Catalytic Behavior of Hydrogen Bonded Water in Oligomerization of Silicates.

Even though much research has been done to demonstrate the oligomerization of zeolites and silicates, there has been almost no study that investigates the role of hydrogen bonds in these reaction pathways. This study demonstrates the catalytic activity of hydrogen bonds in the silicate oligomerization reaction pathway. The presence of hydrogen bonding has been shown to enhance the energetic favorability of the anionic-I mechanism. Catalysis is prevalent in the Si-OH rupture process of the reaction pathway. Simultaneously, the dependence of the activation barrier on the equatorial or apical nature of the cleaving hydroxyl group has also been shown. The preceding steps such as condensation and fluxional influence the strength of hydrogen bonds. An increase in hydrogen bond strength enhances its catalytic effect, leading to a higher extent of reduction in the activation barrier of the particular reaction step. Even though the quantum study focuses on the oligomerization of calcium silicate as a test case, it can be anticipated that such similar effects can be perceived in general for the oligomerization of silicates containing metallic ions in sol-gel chemistry and zeolite synthesis.

[1]  Nicholas H. C. Lewis,et al.  Crossover from hydrogen to chemical bonding , 2021, Science.

[2]  Nicholas H. C. Lewis,et al.  Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ proton hydration structures in acid solutions , 2018, Nature Chemistry.

[3]  Wanrun Jiang,et al.  The electron density delocalization of hydrogen bond systems , 2018 .

[4]  Hua Hou,et al.  Theoretical characterizations of the mechanism for the dimerization of monosilicic acid in basic solution. , 2013, Physical chemistry chemical physics : PCCP.

[5]  Siddharth V. Patwardhan,et al.  A solution study of silica condensation and speciation with relevance to in vitro investigations of biosilicification. , 2010, The journal of physical chemistry. B.

[6]  H. Henschel,et al.  Initial Steps of the Sol−Gel Process: Modeling Silicate Condensation in Basic Medium , 2010 .

[7]  J. Goodman,et al.  Enzyme catalysis by hydrogen bonds: the balance between transition state binding and substrate binding in oxyanion holes. , 2010, The Journal of organic chemistry.

[8]  A. Jansen,et al.  Effect of counter ions on the silica oligomerization reaction. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[9]  A. Jansen,et al.  The role of water in silicate oligomerization reaction. , 2009, Physical chemistry chemical physics : PCCP.

[10]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[11]  C. Catlow,et al.  H-Bond interactions between silicates and water during zeolite pre-nucleation. , 2008, Physical chemistry chemical physics : PCCP.

[12]  J. Vermant,et al.  Characterization of nanoparticles in diluted clear solutions for Silicalite-1 zeolite synthesis using liquid 29Si NMR, SAXS and DLS. , 2008, Physical chemistry chemical physics : PCCP.

[13]  D. Vlachos,et al.  Thermodynamics of Silica Nanoparticle Self-Assembly in Basic Solutions of Monovalent Cations , 2008 .

[14]  Kendall T. Thomson,et al.  Density Functional Theory Investigation into Structure and Reactivity of Prenucleation Silica Species , 2008 .

[15]  M. Head‐Gordon,et al.  Systematic optimization of long-range corrected hybrid density functionals. , 2008, The Journal of chemical physics.

[16]  M. Mora-Fonz,et al.  Modeling Aqueous Silica Chemistry in Alkali Media , 2007 .

[17]  B. Weimann,et al.  Dynamics of silicate species in solution studied by mass spectrometry with isotopically labeled compounds. , 2007, Angewandte Chemie.

[18]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[19]  A. Jansen,et al.  Mechanism of oligomerization reactions of silica. , 2006, The journal of physical chemistry. B.

[20]  M. Swart,et al.  Performance of various density functionals for the hydrogen bonds in DNA base pairs , 2006 .

[21]  F. Schüth,et al.  Monitoring temporal evolution of silicate species during hydrolysis and condensation of silicates using mass spectrometry. , 2006, Journal of the American Chemical Society.

[22]  R. Parthasarathi,et al.  Hydrogen bonding without borders: an atoms-in-molecules perspective. , 2006, The journal of physical chemistry. A.

[23]  C. Catlow,et al.  Oligomerization and cyclization processes in the nucleation of microporous silicas. , 2005, Angewandte Chemie.

[24]  A. Warshel,et al.  The low barrier hydrogen bond (LBHB) proposal revisited: The case of the Asp ··· His pair in serine proteases , 2004, Proteins.

[25]  Giovanni Scalmani,et al.  Energies, structures, and electronic properties of molecules in solution with the C‐PCM solvation model , 2003, J. Comput. Chem..

[26]  E. Glendening,et al.  Natural bond orbital methods , 2002 .

[27]  Mark E. Davis,et al.  Si-MFI Crystallization Using a "Dimer" and "Trimer" of TPA Studied with Small-Angle X-ray Scattering , 2000 .

[28]  P. Jacobs,et al.  Identification of precursor species in the formation of MFI zeolite in the TPAOH-TEOS-H2O system , 1999 .

[29]  G. D. Price,et al.  Ab Initio Studies of Silica-Based Clusters. Part II. Structures and Energies of Complex Clusters , 1999 .

[30]  G. D. Price,et al.  Ab Initio Studies of Silica-Based Clusters. Part I. Energies and Conformations of Simple Clusters , 1999 .

[31]  Mark E. Davis,et al.  SAXS and USAXS Investigation on Nanometer-Scaled Precursors in Organic-Mediated Zeolite Crystallization from Gelating Systems , 1999 .

[32]  C. Catlow,et al.  Computer modeling of nucleation, growth, and templating in hydrothermal synthesis , 1998 .

[33]  M. Gordon,et al.  THEORETICAL STUDIES OF THE MECHANISM FOR THE SYNTHESIS OF SILSESQUIOXANES.1. HYDROLYSIS AND INITIAL CONDENSATION , 1998 .

[34]  S. D. Kinrade,et al.  Silicon-29 NMR Studies of Tetraalkylammonium Silicate Solutions. 2. Polymerization Kinetics. , 1998, Inorganic chemistry.

[35]  V. Barone,et al.  Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model , 1998 .

[36]  G. D. Price,et al.  Silica condensation reaction: an ab initio study , 1998 .

[37]  A. Becke.  Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals , 1997 .

[38]  V. S. Murthy,et al.  Nucleophilic Reactions with Tetramethoxysilane and Tetraethoxysilane under Negative Ion Chemical Ionization Conditions , 1995 .

[39]  Mark E. Davis,et al.  Mechanism of Structure Direction in the Synthesis of Si-ZSM-5: An Investigation by Intermolecular 1H-29Si CP MAS NMR , 1994 .

[40]  J. Knowles,et al.  Segmental motion in catalysis: investigation of a hydrogen bond critical for loop closure in the reaction of triosephosphate isomerase. , 1992, Biochemistry.

[41]  R. Ménard,et al.  Oxyanion hole interactions in serine and cysteine proteases. , 1992, Biological chemistry Hoppe-Seyler.

[42]  A. Warshel,et al.  How do serine proteases really work? , 1989, Biochemistry.

[43]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[44]  Frank Weinhold,et al.  Natural localized molecular orbitals , 1985 .