INDEX

Note: Page numbers in italics refer to figures; those in bold type refer to tables.

Absorption bandsadsorbed ammonia, 81aryl halides, 378assignment, 309band widening, 36benzene, 367carbenium ions, 317, 361carbon dioxide, 134carbon monoxide, 96chlorofluorocarbons, 409chromium oxide systems, 33, 34, 270copper carbonyls, 201and copper content, 188ethene, 330, 332formates, 448, 450heteropoly compounds, 297, 302, 303, 305hydroxyl groups, 5859, 63intensities, 34iron oxide systems, 3738manganese dioxide, 39Ni-Y zeolites, 207nitric oxide, 126nitrogen, 120oxide systems, 32palladium carbonyls, 229platinum catalysts, 240surface isocyanate complexes, 157, 159vanadium catalysts, 260, 268

Absorption coefficients, 168Acetaldehyde

from ethene oxide, 496oligomerization, 431polymerization, 431

Acetaldehyde adsorption, 430435on vanadium systems, 435on zeolites, 430

Acetamide, 415Acetate ion, 453

Acetatescarboxylates, 453Acetic acid, complexation, 453Acetone, 256, 321, 423, 431

desorption, 445dissociation, 444from propene, 507transformation, 531532

Acetone complexation, 442445absorption frequencies, 444on alumina, 443on oxides, 442445on titanium dioxide, 445on zeolites, 442

Acetonitrile, 84, 411415, 520cation complexes, 413414hydrogen bonding, 412413ion pair complexes, 414415IR frequencies, 414IR spectra, 412, 413polymerization, 415silicon dioxide, 412413zeolites, 413

Acetylene, 138, 174, 348adsorption, 381, 385polymerization, 382as probe, 385spectral data, 384

Acetylide, 386, 388Acid-base pairs

alumina, 101hydrogen adsorption, 117, 118

Acidic protons, 291Acidic surface properties, 161171Acidity, measurement, 164Acrolein, 321, 351, 435439, 520

absorption bands, 437catalysis rates, 530hydroxyl groups, 436

Molecular Spectroscopy of Oxide Catalyst Surfaces. Anatoli Davydov 2003 John Wiley & Sons, Ltd ISBN: 0-471-98731-X

644 INDEX

Acrolein (continued )with metal cations, 436438molecular orbitals, 435oxidation, 526531on oxides, 439polymerization, 528production, 499505surface complexes, 438with surface oxygen, 438439thermal desorption, 503

Acrylates, 321, 354, 438439, 455, 527Acrylic acid, 406

adsorption, 527, 529complexation, 453455IR characteristics, 454thermodesorption, 453

Acrylonitrile, 520, 522Active centers, numbers of, 169, 177Active sites, 2831Adipodinitrile, 415Adiponitrile, 524Adsorbateadsorbent systems, 10Adsorption capacity, and pH, 254Adsorption centers, 29

cations, 200Adsorption sites

charge states, 271and stretching frequencies, 271275

Aerogels, 60Aerosil

hydrogen bonding, 431proton affinity, 164spectra, 152

Aerosilogel, 413Aerosols, silica, 60Ag/CaO systems, 225AgX zeolite, 330Air pollution, 146Al-O vibration mode, 41Al-O-Al bonds, 67Alcoholates, 341, 400, 401, 421425,

533Alcohols

chemisorption energies, 419complexation, 416430copper-containing catalysts, 477dehydration, 532536dehydrogenation, 536538halogenated, 427hydrogenation, 477on oxides, 421427saturated, 416427silver catalysts, 539542synthesis and decomposition, 475479

transformation, 532545zeolites, 416420on zinc oxide, 476

Aldehydes and ketonescomplexation, 430445hydrogenation, 532transformations, 526531

Aldol condensation, 430Alkali earth metal oxides, surface properties, 4143Alkali halides, hydrogen adsorption, 114Alkanes

oxidation, 480partial oxidation, 515518

Alkanes adsorptiondissociative forms, 399407effects on OH groups, 390HNaY zeolites, 390IR spectra, 397, 403two-center, 396zirconium dioxide, 404

Alkanes complexation, 389407interactions with cations, 392395interactions with OH groups, 389392, 399

Alkenesat Brnsted acid sites, 487at Lewis acid sites, 487and cation-anion pairs, 342350coordination, 336deuterated, 489fragmentation, 354hydrogen bonding, 484hydrogenation, 488490interactions with cations, 327350isomerization, 483488metal oxide systems, 319327metathesis, 499nickel-containing systems, 493495oligomerization and polymerization, 490498oxidation, 480partial oxidation, 499509 -complexes, 324, 488selective transformations, 483499

Alkenes complexation, 310355with OH groups, 310313with surface oxygen, 351355

Alkenoxides, 351353Alkoxides

bonding, 319formation, 315, 401, 538, 539interactions, 535surface, 421

Alkoxy compounds, 313327, 402, 417, 422, 425Alkylaromatic compounds, 511, 512

absorption frequencies, 371

INDEX 645

Alkynesaromatic, 388IR spectra, 387oxidation, 480

Alkynes complexation, 381388aluminum oxide, 385386silicon dioxide, 381titanium dioxide, 387388zeolites, 381382zinc oxide, 386

Allyl anions, 485486Allyl bromide, 501

thermal desorption, 503Allyl carbocations, 315Allyl cations, 518Allyl fragments, 314, 315, 347Allyl halides, 351Allyl radicals, 321Allylbenzene, 373, 374, 375

IR frequencies, 374Allylcyanide, 415Allylic cations, 392Allylic complexes, 342348

aluminum oxide, 344345Bi-Mo catalysts, 499500copper-containing systems, 346348energy diagram, 348magnesium oxide, 345346zinc oxide, 343344

-centers, 138-sites, 487Alumina

ammonia and pyridine adsorption, 7880,8687

boron-containing compounds, 292carbon monoxide adsorption,

101102chromium catalysts, 269defect sites, 101fluorinated, 251hydrated, 41Lewis acid sites, 8687model surface, 65, 66surface dehydration, 86

Alumina-palladium catalysts, 235Aluminosilicates, 291

fluorination, 285zeolites, 63

Aluminumcoordination number, 65four-coordinated, 65

Aluminum ionscoordination, 87in zeolites, 185

Aluminum oxidecarbon dioxide adsorption, 175hydrogen adsorption, 116hydrogen sulfide adsorption, 142hydroxyl groups, 6568, 66proton-donating centers, 92spectra, 38sulfur dioxide adsorption, 150, 151surface isocyanates, 158surface properties, 4041unsaturated cations, 169water adsorption, 122

Aluminum oxifluoride, 409Aluminum sulfate, 290Aluminum-alkyl compounds, 404Amides, 83

vibrational frequencies, 83Amines, 84, 147, 325Ammonia

coordinated, 78deformation vibrations, 85dehydrogenation, 518, 522desorption, 190dissociation, 69heat of adsorption, 85, 170ionization potential, 170pre-dissociation states, 88as probe, 142spectral characteristics, 79, 81, 82

Ammonia adsorption, 7884alkenes, 320, 325326chromium oxide, 8890copper oxides, 86Cu zeolites, 183184, 189, 193hydroxyl groups, 8084IR spectra, 267magnesium oxide, 87molybdenum oxide, 9192NiY zeolites, 208on platinum, 246schemes, 87spectra, 40, 285, 286titanium dioxide, 49, 88vanadium catalysts, 9192, 165, 260, 262,

264266zinc oxide, 8788

Ammonia centers, Lewis acids, 284Ammonia complexes, oxidised, 86Ammonia (pyridinium) ions, 78Ammoniates, 189Ammonium paramolybdate, 252, 256,

307Ammonium vanadate, 259Ammoxidation reactions, 518526

646 INDEX

Anatase, 48ethene -complexes, 331Lewis acid sites, 260nitrogen dioxide reactions, 133sulfate modified, 287surface, 72, 104surface forms, 104

Anatase-molybdenum oxide solid solution, 256Angle deformations, 10Anharmonicity constant, 10

OH bonds, 162Aniline, 367Anions, coordination environments, 171Anthracene, 368Antimonates, 75, 94, 518Antimony hexafluoride, 30Antimony oxide, 44

acrylic acid adsorption, 455ammonia adsorption, 91propene adsorption, 505surface, 428

Apparent absorbance, 5Aprotic sites

carbon dioxide adsorption, 138complex formation, 173

Aragonite structures, 292Aromatic compounds

chemisorption, 369on ferric oxide, 370ionic pair interactions, 373376IR spectra, 357, 361and oxide systems, 368373oxidised complexes, 376377ring opening, 379, 381side chains, 365surface oxygen complexation, 376378vanadium systems, 358362, 364, 375and zeolites, 366368

Aromatic structuresformation, 314ring vibration, 367, 381

Arrhenius plots, 462, 462Aryl compounds

complexation with oxygen, 376377oxidised complexes, 376377partial oxidation, 509514

Aryl compounds and aryl halides, complexation,355381

Aryl halide complexes, 378381cation interactions, 378379copper-containing systems, 379380IR spectra, 379, 380oxygen interactions, 379381vanadium systems, 378379

Arylaldehydes, 513Aryloxides, 362Asymmetric deformation, ammonia, 85Attenuated total reflection spectroscopy, 11, 1718

BO bond, 292Back-bonding, 337, 551Band splitting, copper, 182Barium oxide

carbon monoxide adsorption, 105oxygen absorption, 5253Raman spectra, 53surface properties, 41

Barium peroxide, 53Barium sulfate, 453Bases, protonated, 80Basic surfaces, properties, 171177Basicity, ammonia and pyridine, 78Bending vibrations, ammonia, 85Benzaldehyde, 375, 439440, 526Benzamide ion, 416Benzene

amine derivatives, 367hydrogenation, 490ionization, 178IR spectra, 356, 356oxidation, 510511ring opening, 376, 510

Benzene adsorptionon alumina, 369on haematite, 371on oxides, 348, 368on palladium, 234on platinum systems, 246on vanadium systems, 360and water, 370on zeolites, 367

Benzenium ions, 360Benzidine, 514Benzoate ions, 372, 376377, 439, 483Benzoic acid, 377, 455456, 511Benzonitrile, 84, 415416, 524Benzyl compounds, 372, 375, 513, 525Benzylacetophenone, 443Benzylimine, 416Bi-Mo oxide catalysts, 499500Bicarbonate structures, 136Bimolecular initiation, 392Binary oxides, 86, 425Binuclear bridging complexes, 287Biphenyl, 368Bismuth molybdate, 500Bismuth oxide, hydrogen sulfide adsorption, 145Bismuth vanadomolybdate catalysts, 520

INDEX 647

Bisulfite complexes, 150, 153Bisulfite ion, 149Boemite, 67Bond dissociation energy, OH bonds, 162Bond multiplicity, 34Bond stability, 274Bond stretching, 10Bond synergy, 201Borates, 292Boron oxide, 292Boron-modified systems, metal oxides,

291294Boron-oxygen surface compounds, 292Boron/titanium dioxide IR spectra, 293Bragg reflection, 23Branched oligomers, 3144-Bromoacetophenone, 443Brnsted acid sites

alcohols, 539alkenes, 319ammonia and pyridine adsorption, 9295methane adsorption, 390oligomerization, 314properties, 166sulfate-modified systems, 290, 291vanadium catalysts, 263, 267, 268water adsorption, 122

Brnsted acids, 30criteria, 78hydroxyl groups, 63, 75, 122strengths, 165

Brnsted basesmagnesium oxide, 348350zinc oxide, 350

Brukite, 71Bulk adsorbents, IR absorbance, 31Butadiene

adsorption, 318, 323, 325326, 494hydrogen bonding, 313hydrogenation, 489ionic structures, 325spectra, 318, 324, 325

Butane, 406dehydrogenation, 506, 518oxidation, 480, 481zirconia interactions, 391

tert-Butanol, 5351-Butanol, on zeolites, 419Butenes, 138, 375

chemisorption, 350complexes, 506isomerization, 485, 486, 487, 493oxidation, 506 -complexes, 341

vanadium catalysts, 322on ZnO, 344

tert-Butyl acetylene, 386But1-yne, 386

CH bondsactivation, 389, 395407, 500, 515dissociation, 342, 400, 486, 505loosening, 395399polarization, 396, 527

CaA zeolites, 140methane adsorption, 392

Cabosils, 60CaCo-Y zeolites, 218Calcite structures, 292Calcium molybdate, IR spectra, 307, 307Calcium oxide

carbon dioxide adsorption, 175carbon monoxide adsorption, 105, 107hydrogen adsorption, 117hydrogen sulfide adsorption, 142sulfur dioxide adsorption, 150surface properties, 41

Calcium phosphates, 290CaNa-A zeolites, 393CaNa-X zeolites, 218Cannizzaro reactions, 420, 434, 534Carbanions, 342, 473474Carbene complexes, 406, 478, 491, 496Carbenium ions, 165, 313327, 342

alcohols, 416, 420alkenyl, 315, 318, 319, 324, 391alkylaromatic, 358366alkynes, 382385allyl, 316, 317aromatic compounds, 377formation, 323frequencies, 363methanol, 535methyl allyl, 318polyenyl, 317, 325toluene adsorption, 525unsaturated, 314

Carbocationic complexesalcohols, 420, 534alkylaromatic compounds, 512allyl, 488, 502transformations, 382

Carbon, Raman spectra, 457Carbon dioxide

absorption bands, 134cation interactions, 134chemisorption, 133, 137dissociation, 477

648 INDEX

Carbon dioxide (continued )formation rates, 482heat of adsorption, 177hydrogenation, 479interaction energies, 177poisoning experiments, 487as probe, 174and sulfur compounds, 142surface compounds, 138

Carbon dioxide adsorption, 133139aluminum oxide, 175calcium oxide, 175interaction with oxygen, 134136magnesium oxide, 175oxides, 137139strontium oxide, 177zeolites, 137

Carbon isotopes, 242, 246Carbon monoxide

activation, 472adsorption sites, 271and allyl anions, 350binding energy, 275in carbonyl complexes, 220chemisorption, 204, 231conjugated cyclic compounds, 106dimers, 106, 207electron donor properties, 272extinction coefficient, 105heat of adsorption, 95, 171hydrogenation, 476interaction with cations, 9597islands, 242molecular orbitals, 95, 96polymers, 106as probe, 48, 95, 142, 167, 217re-adsorption, 204 complexes, 96stretching vibrations, 216, 246, 272thermodesorption, 250

Carbon monoxide adsorption, 95114alumina, 41, 101102barium oxide, 105calcium oxide, 105, 107carbonate formation, 105cerium oxide, 478chemical shift, 109chromium oxide, 103, 114cobalt oxide, 112113, 218, 219copper chromate, 111copper oxides, 111112coverage and spectral data, 109Cu zeolites, 186, 190, 195, 196Fe zeolites, 222

ferric oxide, 102and hydrogen adsorption, 115magnesium oxide, 105109, 108molybdenum systems, 114, 257Ni zeolites, 211nickel oxide clusters, 216oxides, 100101, 258259palladium, 233, 248platinum systems, 240, 240, 245247, 249rare earth metal oxides, 109silver cations, 225solid solution spectra, 206spectral features, 99100, 258259strontium oxide, 105sulfate-modified systems, 290titanium dioxide, 103105tungsten oxide, 114vanadium catalysts, 114, 260, 263zinc chromates, 110zinc oxide, 96, 109110zirconium dioxide, 113, 476

Carbon monoxide IR spectra, 98cobalt systems, 113copper-containing systems, 196, 198, 471Fe zeolites, 223nickel-containing systems, 211, 214palladium compounds, 228, 229, 230platinum distribution, 241silver compounds, 226, 227on solid solutions, 206supported platinum, 238248vanadium catalysts, 264, 268on zinc oxide, 463

Carbon monoxide oxidation, 461466chromium oxide catalysts, 461462high temperature, 464rates, 464

Carbon monoxide reactions, 461479carbonization and hydroformylation, 473475

Carbon monoxide-ammonia co-adsorption, 105Carbon-carbon stretching frequencies

butenes, 344 -complexes, 333, 334

Carbon-halogen bonds, 352Carbon-oxygen bond, 96Carbonaceous deposits, 456Carbonate formation, 105, 110Carbonate groups, on surfaces, 34, 175Carbonate structures, 135, 138, 418Carbonate-carboxylate compounds, 461, 462

correlation, 135Ni zeolites, 212types, 135vibration frequencies, 134

INDEX 649

Carbonatesadsorbed, 174Cu zeolites, 196intermediates, 462, 465spectral features, 175

Carbonium ions, 322, 324, 488Carbonyl complexes

cations, 9597, 100copper systems, 465iron, 102palladium, 158spectral properties, 169zinc-containing systems, 110, 476

Carbonyl ligands, 282Carbonyls

formation, 402four-electron donor, 207

Carboxylatesalkanes, 402alkenes, 353355butene oxidation, 341decomposition, 464, 479formation temperatures, 353as intermediates, 479480, 483, 505,

527Carboxylic acids, 445, 453

as probes, 173Catalysis rates, and temperature, 480Catalyst deactivation, 456458Catalysts

bi-functional, 92industrial, 541

Catalytic cracking, isobutane, 490Cation exchange, zeolites, 64, 366, 442Cation states, 181Cation-oxygen bonds, 31Cationic modification, 308Cations

complexing capacity, 166neutralizing, 234

Cell reactors, 13, 14, 16for electron spectroscopy, 5high-temperature, 14for IR spectroscopy, 12schematics, 17

Cerium oxideadsorbed oxygen, 52CFCs, 410, 411silver stabilization, 226, 542

Cesium iodide disks, 31Cesium oxide, 226, 542Charge delocalization, 317Charge transfers, 2

sulfur dioxide, 148

Charge-transfer bandsCu zeolites, 190195Ni zeolites, 210

Chemical shift, 242, 394Chloride ions, site blocking, 105Chloroalkyls, 173Chloroaromatics, 173Chlorobenzenes, 378381Chlorofluorocarbons

aluminum oxide systems, 409cerium oxide, 410, 411chemisorbed species, 409chromium oxide, 409complexation, 407411Raman spectra, 410, 411silicon dioxide, 410, 411titanium dioxide systems, 408vibration frequencies, 408

Chloroform, as probe, 173, 174Chromate ion, 36Chromatography, desorption products, 309, 325Chromites, 483Chromium ions

alkene complexes, 352clustering, 269coordination by hydroxyl groups, 123coordinatively unsaturated, 35electron positivity, 35four-coordinated, 36oxidation potential, 36oxidation state, 491photoreduction, 270and pyridine, 90unsaturated, 103

Chromium nitrosyls, 270Chromium oxide

ammonia adsorption, 8890carbon monoxide adsorption, 103, 114chloride modification, 285desorption spectra, 463ethene adsorption, 354IR spectra, 33, 47Nitric oxide adsorption, 126128oxygen adsorption, 4548oxygen state at surface, 34reduction at surfaces, 48supported, 269water adsorption, 122123

Chromium oxide systems, vibrations, 3337Chromium 3+ states, on chromium oxide face, 34Chromium-CO complexes, 273Chromium-containing systems, 269271

olefin polymerization, 490491Chromium-oxygen bond, 35

650 INDEX

Chromium-oxygen systems, coordination states, 35,89

Chromocene, 284Citraconic anhydride, 511Claus process, 146CN stretching frequency, 412CNDO method, 329Co/Al2O3 catalyst, Raman spectra, 457Co/TiO2 systems, 219Cobalt

hexaaqua complexes, 217interactions with hydrocarbons, 218metallic, 219see also Palladium-cobalt systems

Cobalt aluminate, 219Cobalt carbonyls, 219Cobalt ions

coordination, 217reduction, 112, 219stabilization, 53titania-supported, 219

Cobalt oxidebinding energy, 482carbon monoxide adsorption, 112113, 219Raman spectroscopy, 279, 280surface properties, 43

Cobalt oxide-magnesium oxideadsorbed oxygen surface, 53solid solutions, 53, 112, 219, 505

Cobalt oxide-zinc oxide systems, 219Cobalt-boron-titania catalysts, 294Cobalt-containing systems, 217220

oxides, 218220zeolites, 217218

Combination bands, 10CoNa-X zeolites, 218Conjugated cyclic compounds, carbon monoxide,

106Conjugated mechanism, 481Conjunction mechanism, 464Coordination number, metal atoms, 34, 35Coordination states

chromium-oxygen systems, 35ligands, 35

Coordinative saturation values, surface cations, 34Coordinatively unsaturated ions, 181Copper

absorption spectra, 203coordination states, 111hydrated complexes, 188, 189metallic, 203zero-valent, 203see also Cu

Copper acetate, 455

Copper carbonyl complexesabsorption bands, 201, 203, 204ESR, 186oxide surfaces, 201 -bonding, 274WGS reaction, 470, 471, 472473

Copper chromate, carbon monoxide adsorption, 111Copper chromite, 111

water-gas shift reaction, 471472Copper content, and absorption band, 188Copper dimers, 200

bridged, 194Copper hydrates

charge transfer band, 191splitting parameter, 188

Copper ionscharge transfers, 190195clusters, 197coordination state, 194195dd transitions, 187190electronic states, 182exchange interactions, 185magnetic interactions, 185187paramagnetic interactions, 185redox mechanisms, 550reduction, 185, 202, 549states and transformations, 184types, 184, 189weak adducts, 195weak associates, 189

Copper oxideacrolein production, 499ammonia adsorption, 86carbon monoxide adsorption, 111112nitric oxide adsorption, 128surface properties, 43, 531

Copper oxide-magnesium oxide system, 192, 194,217

Copper oxide-silica fixation, 202Copper phenolate, 381Copper-containing systems

allylic complexes, 346348cation states, 182207oxides, 200207zeolites, 182201

Copper-magnesium oxide catalysts, 188Copper-nitric oxide complex, 200Copper-palladium systems, 237Copper-zinc oxide catalysts, 201Corundum

crystallization, 65decomposition, 67surface planes, 35

Covalent bonds, CuO, 194

INDEX 651

Crotonaldehyde, 430, 435Crotononitrile, 415Crystal fields, copper ions, 182Crystal structures, identification of, 27Crystallographic phases, 32Crystallographic shear, 179Crystobalite, 61, 62Cu zeolites

carbon monoxide adsorption, 186, 190, 195charge-transfer bands, 190195infrared spectra, 195200nitric oxide adsorption, 198

Cu-mordenite, 549Cu-O covalent bond, 194Cu-ZSM-5 zeolites, 207Cu/TiO2 catalysts, 206Cu/Zn/Al oxide solid solutions, 204Cu/ZnO systems, 204, 205

boundary species, 248Cu/ZnOAl2O3 systems, 205Cumene, 355, 368CuNaY zeolites, electron spectra, 188CuO-MgO systems, 205CuO/ZnO/ZrO2 catalysts, 207CuO/ZrO2 catalysts, 207Cutoff frequencies, 31, 36CuY zeolites, 183

ESR spectra, 186CuY-A zeolites, 187, 192, 195, 200CuY-I zeolites, 187

charge transfer spectra, 191, 192dehydration, 191, 192electronic spectra, 187, 193

CuZSM zeolites, 547552Cyclic anhydrides, 322Cyclic structures, haematite, 7071, 70Cyclization, 3141,3,5-Cycloheptratriene, 496Cyclohexane, 395, 398, 399, 404

ammoxidation, 523524IR spectra, 523

Cyclohexanol, dehydrogenation, 536Cyclohexanone, 431Cyclohexene, 3552-Cyclohexen-1-one, 431Cyclopentadienyl chromium, 284Cyclopentanone, 431Cyclopentene, 489Cyclopropane, 315, 392, 406

dd transitionscopper ions, 187190nickel ions, 210

Dative bonding, 271

Deconvolution procedure, 165Dehydroxylation, 77, 94

Lewis acidity, 88Delocalized electrons, 328Delocalized protons, 75Desorption, stepwise, 309Deuteration

pyridine, 93reagents, 315silica, 40

Deuterium adsorption, on zeolites, 116Deuteroacetylene, 386387Deuteroalkenes, 334Deuteroethene, 169Deuteropropene, 169, 485, 487Dewar-Chatt-Duncanson model, 327, 430, 436Diammoniates, 190Dibenzene-chromium, 370Dicarbonyl complexes, 100, 103, 495Dichloromaleic anhydride, 442Dienes, 316, 318Diffuse reflectance electron spectroscopy

boron-modified systems, 292, 293cobalt catalysts, 281copper-containing systems, 203silver-containing systems, 223225, 541zeolites, 181

Diffuse reflectance infrared spectroscopy, 18hydrogen and nitrogen adsorption, 114nitrogen adsorption, 119

Diffuse reflectance spectroscopy, 5, 12basic surfaces, 172

Diffuse reflectance UV spectroscopy, allyliccomplexes, 349

Diffuse reflectance UV-Vis spectroscopy, 260, 263Diffuse scattering spectra, vanadium oxides, 762,5-Dihydrofuran, 506Dilution media, infrared transmission spectra, 11Dimethoxymethane, 537Dimethyl acetylene, 385Dimethyl ether, 419, 534, 5441,3-Dimethylnaphthalene, 356, 364, 366Dinitrosyl complexes, 548Dinitrosyl groups, 126, 127, 128, 257, 262, 269,

495, 548, 549, 551Dioxygen compounds, 38Dioxymethylene, 431, 434, 537

absorption frequencies, 4321,1-Diphenylethene, 358Dipole charges, 5, 22Dipoledipole interactions, 185, 247Dispersed oxide catalysts, vibrational spectra, 31Dispersion, in samples, 34Disproportionation reactions, 420, 434, 514, 534

652 INDEX

Donor capacity, 169Donor-acceptor interactions, metal carbonyls,

282Double-center adsorption, 173Dynamic allyls, 501Dynamic shift, 242

E-sites, 486487Electromagnetic spectrum, 2Electron acceptor capacity, 170Electron concentration, semiconductors, 55Electron delocalization, 332Electron donation, 178Electron energy loss spectroscopy, 5, 2122Electron paramagnetic resonance data, 551Electron paramagnetic resonance spectroscopy,

179Electron positivity, chromium ions, 36Electron proton resonance spectroscopy, 48Electron spin resonance spectroscopy

adsorbed oxygen, 44basic surfaces, 172carbonyl complexes, 96cation-exchanged zeolites, 271copper ion parameters, 184hydrogen sulfide adsorption, 145molybdenum systems, 253, 254, 256palladium zeolites, 232sulfur dioxide, 150, 155vanadium catalysts, 268Y-zeolite spectrum, 183

Electron transfers, 4Electron-adsorbate interactions, 2122Electronic factor, 250, 335Electronic resonance, 21Electronic spectroscopy, 15Emission spectroscopy, infrared, 1415Energy levels, 2, 8Enolates, 426, 443, 445, 536Equilibrium distance, OO bond, 48Erbium oxide, 73Esterification reactions, 362, 422Esters, 147Ethane, ammoxidation, 522523Ethane adsorption

Cr-Mo catalysts, 398399dissociative, 404zirconium dioxide, 396

Ethanoladsorption, 319, 476on alumina, 422conversion to hydrocarbons, 544545dehydrogenation, 543on zeolites, 419

Ethene, 169carbon-carbon stretching, 311, 335copper systems, 337dimerization, 493, 494dissociation, 492formation, 405heat of adsorption, 330hydroformylation, 474475hydrogenation, 490IR frequencies, 333, 338IR spectra, 331low-temperature interactions, 339molecular orbitals, 327nickel-containing systems, 494oligomerization, 493, 494oxidation, 508509, 556 -complexes, 489, 490, 492, 508polarization, 328polymerization, 342, 490496protonation, 165substituted, 386surface-reaction kinetics, 488489symmetry, 337total intensities, 312transition metals, 332vanadium-containing systems, 495wavenumbers, 312

Ethene adsorptionon platinum, 246on silver, 509

Ethene oxidealuminosilicate systems, 496and basic oxides, 497498on oxides, 497polymerization, 496498radical mechanism, 497on silver systems, 509

Ethene-hydroxyl complexes, 311Ethene-metal complexes, 337Ethers, 352, 417, 425Ethoxy groups, 401, 422, 495Ethyl acetylene, 381Ethyl chloride, 401Ethylbenzene, 370, 377

oxidative dehydrogenation, 514Ethylene see EtheneEthylidene complexes, 341342, 493Ethynylbenzene, 373Exchange interactions, copper ions, 185, 187,

198Exciton absorption processes, 42Experimental conditions, choice of, 310Experimental principles, 67Extended Huckel method, 333

INDEX 653

Extended X-ray absorption fine structurespectroscopy, 257

Extinction coefficientsammonia, 165carbon monoxide, 105copper ions, 187

Factor group analysis, 27Faujasite, 149, 328, 368

structure, 30Fe-Y zeolites, 220Fe/Sb oxide systems, 44Fermi level, 228Fermi resonance, 411, 447, 534Ferric ion, coordination states, 90Ferric oxide

alkene -complexes, 337ammonia and pyridine adsorption, 9091carbon monoxide adsorption, 102disordered face, 91heat treatment, 70hydrogen sulfide adsorption, 145hydroxyl groups, 6971IR spectra, 38oxygen adsorption, 52spectra, 517sulfate modification, 287surface properties, 3738water adsorption, 122

Fischer-Tropsch synthesis, 458Flow reactor cells, 464Fluorine and chlorine-modified systems, 285286Fluorobenzene, 362Foliated pie method, 49Formaldehyde, 256, 399, 420, 425

absorption frequencies, 432on cerium oxide, 434chemisorption, 433complexation, 430435industrial production, 541oxidation, 515, 531, 537on oxides, 431435polymerization, 433on vanadium systems, 434435yield, 541, 542

Formate ions, 431, 433, 446Formate-carboxylate surface compounds, 446, 448Formates

absorption frequencies, 353, 400, 448, 450activation energies, 448in alcohols complexation, 418, 426, 476in alkane complexation, 392in alkene complexation, 352in alkyne complexation, 387

formation mechanisms, 448as intermediates, 481IR spectra, 449in propene oxidation, 502thermal stability, 448WGS reaction, 467469zinc-containing systems, 110

Formic acid, 531complexation, 445452copper-containing systems, 450452dehydration, 445hydrogen bonding, 446, 449IR band assignments, 451IR spectra, 447physisorption, 446vanadium systems, 452

Formyl formation, 478Formylacetates, 439, 527, 528Fourier transform IR spectroscopy, 11, 15

alkanes, 390carbon monoxide, 100cerium oxide, 52metal oxide systems, 281platinum clusters, 251

Fundamental vibrations, 27Furan, 322, 440, 5062(5H )-Furanone, 506

Gallium sulfate, 290Gallium-containing systems, 519Gallium-molybdenum catalysts, 501gamma spectroscopy, 220Geometric effect, 243Geometric factor, 242, 247Glass, porous, 114Goethite, 69, 70, 122

modification, 287Gold, optical absorption spectra, 228Grain size effects, 281Graphite, 458Grinding, defect formation, 179Group characteristic, 10

H-H vibrations, 115Haematite, 69, 70

crystal structure, 70pyridine adsorption, 90water adsorption, 122

Hafnium oxide, 290Halogen atoms, donor ability, 407Halogen exchange reactions, 409Halomethanes, 402Hammet method, 161Hard acids and bases, 77

654 INDEX

Harmonic frequency, OH bond, 162Harmonic vibrations, Raman effect, 20Harrick Collector, 18Heterogeneous catalytic reactions, 459558Heterometallic groups, 251Heteropoly acids

acidic properties, 300303acrylic acid formation, 406ammonia and pyridine adsorption, 300effect of concentration, 301302effect of support type, 302FTIR, 281IR spectra, 255, 304, 306Lewis acid centers, 303pre-treatment, 302proton affinity, 166, 302proton replacement, 302303strengths, 164, 166supported, 68thermal stability, 303308

Heteropoly compounds, 30, 95, 128, 256, 294303alumina-supported, 298effects of supports, 295300IR spectra, 296, 297, 299, 301structure, 295

Heteropolyanions, 295Heteropolyoxoanions, 407Heteropolyoxometalates, 515Hex-1-ene, adsorption, 314Hexaammoniates, 208Hexachloroacetone, 443Hexafluoroacetone, 444Hexafluoropropane-2,2-diol, 444Hexafluoropropene, 409Hexamethylbenzene, 360, 364n-Hexane, aromatization, 2511-Hexene, production, 493High temperature treatment, 43

molybdenum systems, 95High-resolution electron energy loss spectroscopy,

29hydrogen adsorption, 118

Highest-occupied molecular orbital, 160, 430, 436,438

HM zeolites, 311HNaY zeolites, 149Holmium oxide, 73HY zeolites, 140, 149, 311, 355, 368, 417Hydride transfer, 389, 392Hydrides, 118, 496

linear, 116Hydroamino complexes, 195Hydrocarbon oxidation, 29, 479483

thermal desorption, 480

Hydrocarbonsactivation temperatures, 402alkylation, 544ammoxidation, 518526carbonization, 474chain fragmentation, 481demethylation, 483hydroxyl groups, 484partial oxidation, 499518reactions involving, 479526saturated, 315synthesis, 478479

Hydrocyanic acid, 520Hydrofluorocarbons, 407Hydrogen

activation, 488dissociation, 69, 350, 477dissociative adsorption, 117liquid and solid phases, 117oxidation, 465as probe, 114, 115production, 466

Hydrogen adsorption, 114119acid-base pairs, 117, 118aluminum oxide, 116bridged structures, 118calcium oxide, 117and carbon monoxide adsorption, 115dissociative, 348magnesium oxide, 117mode frequencies, 118platinum, 118, 119silanol groups, 115spectral characteristics, 115spectral features, 117strontium oxide, 117zinc oxide, 117zirconium dioxide, 116

Hydrogen atoms, in INSS, 23Hydrogen bonding

acetonitrile, 412413aerosil, 431alkanes, 395399alkenes, 311, 351, 483alkynes, 381382ammonia, 78, 80, 260aryl compounds, 376aryls, 355358, 376Brnsted acids, 92butadiene, 313formic acid, 446, 449haematite, 70halogenated hydrocarbons, 407hydrogen sulfide, 139, 144

INDEX 655

methanol, 426nitrogen dioxide, 132nitrogen dioxide dimers, 132propene -complexes, 336pyridine, 84silanols, 60, 62, 64sulfate-modified systems, 289titanium systems, 288unsaturated hydrocarbons, 337vanadium and molybdenum systems, 75water, 120

Hydrogen chloride, 138Hydrogen molecules

adsorption, 115dissociation, 116

Hydrogen reduction, spectra, 40Hydrogen sulfide

absorption forms, 144adsorption, 139145co-adsorption, 142deformation vibration, 144dissociative adsorption, 140, 142heat of adsorption, 144interaction with water, 142oxide system interactions, 145spectra, 143spectral bands, 141stretching vibration, 144surface compounds, 142

Hydrogen sulfide adsorptionaluminum oxide, 142calcium oxide, 142magnesium oxide, 142oxides, 141145silicon dioxide, 139140titanium dioxide, 142vanadium oxides, 145zeolites, 139140

Hydrogen-scrambling, 491Hydrosulfide ion, 140Hydroxo complexes, 208Hydroxoamino complexes, 193Hydroxonium ions, 121, 417Hydroxyl groups

absorption bands, 5859, 63acrolein, 436alcohols, 421alkanes, 392aluminum oxide, 6568, 66, 67ammonia adsorption, 8084aromatic compounds, 369bending vibrations, 61bridge type, 92, 122Brnsted acids, 122

on chromium oxide, 122123cluster models, 66and crystalline structure, 57CuO-MgO systems, 470ferric oxide, 6971hydrocarbons, 484and hydrogen adsorption, 115interactions with alkanes, 389392IR spectra, 418magnesium oxide, 6869molybdenum oxide, 7577rare earth metal oxides, 73, 74spinels, 7475stretching frequencies, 57, 60sulfate modification, 287titanium dioxide, 7273toluene, 356vanadium oxides, 7577zeolites, 6365zinc oxide, 7374zirconium dioxide, 73see also Surface hydroxyl groups

Hydroxyl stability, alkenes, 313Hydroxylation, solid, 120Hyponitrite ions, 553HZSM zeolites, 64, 115, 121, 132, 139

alcohols, 417aldehydes, 430alkanes, 390391alkenes, 311, 315, 317alkynes, 381, 382aromatic compounds, 365copper in, 207methane, 390, 394methanol, 418platinum, 250

I-sites, 486Imines, 526Imino compounds, 526Impact scattering, 22In situ measurements, 2425Inclusions, defects, 178Indicators, 161

spectroscopic peaks, 162Indium

ligand effect, 243and platinum, 251

Inelastic electron tunnelling spectroscopy, 22Inelastic neutron scattering spectroscopy, 5, 23Inelastic scatter, 19, 22Infrared cells, as reactors, 459Infrared diffuse scattering spectroscopy, hydroxyl

groups, 64

656 INDEX

Infrared ellipsometric spectroscopy, 23Infrared frequencies, oxygen bonds, 47Infrared spectra

adsorbed oxygen, 17oxidized catalysts, 40

Infrared spectroscopy, 5, 1118emission, 1415experimental installation, 24molybdenum systems, 256optical materials for, 13reflection, 1518transmission, 1114

Inorganic compounds, on active surfaces, 277308Integral absorbance, 168Integration spheres, 18Intermetallic compounds, 248Intermolecular interaction, 275Internal reflection spectroscopy, 1718Iodobenzene, 362Ion exchange conditions, copper ions, 183Ion exchange salts, hydrolysis, 194Ionic pair interactions, aromatic compounds,

373376Iridium

isocyanate complexes, 161nitrogen adsorption, 119SO2complexes, 148

Ironclusters, 478nitrogen adsorption, 119see also Fe, Ferric

Iron carbonyl, 102Iron containing systems, 220223

in benzene oxidation, 511oxides, 223types of sites, 222zeolites, 220222

Iron peroxide, 406Iso-synthesis, 478Isobutane

adsorption, 396catalytic cracking, 490IR spectra, 391, 397

Isobutanoladsorption, 476, 535ammoxidation, 526

Isobutene, 322Isobutyonitrile, 526Isocyanate, as probe, 161Isocyanate complexes see Surface isocyanate

complexesIsocyanates

extinction coefficient, 519molecular orbitals, 160

Isopentene, 495Isopolyanions, 295Isopolymolybdates, 252Isopropanol

adsorption, 319, 423, 425, 476, 534, 536as intermediate, 507

Isopropoxy compounds, 321, 423, 507508Isopropyl alcohol see IsopropanolIsopropylbenzene, 356Isotopic effects, band shifts, 34, 318, 335Isotopic exchange, 8, 315

Jahn-Teller effect, 182

Keggin structure, 30, 166, 303, 304, 438, 518Ketones, 147, 170, 443Kirchoff law, 15KL zeolite, 251KramerKronig equation, 15KRS crystal, 18Ksonotolite, 62Kubelka-Munk function, 5, 18, 187KX zeolites, 137

Lactones, 506Lambert-Beer law, 4, 11, 14, 15, 25Langmuir-Hinshelwood mechanism, 460, 514, 557Lanthanide ions, 479, 558Lanthanum oxide, 175, 226, 235, 279Laser development, for Raman spectroscopy, 20Lattice absorption limit, 31Lattice defects, 27, 178Lattice modes, overtones, 43Lewis acid sites, 85, 166171

absorbance coefficients, 168anatase, 260benzonitrile, 416concentration, 171heteropoly acids, 303oligomerization, 314properties, 171sulfate-modified systems, 291vanadium catalysts, 264

Lewis acids, 30, 40adsorbed pyridine, 84, 93on alumina surfaces, 67, 102, 402centers, 78chromium oxides, 90classification, 77hydrogen sulfide adsorption, 142

Lewis acids and bases, classification, 77Lewis bases, on rutile, 72Ligand effect, 243Ligand-metal bonds, degree of covalence, 191

INDEX 657

Ligandscoordination state, 35coordinative, 195

Linear defects, 178Linear oligomers, 314Linkam Scientific Instruments, 20LiX zeolites, 137, 430Low-temperature measurements, 114Lowest-unoccupied molecular orbital, 148, 438Luminescence, emission, 42

Madelung energy, 41, 42, 172Magic angle spinning, 392Magnesia, incorporation of molybdenum, 92Magnesium acrylate, 439Magnesium methylate, 404Magnesium molybdate, 92Magnesium oxide

ammonia adsorption, 87as Brnsted base, 348350carbon dioxide adsorption, 175carbon monoxide adsorption, 105109, 108defect sites, 108desorption spectra, 69hydrogen adsorption, 117hydrogen sulfide adsorption, 142hydroxyl groups, 6869solid solutions, 109spectra, 42surface plane, 43, 68surface properties, 41water adsorption, 122

Magnesium sulfate, 290Magnetic interactions, copper ions, 185187Maleates, 440442Maleic acid, 440Maleic anhydride, 322, 341, 406, 440442

absorption frequencies, 441in butene oxidation, 506

Malonates, 439, 528Manganese, ligand effect, 243Manganese dioxide, surface properties, 39Manganese hydroxides, 39Mars-van Krevelen mechanism, 460, 514, 515Mass spectroscopy, desorption products, 309Matrix-isolated techniques, 201Mechanical activation, 179Mesityl oxide, 443Mesitylene, 360, 364Metal carbonyls, 95, 274, 282284Metal clusters, 181Metal dispersion, 228Metal nitrosyls, 282284Metal oxide crystallites, 278

Metal oxidesboron-modified systems, 291294dehydrated, 278interactions with acids and bases, 284294modifiers, 281monolayers, 278, 281sulfate modification, 286290

Metal peroxides, 52Metal reflectors, 17Metal sulfides, 139Metal-CO complexes

adsorption sites, 272275molecular orbitals, 273stability, 272

Metal-dioxygen interactions, 45Metal-methyl groups, 516Metal-oxygen bonds, vibrations, 3244Metal-oxygen double bonds, 31Metal-support interaction, 223

platinum, 248Metallocyclic compounds, 493Metals

NO adsorption, 125sorption capacity, 247

Methacrylonitrile, 415Methane

carbonization, 475coupling catalysts, 177dissociation, 404, 405heat of adsorption, 394interactions with OH groups, 389392NMR spectroscopy, 394oxidation, 400, 516518oxidative dimerization, 515spectral characteristics, 389vibration frequencies, 389

Methane activation, 392Methane adsorption, 43

alumina, 398, 402aluminum oxide, 392Brnsted acid sites, 390CaA zeolites, 392calcium oxide, 396chromium oxide, 400CsY zeolites, 395DRIR spectra, 400ferric oxide, 400IR spectra, 398IR spectral data, 393magnesium oxide, 398, 404NaA zeolites, 392NaX zeolites, 392NaY zeolites, 395silicon dioxide, 390, 399

658 INDEX

Methanoladsorbed forms, 424chromium oxide, 423conversion to hydrocarbons, 544546decomposition, 533dehydration, 533dehydrogenation, 543desorption, 417on ferric oxide, 427hydroformylation, 474and hydroxyl groups, 422IR spectra, 418, 517IR spectral data, 427oxidation, 256, 434, 538545radical reactions, 544synthesis, 450, 475477on titanium dioxide, 423on zeolites, 419

Methanol to gasoline reactions, 535Methoxides, 401, 427Methoxy groups, 404, 417, 423, 425, 431, 476,

516, 534Methoxylation, silica, 40Methoxyls, 418, 419, 420, 422Methyl acetylene, 350, 381, 386, 387Methyl ethyl ketone, 322Methyl formate, 473, 537Methyl groups, 521

IR spectra, 4052-Methyl propane see Isobutane2-Methyl-2-propanol, on zeolites,

419Methylallyl compounds, 345Methylaryls, ammoxidation, 510Methylates, 401Methylbenzenium ion, 360Methylcyclopropane, 496Methylene groups, 375, 521Microcalorimetry, 122Microgravimetric measurements, 201MINDO/3 method, 66Mirror reflection see Reflection-absorption IR

spectroscopyMobile protons, 288, 301Model catalytic systems, 31, 294Molar absorption coefficient, 4Molecular orbitals

carbon monoxide, 96dioxygen molecule, 45ethene bonding, 327isocyanates, 160metal-CO complexes, 273NH, 85Nitric oxide, 124

nitrogen dioxide, 128, 131sulfur dioxide, 147

Molecular radical-ion adsorption, 44Molecular spectroscopy, used for analysis, 309Molecules

diatomic, 8fingerprints, 27polarizability, 19

Molybdates, 75, 94, 252253, 518modified, 305308

Molybdenumorganometallic compounds, 282see also Heteropoly acids; Heteropoly

compoundsMolybdenum carbonyls, 283284Molybdenum compounds, thermal stability,

303308Molybdenum ions

Brnsted acidity, 539coordination, 253, 254, 256reduction temperature, 305

Molybdenum oxideammonia and pyridine adsorption, 9192carbon monoxide adsorption, 114DRES spectra, 179hydroxyl groups, 7577IR spectra, 307stability, 303305surface properties, 39

Molybdenum systems, 94Molybdenum tartrate, 255Molybdenum-aluminum oxide catalysts, 252253

Raman spectra, 279Molybdenum-containing systems, 252257Molybdenum-oxygen bonds, 295Molybdenum-silicon oxide systems, 253255

products, 254Molybdenum-titanium oxide catalysts, 255257Monoammoniates, 190Monovanadate groups, 259Mordenite, 100, 117, 150, 174, 251, 548, 558Mossbauer spectroscopy, 220, 271Multilayer coating, 151

NaA zeolites, 54, 140methane adsorption, 392, 393

Naphthalene, 368, 510Naphthylamine, 368Natural gas, 515NaX zeolites, 116, 137, 140, 149, 392NaY zeolites, 115, 140, 149Nephelauxetic series, 191Neutron scattering, methane adsorption,

393394

INDEX 659

Ni zeoliteselectronic spectra, 207211infrared spectra, 211215

Ni-Cu-Cr oxide catalysts, 207Ni-Y zeolites

absorption bands, 207electronic spectra, 208

Nickelemission spectra, 241hexaaqua complexes, 208metallic, 214, 217SO2 complexes, 148supported, 241titania-supported, 217see also Ni

Nickel allyl, 282Nickel ammoniate, 208Nickel carbonyls, 215, 283Nickel ions

in alkene polymerization, 494clusters, 208coordination, 209, 210, 217oxygen bridges, 212

Nickel oxideadsorbed oxygen, 54clusters, 217oxygen chemisorption, 56surface properties, 44

Nickel oxidemagnesium oxide solid solutions,217, 505

Nickel-containing systems, 207217oxides, 215217zeolites, 207215

NiO/NiY, 212Niobia, 269Nitrate ions, 132, 554Nitrates, 123, 128, 132, 133Nitric oxide

absorption bands, 126activation energy, 547adsorption, 123130and ammonia, 556decomposition, 127, 545552, 553dimers, 126, 128, 200molecular orbitals, 124and oxygen adsorption, 127as probe, 217spectral characteristics, 129spectral features, 125, 127surface treatment, 86

Nitric oxide adsorptionchromium oxide, 127128copper oxides, 128, 545Cu zeolites, 198, 545547

Fe oxides, 223Fe-Y zeolites, 220Ni zeolites, 213palladium zeolites, 231235ruthenium, 126spectral characteristics, 127, 198vanadium catalysts, 262, 268, 556557

Nitric oxide IR spectraCu zeolites, 201Fe zeolites, 221Ni zeolites, 213, 215Pd zeolites, 232, 233vanadium catalysts, 262, 262, 268

Nitric oxide-copper complexes, 546Nitric oxide-metal complexes, 125Nitric oxide-propene-oxygen mixtures, 556Nitrides, 119Nitriles, 84, 147, 518Nitriles complexation, 411416Nitrite ion, 132, 553Nitrites, 123, 128p-Nitroaniline, 367Nitrobenzene, 179, 367, 513Nitrogen

absorption bands, 120heat of adsorption, 119as probe, 114

Nitrogen adsorption, 119120iron, 119Raman spectra, 119spectra, 120

Nitrogen dioxidedimerization, 130, 132free radical species, 132molecular orbitals, 131

Nitrogen dioxide adsorption, 130133Pd zeolites, 232titanium dioxide, 133, 557zeolites, 132

Nitrogen oxide see Nitric oxideNitrogen oxides

and ammonia, 556558reduction, 552556reduction by hydrocarbons, 554556selective catalytic reduction, 554, 556stretching vibrations, 124, 125

Nitrogen-containing systems, transformations,545558

Nitronium ion, 130, 133Nitrosobenzene, 514Nitrosonium ion, 123, 128, 551Nitrosyls, 551

chromium, 270iron, 160

660 INDEX

Nitrosyls (continued )Mossbauer spectroscopy, 220stability, 275

Nitrous oxide, 200, 269, 554formation, 548

NiY zeolitesammonia adsorption, 208dehydrated, 208209electronic spectra, 209

NiY-A zeolites, 211, 212dehydration, 208

NiY-I zeolites, 209NO + CO mixtures, 552554NO + hydrocarbons reactions, 554556NO bonding, classification, 125NO stretching vibrations, 130Noble metals

carbonyl complexes, 227hydroformylation, 474

Non-crystalline phases, 28Nuclear magnetic resonance spectroscopy

methane, 394mordenite, 166propane, 392

Nucleophilic attack, 44Nucleophilic substitution, 438

O-O bond, equilibrium distance, 49O-O vibrations, 45, 48OH groups see Hydroxyl groupsOH stretching vibration, 57, 311

haematite, 71Olefin complexes, on oxide surfaces, 331Olefin-oxygen complexes, 482Olefins, 168

adsorption centers, 504aluminum systems, 355bending modes, 311heat of adsorption, 331isomerization, 485molybdenum-containing systems, 495partial oxidation, 499509vanadiumphosphorus systems, 341

Oligomerization, 314, 322, 345acetaldehyde, 431alkynes, 388nickel ions in, 216

Oligomersformation, 314, 315, 317, 326neutral, 384

Optical density, 4Optical materials, for infrared spectroscopy, 13Optical spectroscopy, cation-exchanged zeolites,

271

Organic acids, complexation, 445456Organic molecules, surface complexes,

309458Organometallic complexes, 281282

supported, 277Orthoborates, 292Orthophosphoric acid, 305Oscillator

anharmonic, 10harmonic, 8

Oxalates, 287Oxidant molecules, 181Oxidation, catalytic, 194Oxide conductivity, 5556Oxide ions, low coordination, 42Oxide particle size, 11Oxide surface centers, solid structures, 2728Oxide surfaces, spectra, 3176Oxide systems

absorption bands, 32surface properties, 4344

Oxide-hydroxyl-hydrate systems, 77Oxides

carbon monoxide adsorption, 100101supported, 20

Oxidized catalysts, infrared spectra, 40Oxo-cations, 549Oxoanions, polymeric, 295Oxonium ions, 419, 533, 544Oxygen

dissociative chemisorption, 462and hydrocarbon oxidation, 481isotopic exchange, 5455isotopic mixtures, 46, 48molecular forms, 4456, 481non-lattice, 209reactive, 354reactivity, 197uncharged species, 5455

Oxygen adsorptioncarbonate formation, 462chromium oxide, 4548cobalt oxide-magnesium oxide, 53ferric oxide, 52interactions with carbon dioxide, 134136low temperature, 54model, 49nickel oxide, 54tin dioxide, 5052titanium dioxide, 4850

Oxygen bondsinfrared frequencies, 47vibrational frequencies, 46

Oxygen ions, adsorbed on cations, 34

INDEX 661

Oxygen moleculesdissociation, 48inactivity, 54

Oxygen spectraon tin dioxide, 50, 51on titanium dioxide, 49

Oxygen states, on oxide surfaces, 44Oxygen-cation bonds, 34, 233Oxygenates, 474Oxymethyl groups, 405Ozone see Trioxygen molecule

P-Mo-anhydride, 304Palladium

carbonyl complexes, 158, 228, 228231,233

clusters, 231(CO)(NO) complexes, 234metallic, 231, 234oxides systems, 235237re-oxidation, 234see also Pd

Palladium catalysts, spectroscopic characteristics,236

Palladium ions, 228coordination, 232reduction, 237

Palladium nitrosyls, 234Palladium oxide, 237Palladium zeolites

carbon monoxide adsorption, 232nitric oxide adsorption, 231235

Palladium-cobalt systems, 235Palladium-containing systems, 228237

oxides, 235237zeolites, 228235

Paraffins, 174activation, 400ammoxidation, 520523dehydrogenation, 406

Paramagnetic ions, ESR, 185Paramagnetic oxides, 44Paramagnetic sites, 172Paramagnetic species, sulfur dioxide adsorption,

150Partial oxidation, olefins, 499509Particle sizes, decreasing, 179Pd-Y zeolites, 228Pd/Al2O3, 235Pd/MgO catalysts, 235Pd/SiO2 catalysts, 235Penta-ammoniates, 183, 189190Pentadienes, 326

IR spectra, 326

Peroxide intermediates, 502Peroxide species, 406, 515Peroxide systems, 52Phase states, IR spectroscopy in, 111Phase transitions, chromium oxide systems, 33Phenol, 427430, 510

absorption frequencies, 429acidity, 163IR spectra, 379

Phenolate complexes, 381, 428, 430Phenols, as probes, 173Phenylallyl anions, 373p-Phenylenediamine, 367Phenylpropynes, 373Phenyl-1-propynes, 388Phillips-type catalysts, 490Phosphates, 287, 290

protic acid sites, 166Phosphomolybdic acid, 166Phosphorus, as modifier, 305306Phosphotungstic acid, 128Photoacoustic spectroscopy, 1819Photoemission spectroscopy, 274Photoionization, zinc oxide, 204Photoluminescence, defect induced, 178Photoluminescence spectroscopy, 172Photoradiation, 493Photothermic effect, 18Phthalic anhydride, 511Phthalide, 511Phthalocyanine complexes, 284Physisorption, 311, 341

methanol, 419 -acceptors, 171 -allylic complexes, 342 -allyls

band intensities, 501propene adsorption, 502

-bonds, 271, 274borates, 292polarization, 367

-complexes, 166acrolein, 436alkenes, 327, 487see also specific alkenesalkynes, 385aryl compounds, 356, 366373benzene, 368binding energies, 336carboncarbon stretching frequencies, 333with cations, 328341heat of adsorption, 332on oxides, 331341stability, 334

662 INDEX

-complexes (continued )toluene, 359, 362on zeolites, 328331, 366368

-orbitals, NO, 123125pKa, X-H molecules, 349Planar defects, 178Plasma resonance absorption, 224Platinum

boundary complexes, 248boundary species, 248, 248cation states, 248252deposition, 239dicarbonyls, 251dispersivity, 239241, 239, 246electron density, 241, 246electronic states, 245, 246heat treatment, 235, 239hydrogen adsorption, 119isocyanate complexes, 161lateral interactions, 241242metal-support interaction, 248metallic, 235243molecular orbitals, 245particle sizes, 239, 241, 244promoters, 251re-oxidation, 251SO2 complexes, 148stabilization centers, 245, 246supported, 242, 243247, 246, 251surface inhomogeneity, 242see also Pt

Platinum carbonyls, 239, 244stretching vibrations, 244

Platinum distribution, carbon monoxide IR spectra,241

Platinum films, 248Platinum ions, oxidation state, 248Platinum silicides, 247Platinum-cobalt systems, promoters,

243Platinum-containing systems, 235249Point defects, 178Poisoning effects, 142Polarizable molecules, 77Polarization, paraffins, 174Poly-oxides, 304Polyacetylenes, 388Polycarbonium ions, 456Polycarbonyl complexes, 100Polycyclic aromatics, 392Polyenes, 317Polyenyl cations, 392

stability, 317Polyethene, 492

Polymerizationacetylene, 382cationic, 324ethene, 342, 490496ethene oxide, 496498

Polymolybdates, 253Polyolefins, 417Polyoxymethylene, 431, 434

absorption frequencies, 432Polysorption, water, 121Polyvanadates, 259Potassium bromide disks, 31Potential energy functions, 9, 11Precise catalysts, 277Preserved center of gravity, 182Probes

for adsorption centers, 181ammonia, 78for basic sites, 173criteria for, 78protonated, 68pyridine, 78

Promoted metallic systems, 251Promotional additives, 235Propane

adsorption, 395, 401ammoxidation, 519, 519dehydrogenation, 516IR spectra, 401, 521nuclear magnetic resonance spectroscopy, 392

1-Propanol, on zeolites, 4192-Propanol, on zeolites, 419Propargyl ions, 350Propargyllic anion, 386, 388Propene, 169

adsorption, 262, 319on alumina, 344345ammoxidation, 518, 521copper oxide systems, 503deuterated, 343, 344, 350, 501dimers, 504dissociation, 522dissociative adsorption, 343, 345, 347heat of adsorption, 321, 344, 347interaction with zeolites, 315IR frequencies, 333, 339IR spectra, 320, 340, 346, 351, 353, 475, 504,

507magnesium oxide systems, 500metathesis, 499oligomerization, 493oxidation, 256, 482, 483, 513oxydehydrogenation, 507508partial oxidation, 351, 499505

INDEX 663

-complexes, 331, 336, 495, 500, 505polymerization, 504protonation, 165, 359spectra, 316zinc oxide systems, 502

Propene adsorption, on alumina, 101Propene peroxides, 502Propene-hydroxyl complexes, 3112-Propoxy group, 4952-Propylate complexes, 319, 320Propylene see PropeneProtic acid sites, 92, 162166

etherification, 425modified transition metal oxides, 285,

288strength determination, 163vanadium catalysts, 263, 425

Protic centersconcentration of, 68, 323oligomer formation, 322strength, 163

Proton affinity values, 162, 163, 164, 166Proton transfer

alcohols, 419ammonia, 80conjugate bases, 419

Protonic acid centers, 145Protons, mobile, 92, 93Pt/Si alloys, 247PtIn sites, 251Pyrazine, 385Pyridinates, 183, 190Pyridine

and chromium ions, 90complex formation, 167desorption, 84deuteration, 93heat of adsorption, 167, 413as probe, 93ring vibration, 84spectra, 93spectral ranges, 79

Pyridine adsorption, 75, 7880, 84alumina, 41Cu zeolites, 190on platinum, 246, 251rutile, 88zeolites, 183

Pyridine-SO2 complexes, 151Pyridinium ions, 84, 93, 286Pyrrole, 173

Quantitative measurements, 25Quartz, bulk phase, 61

Quartz cells, 13Quinine, 510

R-phase compounds, 74Raman anti-Stokes scattering, 19Raman effect, energy-level transitions, 20Raman spectra

barium oxide, 53cobalt oxide, 280Mo/Al2O3 catalysts, 279nitrogen adsorption, 119

Raman spectroscopy, 5, 1921advantages and disadvantages, 21Al-Mo catalysts, 252aromatic compounds, 368CFCs, 409cobalt oxide, 279hydroxyl groups, 77molybdenum systems, 257supported catalysts, 278

Raman Stokes scattering, 19, 20Rare earth metal oxides, 52

carbon monoxide adsorption, 109copper catalysts, 206DRIR spectroscopy, 64hydroxyl groups, 73, 74

Rayleigh effect, 19, 20Reaction intermediates, surface complexes,

459460Reaction kinetics, IRS in, 25Redox catalysts, 165Redox mechanism, 460Redox systems, 29References, 559641Reflectance ellipsometry, 23Reflection spectroscopy, infrared, 1518Reflection-absorption IR spectroscopy, 17Resonance interactions, vibrational dipoles, 109,

242Resonance Raman spectroscopy, 21, 388Reverse transfer bonding, 271Rhenium oxide, 278Rhenium-containing systems, 237238Rhodium

isocyanate complexes, 161SO2 complexes, 148

Rhodium carbonyls, 237238, 475Rhodium-containing systems, 237238, 479Rideal mechanism, 460Rock salt

coordination number, 42structure, 68, 339

Rocking vibrations, ammonia, 85Rubidium oxide, 226

664 INDEX

Ruthenium, Nitric oxide adsorption, 126Ruthenium carbonyls, 283Ruthenium oxide, 280Ruthenium-containing systems, 237238, 473Ruthenium-palladium systems, 283Rutile

carbon monoxide adsorption, 103crystalline structure, 28, 73hydroxyl groups, 7273low-temperature formation, 256pyridine adsorption, 88

Samarium oxide, 175Sample amorphization, 179Sample holders, 15Sample mold, 12Sample preparation, 12, 38Sapphire, in cells, 13Scattering

multiple, 5, 17reduction of, 11

Scissors deformation mode, 122, 144Selective oxidation reactions, 460Selenates, 287Semiconductors

n-type, 37, 55p-type, 56, 503

Sensitivity, ultraviolet and visible spectroscopy, 5Si-Mo system, 254 bonds, 271

metal carbonyls, 95 -allylic complexes, 342, 501 -donation, pyridine, 84 -donors, 167, 170 - bonds, 44Silane diol, 61Silanol, 382

modes, 40Silanol absorptions, 385, 412Silanol groups, 6061

bending vibration, 61ethene polymerization, 491hydrogen adsorption, 115hydrogen bonding, 413

Silanone groups, 179Silica

outgassing, 40pyrogenic, 60structure, 62

Silica gels, 60Silica-alumina catalysts, 29Silica-based zeolites, CO absorption, 97100Silicalites, 97, 395Silicon dioxide

hydrogen sulfide adsorption, 139140hydroxyl groups, 6063modified, 277surface properties, 3941water adsorption, 121

Silicon windows, 13Siloxane bridges, 40, 400Siloxane groups, 60Silver

charge transfer, 224clusters, 224, 225DRE spectra, 540electronic characteristics, 539ions, 225, 226see also Ag

Silver fluoroborate, 331Silver-containing systems, 223228

additives, 542, 542543DRE spectra, 542effects of nitric acid, 541ethene adsorption, 330331spectra, 225spectral characteristics, 543supports, 540541

Silylacetates, 431Singleton frequencies, 247Sodalite, 218Soft acids and bases, 77, 119Solid structures, oxide surface centers, 2728Solvation effects, 78, 323, 378, 474Spatial defects, 178Spectra, oxide surfaces, 3176Spectra-Tech Collector, 18Spectro-kinetic measurements, 477Spectroscopic methods, 125

characteristics, 3experimental principles, 67

Spectroscopy, see also specific types, e.g.Electronic, Vibrational etc.

Spinspin interactions, 394Spinels, 36

hydrocarbons on, 402hydroxyl groups, 7475NO-CO systems, 552transition aluminas, 64

Splitting parameter, copper hydrates, 188Static shift, 242Stearic acid, 453Steric effects, 364, 367, 393, 495Stishovite, 40Stoichiometric surfaces, chromium oxide, 35Stretching frequencies, and adsorption sites,

271275

INDEX 665

Stretching vibrations, vanadium and molybdenumoxide, 39

Strong associatesCu zeolites, 192194Fe zeolites, 221paramagnetic ions, 185

Strong metal-support interaction, 247248Strontium oxide

carbon dioxide adsorption, 177carbon monoxide adsorption, 105hydrogen adsorption, 117surface properties, 41

Structural looseness, 170Styrene, 365, 366, 370, 372

IR spectra, 366Succinates, 440Sulfate ion, 145, 558Sulfate modification, metal oxide systems, 286291Sulfates, 155Sulfide ion, 140Sulfite ion, 145Sulfites, 150, 151, 153Sulfones, 148Sulfonyl group, 148Sulfur, elemental, 145Sulfur compounds

catalyst deactivation, 456spectral features, 146147

Sulfur dioxideacceptor properties, 147amphoteric nature, 155bond-stretching vibrations, 146charge transfer, 148chemisorption, 151complex formation, 151dissociation, 153heat of adsorption, 144molecular orbitals, 147radicals, 150, 153spectra, 152spectral bands, 141surface process schemes, 154surface-adsorbed species, 156

Sulfur dioxide adsorption, 146157aluminum oxide, 150, 151calcium oxide, 150donor-acceptor complexes, 151oxides, 150157spectra, 152spectral characteristics, 153titanium dioxide, 150zeolites, 149150

Sulfur radicals, 140Sulfur-containing compounds, spectral data, 288

Super-acids, 30, 287, 289, 391, 558Superoxides, 52Support structure, and surface isocyanate

complexes, 160Supported oxides, surface properties, 39Surface active sites, reagent interactions, 281Surface cation-oxygen bonds, 39, 44Surface cations, coordinative saturation values, 34Surface centers, 29Surface chemistry, in situ studies, 20Surface compound concentrations, and time, 529,

530, 531Surface coverage effects, 231Surface defects, 29, 177179

aluminum oxide, 41Surface diffusion, 32, 44Surface electromagnetic wave spectroscopy,

2324coordinate systems and fields, 24methane adsorption, 404

Surface hydroxyl groups, 31, 5677chromium oxide, 34

Surface impurities, 3132titanium dioxide, 48vanadium and molybdenum systems, 39

Surface interaction energy, 49Surface isocyanate complexes, 157161

absorption bands, 157, 159copper, 553spectra, 158, 159stabilization, 158and supports, 160

Surface modification, reagent interaction, 277Surface organometallic chemistry, 277Surface oxygen, basicity, 396Surface reactions, 25Surface vibrations, 11Surface-enhanced Raman spectroscopy, 21, 281Surfaces, 2829

structural flexibility, 170vibrational modes, 31

Symmetric deformation, ammonia, 85Symmetry groups, 10Synchronous radiation excitation, 241

Temperature programmed desorption method, 55Tetraammoniates, 190Tetracyanoethene, 179Thermal stability, molybdenum compounds,

303308Thermodesorption spectroscopy, 25Thiocarbonate compounds, 143Thiolate compounds, 142Ti/Sb oxide systems, 44

666 INDEX

Tin dioxideadsorbed oxygen spectra, 5052defected sample, 51

Tin oxide, spectra, 44Tin-containing catalysts, 507Tinoxygen bonds, 51Titanium, coordination states, 104Titanium dioxide

ammonia adsorption, 88boron-modified, 292carbon monoxide adsorption, 103105chromium catalysts, 269DRIFT spectra, 293hydrogen sulfide adsorption, 142hydroxyl groups, 7173IR spectra, 289, 293nitrogen dioxide adsorption, 133oxygen adsorption, 4850sulfate modified, 287sulfur dioxide adsorption, 150surface impurities, 48surface properties, 37surface vibrations, 37vanadyl groups, 260

Titanium hydroxide, 256Titanium ions, unsaturated, 105, 288Titanium-CO complexes, 273Titanium-molybdenum catalysts, 256

see also Molybdenum-titanium systemsTitration methods, 172o-Tolualdehyde, 511Toluene

ammoxidation, 524526dissociation, 373frequency characteristics, 375IR spectra, 357, 358, 359, 377, 512oxidation, 510, 513spectral data, 360

Toluene adsorption, 348, 350, 356on alumina, 377copper-containing systems, 369, 377frequencies, 375376on oxides, 368on titania, 370two-centred, 369on zinc oxide, 373

o-Toluic acid, 511Transition aluminas, 64, 65, 66Transition metals

acrolein complexation, 436carbonates, 139CO complexes, 273local symmetry, 5oxidation state, 5

Transition temperatures, 32Transition-metal oxides, 64, 153, 157

Brnsted acid sites, 92CO oxidation, 465

Transitionsclassification, 2electronic, 12

Transmission spectra, 45Transmission spectroscopy, infrared, 1114Transmittance, defined, 4Treatment temperature, 321,1,1-Trichloroethane, 402Triene, 360, 362, 364Triethylamine-SO2 complexes, 151Triethylphosphine, 4941,1,1-Trifluoro-2-fluoro-2,2-dichloroethane, 407Trifluoroacetates, 409, 444Trifluoromethane, 174Trimethylamine, 413Trimethylamine-SO2 complexes, 1512,3,4-Trimethylpent-1-ene, 322Trioxygen molecule, adsorption, 55Triphenylcarbenium ions, 360, 362Triphenylcarbinol, 360, 362, 365Triphenylmethane, 358, 364Triphenylmethanol, 362Tungstates, 75, 94Tungsten oxide

ammonia and pyridine adsorption, 91carbon monoxide adsorption, 114

Turbid media, techniques for, 19

Ultraviolet and visible spectroscopy, 2acidic surface characterization, 161sensitivity, 5

Unsaturated atoms, at surfaces, 31

Vacuum cells, 12, 14Vacuum conditions, ultra-high, 32Vacuum treatment

Ni zeolites, 212Pd zeolites, 230

Valence electrons per bond, 34van der Waals interactions, 282, 394Vanadates, 75, 94Vanadium carbonyls, 265, 266, 322Vanadium catalysts

butene isomers, 322iso-butene, 322

Vanadium ions, coordination, 264, 268Vanadium oxide trichloride, 262Vanadium oxides

acid sites, 164, 165alkenes, 321

INDEX 667

ammonia and pyridine adsorption, 91carbon monoxide adsorption, 114diffuse scattering spectra, 76dimers, 259hydrogen sulfide adsorption, 145hydroxyl groups, 7577polymeric, 268surface properties, 39

Vanadium-aluminum oxide compounds,266269

Vanadium-containing systems, 257269Vanadium-silicon oxide compounds, 263266Vanadium-titanium oxide systems, 259263

IR spectra, 261reduction temperature, 265

Vanadyl groups, 260, 266Vehicle emissions, 555Vibration, energy of, 8Vibrational dipoles, resonance interactions, 109,

242Vibrational frequencies, oxygen bonds, 46Vibrational modes, 10, 22

at surfaces, 31Vibrational spectra, crystalline solids, 27Vibrational spectroscopy, 511Vibrations, metal-oxygen bonds, 3244Vinyl group, 348, 350, 372

Wacker reaction, 237Waste gas combustion, 284Water

in carbonyl complexes, 207chemisorption, 89dissociative adsorption, 72dissociative chemisorption, 121hydrogen bonding, 120interaction with carbon dioxide, 137interaction with hydrogen sulfide, 142polysorption, 121

Water adsorption, 120123Aluminum oxide, 122chromium oxide, 122123Cu zeolites, 189ferric oxide, 122magnesium oxide, 122silicon dioxide, 121zeolites, 121122

Water molecules, dissociation, 56Water-gas shift reaction, 56, 447, 448, 460,

466473chromium oxide, 468469copper chromite, 471472CuO-MgO catalysts, 470471high-temperature catalysts, 466467

iron and chromium catalysts, 466467low-temperature catalysts, 469473magnesium oxide catalysts, 467468middle-temperature catalysts, 467469other catalysts, 472473zinc oxide, 469, 473

Weak associatescopper ions, 189, 192, 195, 197paramagnetic ions, 185

Wells-Dawson catalyst, 518Wotton Scientific, 20

X-Ray Absorption Near Engle Spectroscopy,548

X-ray diffraction methods, 27metal oxides, 278molybdenum systems, 256

X-ray photoelectron spectroscopy, 56basic surfaces, 172molybdenum systems, 253, 303

Xerogels, 60Xylenes, 364, 368, 511, 512, 524

Yttrium oxide, 73, 235

Zeises salt, 337Zeolites

carbon dioxide adsorption, 137chemisorption, 137copper-containing systems, 182201for diffuse reflectance electron spectroscopy,

181hydrogen adsorption, 115hydrogen sulfide adsorption, 139140hydroxyl groups, 6365infrared spectra, 98, 102nitrogen dioxide adsorption, 132pre-treatment, 231properties, 29scattering behavior, 181Si/Al ratios, 63silica-based, 97100sorption cavity, 119strongly acidic, 75sulfur dioxide adsorption, 149150supercages, 140water adsorption, 121122see also Faujasite; specific zeolites, eg Cu, Na

zeolitesZinc chromates, carbon monoxide adsorption,

110Zinc formate, 446, 452Zinc hydride, 476Zinc ions, electron-acceptance, 109

668 INDEX

Zinc oxideallylic complexes, 343344ammonia adsorption, 8788as Brnsted base, 350carbon monoxide adsorption, 96,

109110energy levels, 204hydrogen adsorption, 117hydroxyl groups, 7374oxygen desorption, 5556photoionization, 204surface properties, 37

Zirconia, 29chromium catalysts, 269sulfated, 290

Zirconium dioxidecarbon monoxide adsorption, 113hydrogen adsorption, 116hydroxyl groups, 73ion pairs, 404silver stabilization, 226, 544sulfate-modified, 290

Zirconium sulfate, 290ZSM-5 zeolite see HZSM zeolites