Predic'ng crystal growth via a unified kine'c 3-D par''on model - PowerPoint PPT Presentation

Samara University, Samara, Russia 12 th February 2019 Predic'ng crystal growth via a unified kine'c 3-D par''on model Michael W. Anderson The University of Manchester, UK

Nature , 2017 , 544, 456.

Zeolites

ETS-10 intergrowth defect

Same crystal structure Different synthesis conditions

Microscopy NMR - AFM Mass spectrometry - High-resolu'on SEM - High-resolu'on TEM Computer modelling

Solu'on chemistry complex Structures are complex

h -1 = [Si]/[TPAOH] 1D 29 Si NMR : silicalite-1 h -1 2.78 2.78 1.83 1.28 1.03 0.83 0.36 Figure : 1D- 29 Si spectra of successive aqueous phases obtained during TEOS hydrolysis with TPA OH in the 25 TEOS : 9 TPAOH : 152 H 2 O system. D.P.Petry, M. Haouas, S.C.C. Wong, A. Aerts, C.E.A. Kirschhock, J.A. Martens, S.J. Gaskell, M.W. Anderson and F. Taulelle J. Phys. Chem. C 2009 , 113 , 20827

M. Haouas and F. Taulelle J. Phys. Chem. B 2006 , 110 , 3007

Zeolite Beta C M.E. Chiu et al. , Angew. Chem., 2005 , 44 , 1213

AFM/op'cal microscopy LTA Using Nanowizard AFM from JPK

NanoWizard AFM from JPK Combining op'cal microscopy with AFM

Atomic Force Microscope

HRSEM - correla'on with AFM LTA

ZIF-8

ZIF-8

ZIF-8

Frank-Read Disloca'on Loop F.C. Frank and W.T. Read, Phys. Rev. , 79 , 722 (1950)

Spiral Growth: AFM MOF-5 STA-7 STA-7 SAPO-34 ZIF-76 ZnPO 4 -SOD 26 M. W. Anderson & M. P. Attfield Group publications, University of Manchester

(100) ZnPO 4 SOD (100) M.A. Holden, P. Cubillas and M. W. Anderson Chem. Commun, 2010 , 46 , 1047-1049

ZnPO 4 SOD (100) M.A. Holden, P. Cubillas, M.P. Aaield, J.T. Gebbie and M.W. Anderson J. Amer. Chem. Soc., 2012 , 134 , 13066-13073

ZnPO 4 SOD (100) M.A. Holden, P. Cubillas, M.P. Aaield, J.T. Gebbie and M.W. Anderson J. Amer. Chem. Soc., 2012 , 134 , 13066-13073

ZnPO 4 SOD (100) M.A. Holden, P. Cubillas, M.P. Aaield, J.T. Gebbie and M.W. Anderson J. Amer. Chem. Soc., 2012 , 134 , 13066-13073

ZnPO 4 SOD (111)

M.A. Holden, P. Cubillas, M.P. Aaield, J.T. Gebbie and M.W. Anderson J. Amer. Chem. Soc., 2012 , 134 , 13066-13073

Growth unit in vacuum • Solvent • • • Motherphase • Crystal bulk • • • • • • Crystal surface sites

• • • • • • • • • • • • • • • •

• • • • • • • • • • For growth at this site • • • • • • Δ U

• • • • • • • • • • For growth at this site • • • • • • Δ U

• • • • • • • • • • For growth at this site • • • • • • Δ U

solu'on solid P growth P etch = exp( Δ U kT + Δ µ s s kT ) s

R. Brent, P. Cubillas, S.M. Stevens, K.E. Jelfs, A. Umemura, J.T. Gebbie, B. Slater, O. Terasaki, M.A. Holden and M.W. Anderson J. Amer. Chem. Soc. , 2010 , 132 , 13858-13868 LTL

Zeolite L - growth mechanism, internal defects, deflec'on images Short Cylinders: Side Walls LTL

Zeolite L - growth mechanism, internal defects, deflec'on images Short Cylinders: Side Walls LTL

Zeolite L - growth mechanism, internal defects, deflec'on images LTL

R. Brent, P. Cubillas, S.M. Stevens, K.E. Jelfs, A. Umemura, J.T. Gebbie, B. Slater, O. Terasaki, M.A. Holden and M.W. Anderson J. Amer. Chem. Soc. , 2010 , 132 , 13858-13868

R. Brent, P. Cubillas, S.M. Stevens, K.E. Jelfs, A. Umemura, J.T. Gebbie, B. Slater, O. Terasaki, M.A. Holden and M.W. Anderson J. Amer. Chem. Soc. , 2010 , 132 , 13858-13868

Closed-cage structures (1) (2) 1.3 nm 1.6 nm (3) (4) 1.2 nm 1.0 nm (5) (6) 0.8 nm 0.7 nm (7)

Rate-determining step NOT growth unit Q 3 at surface Closed cage Unit of growth NOT a growth unit Q 4 internally

(100) facet

Internal Energy, U Δ µ bulk double 4-ring sodalite cage alpha cage

Davide Proserpio Vladislav Blatov

CHA AEI

LTL

MFI 10 different 'le types

CrystalGrower Nature – 2017 , 544, 456 New Kine'c Monte Carlo code that can determine growth energe'cs for ANY crystal structure And determine both habit and surface topography • Determines all possible growth sites • Determines consequences of growth on all neighbours • Does this very efficiently allowing growth of micron-sized crystals • Include defects, addi'ves, intergrowths

LTA

LTA

ALPHA

ALPHA

ALPHA

ALPHA

(100) (110)

LTA high supersatura'on CrystalGrower

LTA high supersatura'on CrystalGrower

LTA equilibrium CrystalGrower

LTA equilibrium CrystalGrower

LTA CrystalGrower

ZnPO-FAU P. Cubillas, M.A. Holden, M.W. Anderson, Cryst. Growth & Design , 11 , 3163 (2011)

FAU CrystalGrower

FAU equilibrium CrystalGrower

FAU equilibrium CrystalGrower

UOV

UOV

UOV

UOV CrystalGrower

UOV CrystalGrower

UOV CrystalGrower

ETS-10 intergrowth defect

ETS-10, exposing the titanate chains

ETS-10 CrystalGrower

ETS-10 CrystalGrower

ETS-10 CrystalGrower

ETS-10 confocal Raman spectroscopy N.C. Jeong, H. Lim, H. Cheong and K.B. Yoon, Angew. Chem. , 2011 , 50 , 8697

CrystalGrower

HKUST-1 CrystalGrower

CrystalGrower

S. Piana, M. Reyhani, J.D. Gale, Nature , 438 , 70 (2005) CrystalGrower

Calcite CrystalGrower

L -cys'ne Rimer et al, Science , 330 (2010) 337–341

L -cys'ne CrystalGrower

L -cys'ne growth overhang