", X. Lu, X. Xu, N. Wang, Q. Zhang, Org. Lett., 4(2002) 4313-4315.
     
  6. "Sidewall oxidation and complexation of carbon nanotubes by base-catalyzed cycloadditions of transition metal oxide: A theoretical prediction", X. Lu, F. Tian, Y.B. Feng, X. Xu, N. Wang, Q. Zhang, Nano Lett., 2(2002) 1325-1327.
     
  7. "Can the Sidewalls of Single-Wall Carbon Nanotubes be Ozonized?"(Letter). X. Lu, L. Zhang, X. Xu, N. Wang, Q. Zhang, J. Phys. Chem. B,106 (2002) 2136-2139.
     

B2. Chemistry of Metal and Metal Oxides Nanoparticles

Chemical reactions on Metal and Metal Oxides Nanoparticles differ significantly from their anologues on bulk solids in both mechanisms and dynamics. A fundamental study of such difference is highly desirable to make full use of the advantages of nanoparticles for practical applications.
This project is supported partially by Xiamen University and partially by the Natural Science Foundation of China (NSFC).
    Selected Publications:
  1. "Convergence from Clusters to the Bulk Solid: Ab Initio Calculations of (MgO)x (x=2-16) Clusters". X. Lu, X. Xu, N. Wang, Q. Zhang, Int. J. Quant. Chem., 73(1999), 377.
     
  2. "Chemisorption of CO at Strongly Basic Sites of MgO Solid: A Theoretical Study", X. Lu, X. Xu, N. Wang, Q. Zhang, J. Phys. Chem. B, 104 (2000), 10024.
     

B3. Structure and Chemistry of Nonclassical Fullerenes and Derivatives

Fullerenes are convex carbon cages comprising hexagons and exactly twelve pentagons. The geometry and stability of fullerenes are, in most cases, governed by the so-called isolated-pentagon rule (IPR), i.e., the pentagons within the most stable fullerenes are surrounded by hexagons. Classical fullerenes are those carbon cages that faithfully fulfill this rule. Non-IPR Fullerenes that have pentagon-pentagon ring fusions are called Nonclassical Fullerenes. There have been several examples non-IPR fullerenes reported thus far. But they are, without exception, either endohedral or exohedral derivatives of Non-IPR fullerenes, e.g. Sc2@C66, Sc3N@C68, and C50Cl10. Stimulated by the recent synthesis of C50Cl10, we have been being conducted theoretical investigations on the Structural and Chemical Properties of exohedral/endohedral derivatives of some classical/nonclassical fullerenes, e.g., C50Cl10, C50, C64H4, Sc2C2@C68, M2C2@C78 (M=Ti, Zr, Hf), ScnC2@C80 (n=3,4).
    Selected Publications:
  1. "C64H4: Production, Isolation and Structural Characterizations of a Stable Unconventional Fulleride", C.-R. Wang,* Z.-Q. Shi, L.J. Wan, X. Lu*, L. Dunsch, H. Shinohara, J. Am. Chem. Soc., 128(2006) 6605-6610.
     
  2. "Isolation and Characterization of Sc2C2@C68: the smallest metal-carbide endohedral fullerene", Zhi-Qiang Shi, Xin Wu, Chun-Ru Wang,* X. Lu* Hisanori Shinohara, Angew. Chem., 118 (2006) 2161-2165;Angew. Chem. Int. Ed., 45 (2006) 2107-2111;
     
  3. "Unprecedented m4-C26- Anion in the Endofullerene Sc4C2@C80", K. Tan, X. Lu*, C.R. Wang, J. Phys. Chem. B, 110(2006) 11098-11102.
     
  4. "Properties of fullerene[50] and D5h decachlorofullerene[50]: A Computational Study", X. Lu*, Zhongfang Chen*, Paul v. R. Schleyer, W. Tiel, R. B. Huang, L. S. Zheng, J. Am. Chem. Soc., 126(2004), 14871-14878. .
     
  5. "Capturing the Labile Fullerene[50] as C50Cl10", S.Y. Xie, F. Gao, X. Lu, R. B. Huang, C.R. Wang, S.L. Deng, X. Zhang, M.L. Liu, L.S. Zheng, Science, 304 (2004) 699.
     
  6. "Ti2C80 is More Likely a Titanium Carbide Endohedral Metallofullerene (Ti2C2)@C78", K. Tan, X. Lu*, Chem. Comm., (2005), 4444-4446.
     
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