Metal-Catalysed Reactions of Hydrocarbons / 15-back-matter

INDEX

Activation energy source of, 245

true and apparent, 222, 246 Active centre, concept of, 229–234

modification for alkane reactions, 633–647 Multiplet Hypothesis, 230

reaction dimension, 231

structure sensitivity, 230, 231, 243 active ensemble, 237–238

in alkane dehydrogenation, 508 in alkane hydrogenolysis

in benzene hydrogenation, 433

in cyclopropane hydrogenation, 479

in dehydrogenation of cycloalkanes, 511 ensemble-size sensitivity, 232, 234–239 in ethene hydrogenation, 298, 303–305,

319–321

face sensitivity, 232

in hydrogenation of alkynes, 406, 414 landing site for alkanes, 260, 262 with nickel-copper catalysts, 238 particle-size sensitivity, 232, 234–239

in reactions of higher alkanes, 628–633 true ensemble requirement, 237

Alicyclic rings, small, hydrogenation of, 473 mono-alkylcyclopropanes, 484, 487

regiospecificity, 485 poly-alkylcyclopropanes, 488–490

1, 2-Alkadienes (allenes), hydrogenation of, 360 propadiene, 360

substituted 1,2-alkadienes, 362 Alkadienes, branched, hydrogenation of,

386–388

Alkadienes, cyclic, hydrogenation of, 388–390 Alkadienes, higher linear, hydrogenation of,

382–385

Alkanes, chemisorption of, 196 Alkanes, dehydrogenation of, 501–503

alkane chemisorption, 504 n-butane dehydrogenation, 509 dehydrocyclisation (DHC), 503 kinetics, 508

modifiers, 507

use in petrochemical industry, 502 platinum-tin catalysts for, 505

alumina-supported, 506 other supports, 506 silica-supported, 505

structure-sensitivity, 508

Alkanes, exchange with deuterium, 257–287 cycloalkanes, 278–285

ethane, 267–271

higher linear and branched alkanes, 271–275

methane, 258–267

Alkanes, higher, hydrogenolysis of, 596; see also Hydrogenolysis of alkanes

Alkanes, isomeric C7 , reactions of, 613 Alkanes, lower, hydrogenolysis of, 528;

see also Hydrogenolysis of alkanes Alkenes, chemisorbed structures of, 170–177 Alkenes, exchange reactions between, 335 Alkenes, higher, reactions with hydrogen and

deuterium, 336–339 l-hexene, 336 racemisation, 338

657

658

Alkenes, hydrogenation of, 292

alkene exchange mechanism, 294, 308, 328 dissociative chemisorption, 318 double-bond migration, 295, 328, 336 exothermicity, 298

mechanism, 294

Z-E isomerisation, 295, 328

Alkenes, reaction with deuterium, 307–319 see also Ethene, Propene, n-Butenes

on bimetallic catalysts, 319 Alkylcyclopentanes, reactions of, 620 Alkynes, hydrogenation of; see also

Hydrogenation of alkynes bimetallic catalysts, 418

ethyne hydrogenation with added ethene, 411

ethyne hydrogenation, 396 on higher alkynes, 421 industrial applications

Alloys, 24–30 amorphous, 25

electron compounds, 26 electronic properties, 27 ferromagnetism, 29 paramagnetism, 28

superparamagnetism, 28 Hume-Rothery rules, 26 intermetallic compounds, 25 interstitial, 26

nickel-copper

dehydrogenation of cyclohexane on, 513 electronic structure, 27–29

ensemble size vs. ligand effect, 238 ethane hydrogenolysis on, 575 ethene-deuterium reaction on, 319 ethyne hydrogenation on, 420 benzene hydrogenation on, 451

physical properties, 26, platinum-rhenium

alkane hydrogenolysis on, 579–582 reactions of higher alkanes on, 635–636

platinum-tin

alkane dehydrogenation on, 505–506 alkane hydrogenolysis on, 579 cycloalkane dehydrogenation on, 512 ethene chemisorption on, 175, 193 hydrogen chemisorption on, 107

regular solution parameters, 29 substitutional, 24

surfaces, 29

INDEX

composition 29 experimental techniques, 30

theoretical models, 27 rigid band model, 27 virtual bound state, 27

two-dimensional, 26 Amorphous (glassy) metals, 15

Anderson-Kempling Scheme, 555, 562, 568–569 Aromatic hydrocarbons, exchange with

deuterium, 453

on bimetallic films, 454 dissociative mechanism, 456 effect of substituents, 454

exchange between benzene and benzene-d6 , 455

particle size effect, 454

Aromatic ring, hydrogenation of, 438, 461 kinetics and mechanism, 440–446

rate expressions, 446 Aromatisation, 634

Arrhenius equation, 212, 231, 242, 547 Atomic XAFS, 73,129

Balandin number, 47,230 Band Theory, 9–12

Benzene hydrogenation: see Hydrogenation of benzene

Benzene, chemisorbed structures, 178 Benzene, resonance energy, 438 Bimetallic catalysts

alkane hydrogenolysis on, 574–583 benzene hydrogenation on, 450 cycloalkane dehydrogenation on, 512–514 cycloalkane exchange on, 283–284 ensemble size effect vs. ligand effect, 236 hydrogen chemisorption on, 122

hydrogenation of 1,3-butadiene on, 379–382 hydrogenation of ethyne on, 418 preparation of, 45

reactions of higher alkanes on, 635–642 uses in catalysis, 234

Buckminsterfullerene (C60 ), hydrogenation of, 468

1,2-Butadiene, hydrogenation of, 363

1,3-Butadiene, hydrogenation of, 365 n-Butane hydrogenolysis, 530–548, 558–562,

571–574, 576, 578 n-Butane, dehydrogenation of, 509

n-Butanes, reaction with hydrogen and deuterium, 328–332

INDEX

659

microwave analysis, 330 on nickel catalysts, 330

on palladium catalysts, 331

on platinum catalysts, 328–330 single turnover method, 333

isoButene, hydrogenation of, 334 Butynes, hydrogenation of, 422–424

Carbonaceous deposits, 205–206, 297, 320 in alkane dehydrogenation, 502

in benzene hydrogenation, 446 effect on active centre, 621–623

formation, structure and function, 516–519 carbon nanotubes, 518

role in catalysed processes, 518

in hydrogenation of cyclobutane derivatives, 497

in hydrogenolysis of higher alkanes, 601 in hydrogenolysis of lower alkanes, 529 reaction of alkenes on, 339

reaction of ethyne on, 406 Catalysis, 210–214

brief history, 210 catalytic cycle, 213, 234 definition, 210

essential nature, 210 Chemisorbed hydrocarbon species,

on alloy surfaces, 175 chemisorbed alkanes, 504

chemisorbed alkenes, detailed structure of, 176 chemisorbed alkenes, π and σ forms,

169–176, 193

intermediate structures of alkenes, 170–171

chemisorbed benzene, structures of, 178 chemisorbed 1,3–butadiene, 366 chemisorbed cyclopropane, 475 chemisorbed ethyne, structures of, 178, 398 comparison with organometallic complexes,

167,168, 193

heats of adsorption on single crystals, 180–185

identification of, 161–169

structures of alkenes on single crystal surfaces, 171

C C bond order, 172 π -σ parameter, 173

theoretical approaches, 190–195

comparison between DFT and experiment, 192

density functional theory (DFT), 191, 205 molecular orbitals, 193–194

quantum mechanical analysis, 190 relativistic phenomena, 195

thermal decomposition of, 186 ethene, 187

Compensation, 239–247

in alkane reactions, 533–540, 605, 611 compensation equation, 239 Constable plot, 241

isokinetic relationship, 240 Temkin equation, 246–247

Cumulenes, 358 hydrogenation of, 365

Cycloalkanes, dehydrogenation of on bimetallic catalysts, 512–514

nickel-copper, 513

single crystals of platinum-tin, 512 chemisorption of hydrogen, 514

on pure metals, 510 platinum, 510 structure-sensitivity, 511

thermochemistry, 510

Cycloalkanes, exchange with deuterium, 278–285

Cycloalkenes, hydrogenation of, 338–348 cyclodecene, 340

cyclohexene, 338 disproportionation, 338

cyclopentene, reaction with deuterium, 339 substituted cycloalkenes, 340–348

alkyl reversal, 341 enantiomeric pairs, 346 octalins, 343–345

product stereochemistry, effect of hydrogen pressure, 347–348

Cyclobutane derivatives, hydrogenation of, 494–498

methylcyclobutane, 494–495 reaction with deuterium, 496

methylenecyclobutane, 498

other alkylcyclobutanes, 497–498 Cyclohexane, reactions of, 616 Cyclopropane

chemisorption, 475

hydrogenation and hydrogenolysis, 477 activation energy, 479–480

kinetics, 477

reaction mechanism, 482 structure-sensitivity, 479

660

INDEX

Cyclopropane (cont.)

reaction with deuterium, 481 regiospecificity of alkyl-substituted, 476 structure and theory, 474

Cyclopropanes with other reactive groups, hydrogenation of, 491

3-carene, 492 cyclopropene, 493

methylenecyclopropane, 491–492 phenyl substituents, 493

Cyclopropanes, alkyl-substituted, hydrogenation of, 484–490

1,1-dialkyl, 490 monoalkyl, 484, 487 polyalkyl, 488–490

Cyclopropylmethanes, hydrogenation of, 490

Dehydrogenation

of cycloalkanes, 510–514 of isobutane, 515

of linear alkanes, 501–509

role of carbonaceous deposits in, 516 Debye temperature, 21

Density functional theory (DFT), applications of to chemisorbed hydrocarbons, 191, 205

to ethene hydrogenation, 320 Dirac equation, 7

Dispersion, measurement of, 52–58, 114–123 free-valence, 48

with hydrogen, 59,115 back-filtration method, 116 dynamic mode, 122 filtration methods, 122–123 volumetric method, 118

Elovich equation, 125

Ethane, exchange with deuterium, 267–271 Ethane hydrogenolysis, 540

formulation of kinetics and mechanism, 540–545

Ethene, chemisorbed structures of, 171–177 Ethene, hydrogenation, 292, 297–307

activation energy, 300, 302 on bimetallic catalysts, 306 deactivation, 297

kinetics, 297–300 mechanism, 301–302

by spillover catalysis, 325–328 structure sensitivity, 298, 303

on model catalysts, 304

on single crystal surfaces, 319–321 specific and areal rates, 304

on unsupported metals, 305

Ethene, reaction with deuterium, 307–319 ethene exchange, 308–314

hydrogen exchange, 308 interpretation of product distribution,

310–315 mechanism, 321–325

advanced deficiency theory, 325 microkinetic analysis, 322

Monte Carlo simulation, 323–324 on nickel, 308

on platinum, 309–311

on single crystal surfaces, 319–312 structure sensitivity, 314–315

Ethyne, chemisorbed structures of, 178 Exchange (equilibration) of alkanes with

deuterium, 257–287 branched alkanes, 273–275 cycloalkanes, 278–286

alkylcyclopentanes, 280–281 bimetallic catalysts, 283–284 cyclopentane mechanism, 276–280,

283–284 cyclopropane, 284 epimerisation, 280

Horiuti-Polanyi mechanism, 275 polycyclic alkanes, 281–283

ethane, 267–271 mechanism, 268–271

multiple exchange with, 268 higher linear alkanes, 271

multiple exchange, 272 methane, 258–267

compensation plots, 261–264 kinetics, 261

landing site, 262 mechanism, 264–267

multiple exchange, 258, 286 stepwise exchange, 258

Exchange of deuterium between alkanes, 285 Extended X-ray absorption spectroscopy

(EXAFS), 54, 73, 120, 505 Extractive chemisorption, 22

Fat-hardening, 360 Fermi surface, 10

Field emission microscopy, 15, 94 Field ion microscopy, 15, 94

INDEX

661

Heats of adsorption alkenes, 180–185 ethyne, 183

hydrogen, 109–112, 128 Heats of hydrogenation, 293, 358

1-Hexene, exchange with deuterium, 336

3-Hexyne, hydrogenation of, 426

n-Hexane, reactions of, 602–609, 624–628, 634 neoHexane, reactions of, 610, 612, 613 Homologation of alkenes, 332

n-butanes, 328–332 ethene, 292, 297–307 mechanism, 321–325 propene, 297–307

by spillover catalysis, 325–328 Homologation of methane, 519

Horiuti-Polanyi mechanism, 275, 294, 313, 316, 332, 341, 505

Hydrocarbons, chemisorption of, 156–161 high-resolution electron energy loss

spectroscopy (HREELS), 158 metal surface selection rule, 158 overview, 156–157

photelectron diffraction, 160 potential energy curves for, 156–157 structures of adsorbed species:

see Chemisorbed hydrocarbon species sum-frequency generation, 160 techniques, 158–161

Hydrogen bronzes, 136, 326

Hydrogen chemisorption on supported metals, 114

adsorption isobar, 116

on bimetallic catalysts, 122 Langmuir equation, 118 on platinum, 514

on ruthenium catalysts, 121–122 stoichiometry, 118

weak state, 120

Hydrogen chemisorption, theoretical approaches to, 129–131

molecular precursor state, 131 potential energy surface, 129 Type C chemisorption, 130

Hydrogen chemisorption on unsupported metals and alloys, 97–114

chemisorbed state, principles, 102–114 adsorption (Langmuir) equation, 108 on bimetallic systems, 107

energetic aspects, 108

geometric aspects, 102

heat of adsorption, 109–112 metal-hydrogen bond, 105, 127 temperature-programmed desorption

(TPD), 111–114 Wigner-Rolanyi equation, 114

exposure, 100

potential energy diagram, 98 sticking probability, 101

Hydrogen chemisorption, characterisation of, 124–129

deuteron NMR for, 126 Elovich equation, 125 heats of adsorption, 128 proton NMR for, 125

vibrational spectroscopies for, 126 Hydrogen chemisorption, in alkane

dehydrogenation, 514

Hydrogen spillover, 69, 74, 116, 132–137, 326 catalytic activity, 135, 326

reducing power, 135 reverse spillover, 326

Hydrogen, interaction with metals, 94 dissolution in palladium, 95, 99 hydrides of intemetallic compounds, 96

Hydrogen, reactions of, 140–142 Hydrogenation of alkadienes

applications, 358

branched alkadienes, 386–388 isoprene, 386

1,2-butadiene, 363

1,3-butadiene, 365

on bimetallic catalysts, 379–382 chemisorbed states, 366, 376 industrial importance, 366

on intermetallic compounds, 380–381 kinetic parameters, 369–371 mechanism, 376–379

on metal catalysts, 368–375 reaction with deuterium, 375 selectivities, 371

on single crystals, 367 support effects, 374

chemoselectivity, 359 cyclic alkadienes, 388

cyclo-octadienes, 388 norbornadiene, 389 terpenes, 390

fat-hardening, 360

higher linear alkadienes, 382

662

INDEX

Hydrogenation of alkadienes (cont.) hexadienes, 384–385

linear alkadienes, 382 1,3-pentadienes, 383

propadiene, 360

kinetic parameters, 362 N-profile analysis, 362 reaction with deuterium, 362

regioselectivity, 359 Hydrogenation of alkynes

ethyne hydrogenation on bimetallic catalysts, 418

industrial practice, 418 Lindlar catalyst, 419 poisoning by mercury, 421

ethyne hydrogenation without added ethene, 396

active centres on palladium, 405 chemisorbed states, 398

deuterium exchange between alkynes, 411 formation of benzene, 407

kinetic parameters, 401 origin of selectivity, 399

reaction in static systems, 401–407 reaction with deuterium, 407–411 structure sensitivity, 406

ethyne hydrogenation, with added ethene, 411 active centres, 414

gaseous promoters, 417 kinetics, 412–413

mechanisms and modelling, 415 oligomerisation, 417

particle size effect, 412

hydrogenation of higher alkynes, 421–429 aryl-substituted alkynes, 428

butynes, 422 multiply-unsaturated alkynes, 429 3-hexyne, 426

propyne, 421

reaction with deuterium, 422–424 industrial applications, 396

Hydrogenation of benzene, 445–458 formation of cyclohexene, 457 ruthenium catalysts for, 457

substituent effects, 457 industrial applications, 439 kinetics and mechanism, 440–446

activities of metals for, 441 nickel catalysts for, 440

over bimetallic catalysts, 450

on nickel-copper catalysts, 451 rate expressions, 446

structure sensitivity, 443 support involvement, 445

temperature-inversion of rates, 448 thermochemistry, 438

Hydrogenation of cyclobutane derivatives, 494–498

Hydrogenation of cyclopropane; see also Cyclopropane

Hydrogenation of methylcyclopropane, 485 Hydrogenation of poly-alkylcyclopropanes, 488 Hydrogenation of small alicyclic rings, 473 Hydrogenation, heats of, 293, 358 Hydrogenolysis and other reactions of higher

alkanes

activities of pure metals, 599 cyclopentane, 599 n-hexane, 600 neopentane, 600

n-alkanes, product selectivities, 596–597 branched alkanes, 609

aromatisation, 616 compensation plots, 611 isomeric C7 alkanes, 613 3-methylpentane, 611, 614 neohexane, 610, 612, 613 neopentane, 610, 626, 631 reactions on ruthenium, 614 reactions on base metals, 615

carbonaceous residues, effect on active centres, 621–623

cyclic alkanes, 616 alkylcyclopentanes, 620 cyclohexane, 616 dimethylcyclopentanes, 620 methylcyclopentane (MCP), 617

selectivity of MCP reactions, 617–621 effect of varying conversion 601

2,2-dimethylbutane, 601 n-hexane, 601

linear alkanes, 602 compensation plot, 605

dehydrocyclisation (DHC), 603 effect of chain length, 605

n-hexane, reaction on platinum black, 604 reactions on nickel, 609

reactions on palladium, 606 reactions on rhodium, 607 reactions on ruthenium, 609

INDEX

663

the literature, 597

mechanisms, overview, 624–628 modification of active centre, 633–647

for aromatisation of linear alkanes, 634 effect of sulfur, 644

by elements of Groups 14 and 15, 637–639 metal particles in zeolites, 634

other bimetallic catalysts, 639–642 platinum-ruthenium, 642 platinum-rhenium, 635–636

strong metal-support interaction (SMSI) 644–647

n-pentane, 596, 608 principal themes, 598 skeletal isomerisation, 625

bond-shift mechanism, 625 C5 cyclic mechanism, 626

dehydrocyclisation (DHC), 628 structure-sensitivity, 628–633

model catalysts, 629 particle-size effects, 630 single-crystal surfaces, 628

Hydrogenolysis of lower alkanes on bimetallic catalysts, 574–583

compensation plots, 577 nickel-copper, 575–576 platinum-molybdenum, 581–582 platinum-rhenium, 574 platinum-rhenium, 579–582 platinum-tin, 579 ruthenium-copper, 577

effects of additives and support interactions, 569–574

apparent SMSI effects, 571 platinum-containing clays, 573

general characteristics, 528 n-butane isomerisation, 533

reaction kinetics, difficulties with, 528 short reaction period, 528

single crystals, 533–565

structure sensitivity, 528, 552–555 generalised model, 549

lower alkanes on platinum, 530–548 kinetic parameters, 531

orders in hydrogen, 532, 536, 538, 545 compensation plots, 533–540 activation energies, 534–536, 538

kinetic formulations and mechanisms, 540 ethane hydrogenolysis, 541–545

kinetic modelling, 543–546

dependence of activation energy on hydrogen pressure, 545–548

lower alkanes on other metals, 552 mechanism of skeletal isomerisation,

564–565

mechanisms based on product selectivities, 562

comparison between metals, 563 particle-size effects, 564

product composition, ways of expressing, 530 fragmentation factor, 530

reactivity factor, 530 product selectivity, 555, 562

Anderson-Kempling scheme, 555, 563 isobutane, 558

n-butane, 558–562

on ruthenium catalysts, 565 effect of potassium, 574

effects of pretreatment conditions, 565–568 Anderson-Kempling scheme, 568–569 ruthenium/alumina, 566

ruthenium/titania, 565

Intermetallic bonds, strength of, 7 Intermetallic compounds, 1,3-butadiene

hydrogenation on, 380–381 Isomerisation

Z-E, in alkenes, 295, 328 skeletal, mechanism of, 563–564

Isoprene, hydrogenation of, 386 Isotopes, use of, 249

Kempling-Anderson scheme;

see also Anderson-Kempling scheme Kinetic analysis

activation energy apparent, 222 Temkin equation, 223 true, 222

formulation of, 214 kinetic control, 214

Langmuir-Hinshelwood formalism, 218–222 mass-transport control, 214–215

modelling, 225–227 order of reaction, 215 rate constant, 221 rate of reaction, 216

areal rate, 217

effect of temperature on, 221 specific rate, 217

664

INDEX

Kinetic analysis (cont.)

turnover frequency (TOF), 217, 234 reaction mechanism, concept of, 227

most abundant surface intermediate (MASI), 229

selectivity, 223 degree of, 224

Langmuir equation, 108, 118, 216, 218, 388, 447 Langmuir-Hinshelwood formalism, 218–222,

246, 446, 478 Lanthanide contraction, 7 Lattice vibration, 20 Lindlar catalyst, 419, 429

Low-energy electron diffraction (LEED) intensity analysis, 177

Mechanisms

dehydrocyclisation (DHC), 628 skeletal isomerisation, 625–628

Metal films, 15, 94 Metal surface, 3, 14

stepped, kinked, 18 structure, 16, 102 surface energy, 21 surface tension, 19

theoretical descriptions, 22

local density of states, (LDOS), 23 molecular orbital description, 23

work function, 22 Metal-hydrogen bond, 105

polarity, 106 strength, 127

Metallic character, 2, 3, 4, 8 energetic, 5

geometric, 4 magnetic, 8 mechanical, 4 Metallic state, 2, 12 theories of, 8, 9

augmented plane wave method, 12 cellular method, 10

density of states, 10 electron band theory, 10, 12

interstitial electron theory, 13 Metal-support interactions, 69, 317 Metal-support interface, 70 Methane, exchange with deuterium,

258–267

Methane, homologation of, 519

Methylcyclohexane (MCP), selective hydrogenolysis of, 617–621

Methylcyclopropane, hydrogenation of, 485 Methylenecyclopropane, hydrogenation of,

491–492 3-Methylpentane, 611, 614

Microkinetic analysis, in ethene hydrogenation, 322

Microscopic metals, 36 Adams oxides, 40 bimetallic particles, 37 colloidal dispersions, 39 dispersion, 36 instability, 38

metal blacks, 39 Raney metals, 39 sintering, 38

Microscopic reversibility, 102 Miller index, 16

Model catalysts, 46, 321

Monte Carlo simulation, 323–324 Mossbauer¨ spectroscopy, 56, 505

Naphthalene, hydrogenation of, 461 exchange with deuterium, 465 hydrogenation of octalins, 464;

see also Alkadienes, cyclic, hydrogenation of

methyl substituent effect, 464–465 structures of decalins, 463

Nickel-copper alloys: see Alloys Norbornadiene, hydrogenation of, 389 Nuclear magnetic resonance (NMR), 56

deuteron NMR, 126 Knight shift, 57

magic angle spinning NMR, 57 proton NMR, 125

Orbitals atomic d-, 12 metallic, 12

molecular, at surfaces, 23, 169–170 Oligomerisation, in ethyne hydrogenation, 417

Palladium

alkane hydrogenolysis on, 606 alkyne hydrogenation on, 396, 406 butadiene hydrogenation on, 373–374

hydrocarbon chemisorption on, 193, 194 isoprene hydrogenation on, 386

INDEX

665

Palladium hydrides, 95–96

role in ethyne hydrogenation, 406 neoPentane, reactions of 610, 626, 631 n-Pentane, reactions of, 596, 608 Periodic Classification, 1

Petroleum reforming, 592–595 bifunctional catalysis, 592–595 hydrotreating, 593

octane rating, 593 principles, 592

Phonon, 20

Photoelectron spectroscopy photoelectron diffraction, 160, 171 ultraviolet (UPS), 66, 107, 161, 186 X-ray (XPS), 66

Platinum-rhenium catalysts, 579–582, 635–636 Poisons, selective, 76

Poly-alkylcyclopropanes, hydrogenation of, 488 Polycyclic aromatic hydrocarbons,

hydrogenation of, 466 Polyphenyls, hydrogenation of, 461 Preparation of supported metal catalysts;

see Supported metal catalysts Propadiene, hydrogenation of, 360 Propane hydrogenolysis; see also

Hydrogenolysis of alkanes Propene, reaction with deuterium, 307–319

on single crystal surfaces, 320 Propyne, hydrogenation of, 421

Racemisation, in alkene hydrogenation, 338 Raney metals, 39

Rare-earth-containing bimetallic catalysts, 307 Reaction mechanism, concept of, 227–228 Reaction mechanisms, philosophical digression

on, 526 Reactors, 247 Redispersion, 77

Relativity, Special Theory of, 7 application to chemisorbed states, 195

Rigid band model, 27

Ruthenium catalysts, for alkane hydrogenolysis, 565–569

Ruthenium catalysts,

for alkane hydrogenolysis, 565–569

partial hydrogenation of aromatic ring on, 457

Selective hydrogenation: see Hydrogenation, selective spiropentane, hydrogenation of, 491

Selective poisons, 76 Single-crystal surfaces, 15, 94, 97

alkane chemisorption on, 197 alkane hydrogenolysis on, 533, 565 1,3-butadiene hydrogenation on, 367 ethene hydrogenation on, 319–321 heats of adsorption on, 180–185 platinum-tin: see Alloys

reactions of higher alkanes on, 628 Sintering, 77

Small metal particles, 47 anomalous structures, 64 dispersion measurement by gas

chemisorption, 52, 58, 118 electronic properties, 66 energetic properties, 65 metal-support interactions, 65, 74 mithohedrical region, 48

particle size effect, 51, 74

physical methods for characterising, 52 cyclic voltammetry, 58

EXAFS, 54, 73

Mossbauer¨ spectroscopy, 56 NMR, 56

transmission electron microscopy (TEM), 52

XANES, (NEXAFS), 55 XPS, 56, 66

X-ray diffraction, 54

physical properties, variation with size, 60 size distribution, 51

structure, 63 theoretical methods, 67 turnover frequency, 47

Spillover catalysis of alkene reactions, 325–328 Standard catalysts, 119

EUROPT-1, 119, 125, 128, 324, 336, 478, 530, 533, 543, 547, 558, 563, 572, 603, 611, 620

EUROPT-3, 558, 563

Strong metal-support interaction (SMSI), 45, 137–139, 317–318, 569–574

Structure sensitivity, 230; see also Active centre, concept of

in reactions of higher alkanes, 628–633 Superconductivity, 8

Supported metal catalysts, 40 bimetallic catalysts, 46, 68

preparation, 46 definition, 40

666

Supported metal catalysts (cont.) model catalysts, 46, 68 preparation, methods of, 41

chemical vapour deposition (CVD), 44 coprecipitation, 44 deposition-precipitation, 44 impregnation, 44

ion exchange, 44 reduction, 45

promoters redispersion selective poisons, 76 sintering, 77

Strong Metal-Support Interaction, (SMSI), 45, 137–139, 569–574, 644–647

Supports, 42 porosity, 42 silica, 42 alumina, 42 zeolites, 42 carbon, 43 titania, 43

physical forms, 43

Taylor fraction, 47, 230

Techniques for catalyst characterisation, 52–58

Techniques for catalytic reactions, 247 isotopes, use of, 249

mass-spectrometry, 250 tritium, 251

INDEX

reactors, 247 pulse-flow mode, 248

transient kinetics, 248

temporal analysis of products (TAP), 249 Temkin equation, 223, 246, 449–450, 543, 548 Terpenes, hydrogenation of, 390

Toluene, hydrogenation of;

see also Hydrogenation of benzene adsorption coefficients, 459

kinetic parameters, 458

Turnover frequency (TOF), 217, 234, 530

Unsaturated hydrocarbons, types of, 154

Valence electrons, 4

Work function, 22

Wulff construction, 21

X-ray absorption near-edge spectroscopy (XANES), 55, 367

X-ray absorption spectroscopy (XAFS); see Extended X-ray absorption fine structure (EXAFS)

X-ray diffraction, 54

X-ray photoelectron spectroscopy (XPS), 56, 66

Xylenes, hydrogenation of;

see also Hydrogenation of Benzene kinetic parameters, 458 stereochemistry, 460