Molecular Heterogeneous Catalysis, Wiley (2006), 352729662X

cuboctahedron 51 current–voltage diagram 350 cyclohexane 41

D

D2/CH4 exchange 46 dangling bonds 103, 227, 228 deacylation 203

decahedron 51

defect sites 41, 239, 240, 253 dehydration 193, 242, 246 dehydrogenation 46, 169 delocalization 56, 90, 116 design 379

desorption 20

deterministic kinetic modeling 457 dextrin 323

diacids 178

diatoms 387, 390, 392

dielectric constant 163, 166, 231 Diels–Alder reaction 325, 353 di usion 20, 207, 300, 416 dimethyl ether 173, 175

diolate 244

direct mechanism 175, 416 disordered overlayer 71, 226, 421 disorder–order transition 154 dissociation 136

DNA 369

double layer 276, 277, 418 downscaling 392

E

edge and kink sites 73, 76, 259 e ective charges 215

E ective Medium Theory 16, 450 e ective volume 205

Eigen 369

electrocatalysis 11, 26, 267, 302, 305 electrochemical 95, 307, 418 electrochemical potential 329 electron a nity 51, 230

Electronic structure methods 424 ab initio function methods 428 B3LYP functional 438

Bloch’s theorem 439 Car–Parrinello ab initio molecular

dynamics 446

Index 467

configuration interaction method 433 coupled cluster methods 436

density functional theory 13, 107, 428, 436, 441

exchange-correlation functional 428, 437 frozen core 430

Gaussian 433

Hartree–Fock self-consistent field approximation 428, 431

Kohn–Sham equations 437 local density approximation 438

linear scaling 443

many-body perurbation theory 435 M¨oller–Plesset perturbation 435 multiconfigurational SCF 424, 434 non-local corrections 438

ONIOM 443

periodic density functional theory 439 pseudopotential approximation 430, 440 self-consistent approximation 425, 428 semi-empirical methods 428

Siesta 444

electron transfer 57, 58, 246, 267, 277, 414 electron–shell 51

electrophilic oxygen 239 embedded 14, 116, 117, 442

embedded atom method 16, 117, 40 emergence 382, 385, 377 enantioselective catalysis 64 enantioselective hydrogenation 66 enantiomeric molecules 37

Energy minimization methods 449 general utility lattice program (GULP)

451

lattice energy minimization technique 450 Metropolis sampling 451

modified embedded atom methods (MEAM 450

Shell model 451 simulating annealing 451

ensemble e ect 41, 43, 243, 246, 247, 362, 413

Enzymes

chymotrypsin 202, 203, 313, 324 cyclin kinase 320

cytochrome 327 dioxygenase 327 fumarase 317

468 Index

hexakinase 316 horseradish peroxidase 393 immunoglobulin 351, 352 lactate hydrogenase 331 monooxygenases 327 myoglobin 392

nitrogenase 330, 331 oxomolybdooxydase 329 papain 388

synthase 313 enzyme catalysis 323

Epoxidation 26, 73, 187, 340, 355 alkenes 186

ethylene 48, 71, 329, 330 propylene 339

equilibrium shape 52 error catastrophe 369 ethyl methyl ether 210 ethylene 44, 111, 201, 202

ethylene hydrogenation 44, 146, 147 ethylidine 44

evolution strategies 360 evolutionary catalysis 351 evolutionary techniques 354 excess ion charge 217

exchange correlation functional 428, 437 excitable systems 420

exponential potential 449 Extended H¨uckel Theory 85 extended system approach 455

F

F2 87

fcc structure 108

Fe, iron compounds, complexes 23, 53, 103, 190, 194, 249, 327, 328, 332, 333

Fermi level 27, 116, 118, 245, 248, 257, 259

Ferrierite 171, 172, 173, 199, 203 field-induced electromigration 283 Filhol–Neurock approach 281 Fischer 334

Fischer–Tropsch 34, 48, 72, 126, 138, 140 fixed-time approach 459

flagellar rotation 321 Fogel mechanism 295, 301 force fields 13, 196, 448

formaldehyde, formyl 126, 372

fractal dimension 390, 396, 397 free energy 335

free radical 62, 253, 327 frontier orbital scheme 94 frozen core 430

fumarate 317

G

Ga, gallium complexes 178, 185 gas phase 307

genetic algorithms 353, 359, 361, 370 genotype 361

glide shear defects 247 glucose 317 glycolaldehyde 372 glycolytic cycles 315

gold, gold compounds 53, 59, 60 graded autocatalysis domain model 375 green chemical process 1

grid size 347, 348 group orbitals 100, 414

H

halides 230

Hammer–Nørskov reactivity model 27 Hammett indicator 234

Hammett acidity 234 Hammett relationship 8

Hammett substituent parameter 32 HCN 87

hcp structure 108 He2 molecule 86

Hellman–Feynman theorem 446, 447 heterolytic 226, 229, 230, 239, 268, 272,

273, 290, 330 heteropolyacids 234, 236 hexamethylbenzene 201 HF 230

histidine 323 HNO 305 homeostasis 375

homogeneous catalyst 65, 292 homolytic activation 229, 230, 238, 268,

272, 290

homopolar chemical bond 86 Hooke’s law 448

hot atoms 75 hybrid methods 68

hybridization 88, 92, 101, 163, 179, 418 hydration, 193, 226

hydration enthalpy 228 hydride, hydrogen 274, 283, 307 hydrodenitrogenation 255 hydrodesulfurization 11, 255 hydroformulation 127

hydrogen 108, 129, 130, 181, 184, 259, 284, 307, 308, 321

hydrogen peroxide 328 hydrogen sulfide 230, 255 hydrogenolysis 42, 46, 169

hydro-isomerization of hexane 197, 199 hydrolysis 185, 318, 323

hydrolysis of carbonates and esters 353 hydronium ion 230, 233, 273, 276, 278,

283, 290, 303 hydroperoxide 339 hydrophobic 165, 314, 323, 326 hydrotreating 255

hydroxyl 60, 136, 216, 218, 220, 295, 383, 296, 306, 307, 419

hypercycles 369

I

icosahedron 51 imidazolinium 328 immunoresponse 7, 351

induced lock and key model 313, 315, 317, 319, 413

infrared 182 inhibition 420

inner-layer Helmholtz 276 inner sphere 290, 420 insulator 257

interface 412 intermittency 381, 382 intrinsic reaction rates 27 ion exchange 48

ionic solids, step, terrace, edge 214, 221, 240

Ir, iridium compounds, complexes 71, 131, 181, 304

iron oxyhydroxy cation 190 irreversible thermodynamics 369 isobutane 169

isobutene 172, 204, 231 isobutyric acid 249

Index 469

Isomerization 66

of hexene in mordenite 198 of pentene 170

of n-butene 170, 203 isopropanol oxidation 240 isotope e ect 194

K

K, potassium 48 Kau mann 369

Keggin structure 235, 248 Keggin unit 234 ketonization 243

kinetic growth model 396 kinetics 361, 448

Kinetic simulations 456 cluster approximation 458

deterministic kinetic modeling 457 master equation 457

mean-field approach 457 stochastic methods 457 transfer matrix technique 458

Knudsen di usion 207, 416 KOAc 293

Koshland 334 Kramers condition 28 Kuhn model 369, 370

L

Labinger interpretation 187, 201 Lagrange multipliers 445 Langmuir model 9, 19, 36, 47, 197 Langmuir–Hinshelwood 207 lanthanides 254

lateral interactions 77, 143, 144, 414 lattice artificial chemistry model 376 lattice relaxation 164

L-Dopa 66 leaching 323

learning system 375 length scales 12

Lennard–Jones-type potential 449

Lewis acidity 178, 185, 215, 223, 249, 415 Lewis basicity 215, 249

Li/MgO 253

ligand field splitting 103, 229 linear scaling 443

lipophilic 373, 403

470 Index

liposome 405 liquid crystals 386

local and global maximum, minimum 426, 438

local density approximation 438 local density of states 91 localization 116

logistic map 379, 380 lone-pair orbital 227, 418 Lotka–Volterra 343 L¨owenstein rule 165 lyotropic liquid 387

M

Madelung constant, potential 221, 222, 257

magic numbers 53 malate 317

maleic anhydride 14

MARI, Major Abundant Reaction, Intermediate 22, 296

Mars–van Krevelen 62, 244 medium e ects 231, 417 MEL-type zeolite 205, 206 membrane 372, 378, 405 Metal

atoms 54 particles 181 support e ect 47

support interaction 55

vapor interface (simulating the) 279 water interface 278

mesoporous silicas 386, 387 metabolic cellular system 368, 372 metastable 247

methane formation 39, 42 Methanol 126, 173

conversion to hydrocarbons 201 oxidation 173, 248, 250 promotion 186

methoxy 173, 175 methylacrylic acid 249 Metropolis sampling 451, 453 MFI 205, 206

Mg, magnesium compounds 55, 60, 73, 178, 180, 215, 221, 249, 315

micelles 387 Michaelis–Menten 197, 313

micr–emulsion 390

micropore occupancy 199, 200 minimum motion principle 318 mixed metal oxide catalyst 61 mixed oxides 410

mixed sulfides 411 Mn 187

MnL6 227

Mo, molybdenum compounds, complexes 60, 61, 62, 214, 250, 255, 256, 257, 296, 334, 417

model catalytic systems 13 Moiseev mechanism 286 Molecular dynamics 444

Born–Oppenheimer approximation 445 Car–Parrinello molecular dynamics 444

molecular imprinting 323

molecular recognition 325, 353, 355, 368, 404, 405, 420

moment of inertia 29 monomolecular reaction 196 Monte Carlo

configurationally biased 454 Gibb’s ensemble 454

grand canonical ensemble 452, 453 kinetic, dynamic 15, 44, 148, 149, 153,

196, 224, 347, 358, 360 methods 196

mordenite 167, 171, 172, 178, 198, 199, 209 Morowitz boundary 375

Morse potential 113 Mo–V–Nb–Te–Ox catalyst 61 multifunctional catalyst 63 multiplication 345, 346, 369, 405 multi-point bonding 317 mutation 353, 359, 405

N

N2O 20, 22, 187, 190, 193, 293, 295, 298 302, 304, 305, 307

Na 189

NADH 314, 330

NADPH 314, 330

Nakamura/Samanos mechanism 285, 286 nanoparticles 51

nano-sized reactors 201 nanoslabs 357

Nb oxide 250

n-butane cracking 169 NH2 252, 304, 307 NH3 oxidation 302

Ni, nickel compounds, complexes 39, 53, 101, 120, 130, 142, 227, 284, 338

nicotinamide adenine nucleotide 314 nitric acid 293

nitrile hydrolysis 323

nitrogen 87, 110, 136, 293, 295, 332 nitrogen fixation 330, 334

N -methylamidpropylamine 389

NMR proton spin–lattice relaxation 394 NO 124, 137, 150, 251, 293, 295, 304,

307, 362 NO2 − 304 NO3 − 302, 304 noble metals 50

non-local gradient corrections 438 non-reducible oxides 239, 253, 255 non-additive behavior 10 non-bonding orbital 95

Noyori 65

NP-complete problem 359 nucleation 355, 420 nucleophylic oxygen 239

O

octahedral 418

one-dimensional open-chain model 114 Oparin model 369, 375

optimum motion principle 318 orbital hybridization at surfaces 226 orbital symmetry control 414 order–disorder transition 349, 350 organophosphorus hydrolase 326 origin of life 367, 368

oscillating phenomena 193 oscillatory dynamics 343, 345, 346 Ostwald 20, 72, 293

outer Helmholtz plane 277

outer sphere 244, 277, 290, 291, 292, 420 overlap 85

overlap energy 85, 114 overlap population density 91 overpotential 308 oxaloacetate 25

oxidation catalysis 187, 238, 326, 328 oxidation of benzene by N2O 193

Index 471

oxidation state 240, 243 oxidative dehydrogenation 249 oxide promoters 48

oxidized Pd clusters 290 oxonium ion 233

oxygen 105, 107, 110, 254, 277, 342 oxygen island 349

oxygen fragment 295 oxygen-atom reactivity 417 oxymetallocycle 74

P

Panov reaction 193 particle shape 257 particle size 350

particle size dependence 349 particle size e ects for Au 55 particle support interaction 38 partition function 29

Pasteur 368 patterning 362

Pauli repulsion 85, 93, 105, 115, 128 Pauling bond strength 216

Pauling ionic charge 418 Pauling valency strength 215

Pd 14, 41, 45, 55, 110, 112, 126, 127, 128, 132, 134, 146, 150, 185, 197, 270, 275, 282, 285, 288, 289, 304

pentene 170

peptide framework 313 percolation 382, 395, 399, 400, 401 periodic doubling 381

periodic trends 105, 272, 275 pH 230

phase diagram 258, 284 phase separation 390, 392 phase transition 52, 349, 384 phosphoramidate 325 phosphoryl 325, 352, 392

photo-catalytic oxidation 2, 187, 189 π–bonded ethylene 112, 146 pinacolate 244

polar adsorbate 165

polar solvent 231, 267, 307 polarization 232 poly(ethylene-oxide) 388, 389 polymer chain reaction 353 polytungstate 234

472 Index

potential energy surface 426 pre-exponential factor 28, 29 pretransition state 173, 176, 177, 178,

190, 317, 318, 334, 413, 415 Prigogine 369

primary carbenium ion 171 principle of least optimum fit 195 probe molecules 178

promotion 47, 186, 239, 248, 255, 259, 285

propane 61, 62, 169, 241, 249 propene 166, 201, 329

proto life 370 protocells 377

protocellular 345, 367, 378, 405 proton 165, 235, 238, 267, 273, 321,

334, 417 pseudomorphic 410

pseudopotential approximation 430, 440 Pt, platinum compounds, complexes 24, 47, 48, 55, 68, 69, 71, 72, 103, 124,

130, 135, 138, 153, 197, 270, 271, 275, 284, 295, 296, 298, 299, 300, 302, 304, 307,342, 362

pulsars 420 pyrite 373

pyrophosphate 325 pyruvate 325

Q

quantum chemical concepts 89 quantum size e ects 57

quasi species 370

R

radical chain reaction 187, 189 random selectivity method 149 reaction energies 272

reaction energy diagram 23, 171, 177, 198 reaction kinetic phase diagram 345 reconstruction 68, 219, 228, 256,

262, 342, 414

redox 187, 239, 243, 244, 247, 249, 250 reducible oxides 250

reduction catalysis 278, 330

reductive coupling of two carbonyl groups 244

refractory 349

relaxed configuration 217 reorganization 7 replication 371, 405

replicative homeostatic early assemblies (RHEA) 375

reproduction 348, 367, 369 reversible potential 277

Rh, rhodium compounds, complexes 42, 49 50, 66, 90, 98, 107, 134, 190, 261, 270, 304

RNA world 369 rotary motion 320

rotating spiral pattern 347

Ru, ruthenium compounds, complexes 94, 73, 107, 130, 138, 140, 228, 269, 271, 304

rutile 219, 220

S

Sabatier principle 7, 20, 21, 22, 24, 55, 56, 409

saddle point 49, 426, 427 Samanos 287, 288, 293 SAPO-34 material 201 SbOV 241

sca olding e ect 173, 176 Schr¨odinger equation 424, 447 screening 167

secular equation 85

selective catalytic reduction 251 selective oxidation catalysis 187

self assembly 337, 354, 355, 367, 368, 403, 420

self learning techniques 353

self organization 7, 71, 190, 337, 342, 344 368, 369, 385, 403, 420

self repair 7, 338, 351, 420

self replication 345, 346, 348, 369, 374 self similarity 397

separation processes 392 serine 202

S–H bond 419 shear planes 417 sheared phases 251 Shell model 451 Si33 cluster 356 σ-type orbital 84 sila n 388, 392

silanol 164 silesquioxanes 340

silica formation 387, 390 silica spheres 390 silicalite 356, 357 silicate oligomer 356 silicateins 388 simulating annealing 351 Sinfelt 41

single center 334

single file di usion 209, 210 SiO2, silica 218, 248, 249 site isolation 242

smectite clays 214 Sn 41

SO2 222

soft cations 415

solid acid catalysis 233, 415 solid-state matrix 36, 307 solution (e ects of) 290 solvent e ect 37, 307 spatial dimension 347 spatial self organization 344

spatio-temporal pattern 346, 347 spin–spin relaxation time 394 spiral waves 346, 420

sponge 388

Sr, strontium compounds 180, 222 [SiF6]2− 388

Stark e ect 277 steam reforming 46

stepped surfaces 123, 306

steps and kinks 121, 134, 136, 137, 409 stereochemical 36, 37

stochastic methods 457 strain 57, 341

strength 215 structural e ects 54

structure directing 388, 392 structure insensitive 36, 43, 135, 413

structure sensitive 36, 44, 135, 143, 409 sulfide catalyst 255

sulfide surface 256 sulfite oxidase 329 sulfur surface 418 sulfuric acid 230 superoxide 330 support e ects 47, 53

Index 473

supported metals 36, 412 supramolecular catalysis 324, 367, 370 surface defect 46

surface di usion 344 surface energy 70

surface enrichment, segregation 46, 247 surface etching facets 72, 241

surface molecule limit 115, 116 surface orbital fragments 414 surface roughness 397

surface topology 108, 409 symmetry breaking 373, 374 synchronization 309, 319, 321, 341, 343, 420

synthesis of vinyl acetate

T

Tafel plots 303, 308

target patterns or spiral waves 347, 348 tartaric acid 63

Taylor model 9, 19, 36, 47 Te oxide 250

temperature-programmed desorption (TPD) 148

template 7, 355, 420, 421 TEMPO molecule 25 tertiary carbenium ion 171

tetradentate triamidoamine ligand 334 tetrapropyl cation 356

thiophene 259, 260, 338 through-space interactions 143 tight binding theory 85, 114

Ti, titanium compounds 48, 55, 57, 186 219, 228, 243, 247, 248, 249

titania-supported Au 56 toluene 167, 189

toxic waste 2

transfer matrix technique 458 transient reaction intermediates 73 transition-metal complexes 101

transition-metal heterogeneous catalysis 294

transition–metal oxide 418

Transition state 28, 73, 166, 167, 169, 334 early 32, 76, 410

late 32, 73, 76, 410 loose, tight 28, 31, 409

reaction-rate expression 27, 28

474 Index

reaction-rate expression 27, 28 selectivity 177, 178

triblock copolymer poly(ethylene-oxide), 390

triblock copolymers of propylene oxide 387

tris(4-nitrophenyl)phosphate (TNP) 326 Triton X-100 388

truncated octahedron 53 turbulence 382

Turing structure 71

U

ultimate catalyst synthesis 368 united atom approach 452 universal relationship 125, 415 unsaturated hydrocarbons 24 upscaling 392

urea 367

V

V, vanadium compounds, complexes 48, 62, 214, 241, 242, 247, 248,249, 250, 251, 296, 417

VAM synthesis 292

van der Waals 165, 195, 214 variable time-step approach 459 Verlet algorithm 455 vibrational frequencies 14

vinyl acetate 44, 288, 289, 291 VMgO 249

volcano plot 22 von Neuman 348 VPO structure 246

(VO)2P2O7 241, 247, 248

W

W¨achtersh¨auser 372, 405

Wacker reaction 25, 288, 290, 293, 329 water 60, 128, 133, 216, 217, 226, 249, 267,

268, 269, 272, 275, 278, 282, 322 waterglass 356

weak adsorption limit 115, 116 WO3 296

W¨ohler 368

Wolfram class behavior 379, 383, 384, 421 work function 108

WS2 255

Wul rule 52, 257

X

X-ray di raction 241 xylene 177

Z

Zaidi 288

zeolite 34, 36, 61, 163, 164, 165, 166,185, 195, 219, 232, 353, 355, 386

zeosil nanoslab 358

zero-point vibrational correction 120 Zn, zinc compounds, complexes 73, 178,

180, 182, 183, 185, 186, 243, 315, 325, 330

ZrO2 248, 249 ZSM-22 209

Zundel ion 234, 276, 283