629

Index

a – – Horvath–Kawazoe (HK) method acid/base catalysis 154–157 525–526 – bimolecular, acid catalyzed reaction 155 – Nonlocal Density Functional Theory – bimolecular, base catalyzed reaction 156 (NL–DFT) 530–532 – Brønsted–Lowry theory 155 – physical adsorption 514–516 – RNA hydrolysis catalyzed by enzyme – theoretical description of adsorption RNase-A 157 519–523 acids 132–143, See also solid acids and bases ––BETtheoryofadsorption 521 Acinetobacter calcoaceticus 181 – – Langmuir isotherm 519–521 activated carbon supports 439 – – standard isotherms 522–523 activation, catalyst 58–64 – – t-method 522–523 – induction periods as catalyst activation – xenon porosimetry 533–534 ® 59–60 Aerosil process 435 active sites 269–273 alcohols activity of catalyst, in homogeneous catalysis – carbonylations of 245–247 54–58 – synthesis 176–177 acylases 185–186, 256 aldolases 190–193 adaptive chemistry methods 370 alkene metathesis 402–406 adiabatic reactor 569 altered surface reactivity 38–39 adsorption entropy 27–30 alumina (Al2O3) and other oxides adsorption methods for porous materials 436–438 characterization 514–534 amidases 185–186 – adsorption isotherms 517–518 amidases catalyzed reactions 256 – application of adsorption methods amino acid dehydrogenases (AADHs) 518–519 177, 253 – Barret–Joyner–Halada (BJH) method amino acids synthesis 177–178 529–530 6-aminopenicillanic acid (6-APA) 256 – classification of porous materials 517 7-aminocephalosporanic acid (7-ACA) 256 – mercury porosimetry 533 ammonia synthesis 114–119, 289–299 – mesoporous materials characterization – activation energies 116 527–532 – based on natural gas 290 – – capillary condensation 527 – catalysis 292–295 – – Kelvin equation 528–529 – composition dependence 114–119 – microporous materials characterization – mechanism of reaction 114 524–526 – process optimization 295 – – Dubinin–Astakhov methods 524–525 – structure sensitivity 114–119 – – Dubinin–Radushkevich (DR) methods – technology development 291–292 emkin 524–525 kinetic expression 118

Catalysis: From Principles to Applications, First Edition. Edited by Matthias Beller, Albert Renken, and Rutger van Santen. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2012 by Wiley-VCH Verlag GmbH & Co. KGaA. 630 Index

ammonia synthesis (contd.) Boltzmann constant 34 – Temkin Pyzhev kinetics 292 Braunauer, Emmett, and Teller (BET) theory – ultra-high-vacuum techniques 292 6, 521 Anderson–Schulz–Flory curve 313 Brønsted acid/base catalysis 132–143, 154, ansa-zirconocene-based olefin polymerization See also acid/base catalysis catalysis 271–272, 275 Brønsted–Evans–Polanyi (BEP) relationship anti-lock and key model 28, 167 14, 22 apparent activation energy 69 Brønsted–Lowry theory 155 aqueous ammonium heptamolybdate Brunauer classification 518 (AHM) 425 Brunauer, Deming, Deming, and Teller Arrhenius law 49, 69 (BDDT) 517 Arrhenius number 85 Burkholderia plantarii 254 Arthrobacter globiformis 255 Butler–Volmer setting 382 aryl halides, carbonylations of 245–247 butylbranching mechanism 329 aryl–X derivatives, carbonylation of 246 asymmetric synthesis 174–175 c atom utilization 17 Candida cylindracea 254 atomic force microscopy (AFM) 494 Carberry number 83, 85 carbon materials 438–440 b carbonylation reactions 234–247 Baeyer–Villiger oxidation 179 – of alcohols and aryl halides 245–247 – Baeyer-Villiger Monooxygenases – – aryl–X derivatives 246 (BVMOs) 180–181 – – Ibuprofen 246 – enzyme-catalyzed, mechanism 182 – – lazabemide 247 ‘band gap’ 218 – – Rhodium-catalyzed carbonylation of Barret–Joyner–Halada (BJH) method methanol 245 529–530 – hydroformylation 235–239 bases 132–143, See also solid acids – of olefins and alkynes 239–244 and bases – – 1,3-butadiene 243 basicity and nucleophilicity, relation – – palladium-catalyzed carbonylation 242 between 154 5-carboxyfluorescein diacetate (C-FDA) batchwise-operated stirred-tank reactors 506–507 (BSTR) 578–579 catalytic partial oxidation (CPOX) 357 Bayer process 436 catalytic reactor engineering 563–624, See bimolecular catalytic reactions 76–77 also fluid–solid reactors; ideal reactor biocatalysis 171–194, 250–259, See also modeling/heat management; microreaction hydrolases; lyases; oxidoreductases engineering; residence time distribution – applications 253–257 (RTD); single-phase reactors – best route, choosing 250–253 – fixed-bed reactors 574 – – enzymatic routes 251–252 – fluid–fluid reactors 571–573 – biocatalysis cycle 173 – liquid–liquid–gas system 573 – case studies 257–259 – principles 67–108 – – lipitor building blocks synthesis – – formal kinetics of catalytic reactions 257–259 68–77, See also individual entry – development 172 – – homogenous catalysis in biphasic – reaction strategy choice 174–175 fluid/fluid systems 103–108 – – kinetic resolution or asymmetric – – mass and heat transfer effects 77–103, synthesis 174–175 See also individual entry – reaction systems, choice 175–176, – slurry–suspension reactors 574–575 250–259 – structured catalysts for multiphase reactions biotransformations 171 575 biphasic fluid/fluid systems, homogenous – three-phase gas–liquid–solid systems catalysis in 103–108 573–575 Bodenstein number 596–597, 607 – types 564–575 Index 631 catalytic selective oxidation 341–363 Coherent Anti-Stokes Raman Spectroscopy – complexity/issues of 354, 356–358 (CARS) 502 – consolidated technologies 341–363 combinatorial approaches in solid catalysts – in continuous development of development 453 more-sustainable industrial technologies – for optimal catalytic performance 453–456 355–356 compensation effect 44–46 – development of industrial process, – exocyclic methylation reaction 45 challenges 353–355 – pairing reaction 45 – directions for innovation 361–363 complex reaction 73 – dream oxidations 359–361 consecutive first-order reactions 82 – fundamentals 341–363 consecutive reactions 92 – main features 341–353 constant selectivity relationship 159 – for organic compounds synthesis in constrained geometry catalysts 279 petrochemical industry 342–352 Continuously Operated Ideal Stirred Tank – – oxidation process PHASE reactor Reactors (CSTR) 580–581 342–353 – space time in 583 C–C bond cleavage 126–132 continuously stirred tank reactors (CSTRs) chain growth 314–315 546–547 chain walking 279 continuous-phase contacting 616–618 chemocatalysis, equivalence of 30–32 – falling-film contactors 617 Chilton–Colburn analogy 84, 100 Corynebacterium glutamicum 253 clariant process 247 coupling of catalytic reaction 42 crystalline catalysts design 222–223 classical chlorohydrin route 18 cumylhydroperoxide (CHP) 362 ‘classical’ guidelines for catalyst testing cycle, catalytic 20–27 536–557 – appropriate laboratory reactor, selecting d 546–548 Damkohler¨ number 81–82, 547 – catalyst stability, assessing 554–555 de Donder concept 32 – data collection 543–546 deactivation, catalyst 58–64 – effective experimental strategies 541–543 – due to irreversible reactions 65–64 – – two-variables system 542 – due to multinuclear complexes formation – encouraging effectiveness 536–540 61–62 – ensuring efficiency 540–555 – due to non-reactive complexes formation – ideal flow pattern, establishing 548–549 61 – isothermal conditions, ensuring 549–551 dehydrogenases 176–178 – quality guidelines 540 – alcohols synthesis 176–177 – selectivity 544 – amino acids synthesis 177–178 – space–time yield 545 – formate dehydrogenase (FDH) 178 – transport, diagnosing and minimizing the – polyethylene glycol (PEG) 178 effects of 552–554 – Prelog-rule 177 – – ‘DrySyn’ Beta vs commercial Beta dehydrogenation 126–132 performance 553 – cyclohexane dehydrogenation 131 – – diagnostic tests for interphase (external) – mechanism of 126 transport 552 – olefin hydrogenation kinetics 126–127 – – diagnostic tests for intraparticle (internal) density functional theory (DFT) 209, 367, transport 553 395–397 – yield 545 deposition precipitation 427–428 cobalt 312 desulfurization 291 – cobalt catalyst formation 321–322 development of catalytic materials 445–459 – cobalt promoter 394–395 – catalytic OCM reaction, reaction mechanism co-catalysts 59 and kinetics of 448–449 co-catalyzed carbonylation 241 – combinatorial approaches in 453–459 cofactor regeneration 178 – fundamental aspects 446–448 632 Index

development of catalytic materials (contd.) electrophilic catalysis 154–157 – high-throughput technologies in enantioselective ring-closing metathesis 405 456–459 enzyme catalysis 8–9, 155 – kinetic analysis 450–451 ethane hydrogenolysis mechanism 127–132 – micro-kinetics and solid-state properties as ethylene/propylene rubber (EPR) 264 knowledge source 448–453 Evonik-Uhde process 361–362 – – electronic conductivity 452 exocyclic methylation reaction 45 – – ion conductivity 452 extended X-ray absorption fine spectroscopy – – redox properties 452 (EXAFS) 400, 499 – – structural defects 451–452 external and internal transfer resistances, – – supported catalysts 453 combination 96–101 – – surface acidity and basicity 452 – external and internal temperature gradient – surface oxygen species in methane 100–101 conversion 449–450 – in isothermal pellets 96–98 development of catalytic processes 11–13 – mass transfer implication on temperature – history 11–13 dependence 98–99 – future 11–13 external mass and heat transfer 78–85 dibenzothiophene 392 dihydroxyacetone phosphate (DHAP) f 191–192 falling-film contactors 617 – DHAP-dependent aldolases 192 ‘fingerprinting’ 267 dilution rate 580 Fischer–Tropsch (FT) synthesis 40, direct alkane activation 139–141 301–323, 569 direct desulfurization (DDS) 392 – catalysts, general 311–313 dispersed phase contacting 619–622 ––cobalt 312 – gas–liquid–liquid 622 – – iron 312–313 – micro packed beds 621 – – nickel catalysts 312 – segmented flow gas–liquid–solid reactors – – Ruthenium 312 620 – gas chromatogram of 303 dispersion model 595–596 – operation ranges 306–308 ‘dormant’ sites 269–273 – processes and product composition dry impregnation 425 308–311 Dubinin–Astakhov methods 524–525 – – commercial FT-synthesis 308–311 Dubinin–Radushkevich (DR) methods – – high-temperature Fischer–Tropsch 524–525 synthesis 310–311 Dusty Gas Model 382 – – hydrocracking 309 dynamic kinetic resolution (DKR) 175 – – hydroisomerization 309 – – isomerization 309 e – – low-temperature synthesis 309–310 efficiency factor 105 – – multi-tubular fixed-bed reactors 309 electric double layer 204–207 – – slurry-phase bubble column reactors 309 – diffuse double-layer 206 – – slurry reactors 310 – inner layer 206 – – synthesis gas 311 electrocatalysis 201–213 – rate equations 306 – electric double layer 204–207 – reaction fundamentals 313–322 – – diffuse double-layer 206 – – ideal polymerization model 313–322 – – inner layer 206 – stoichiometry 304–305 – electrochemical potentials 203–204 – thermodynamic aspects 305–306 – equivalence of 30–32 Fischer-Tropsch Synthesis (FTS) catalyst 509 – theory 203–207 fixed-bed reactors 568–569, 574 electrochemical potentials 203–204 – adiabatic reactor 569 electrolyte-reservoir 205 – multitubular reactor 569 electron backscatter diffraction (EBSD) – staged fixed-bed 569 measurements 502 fluid catalytic cracking (FCC) process 391 Index 633

fluid–fluid MSR 610–612 – catalyst’s performance and its composition – falling film microchannel 610 and structure 4–7 – microchannel 610 – – Brunauer-Emmett-Teller (BET) – micromixer 610 technique 6 fluid–fluid reactors 571–573 – – characterization tools 6 fluidized-bed reactors 569–571 – – dynamic Monte Carlo methods 7 fluid–solid MSR 607–610 – – Langmuir–Hinshelwood–Watson– fluid–solid reactors 568–571 Hougson (LHWH) expressions 6 – fixed-bed reactors 568–569 – – Michaelis–Menten expression 6 – fluidized-bed reactors 569–571 in situ spectroscopic measurements 5 – minimum fluidization velocity and pressure – – T-plot techniques 6 drop 570–571 – – X-ray scattering techniques 6 fluorescence microscopy (focused ion beam – formal kinetics 70–71 (FIB) 502 – molecularly defined systems in 399–413, formal kinetics of catalytic reactions 68–77 See also individual entry – general definitions 69–70 – monomer insertion 274 – heterogeneous catalytic reactions 70–71 – ‘replication’ phenomenon 274, 277 – Langmuir adsorption isotherms 72–73 – steps involved in 68 – reaction mechanisms 73–77 – Ziegler–Natta catalysts 274 formate dehydrogenase (FDH) 178, 254 heterogeneous catalysts 493–510, See also fractional surface coverage 71 framework-substituted redox ions 335–339 in-situ characterization of heterogeneous – Ti-catalyzed epoxidation 335–338 catalysts fumed silica 433–436 – design of, requirements 447 fundamental catalysis in practice 13 heterogeneous chemistry, of high-temperature catalysis 365–385 – heterogeneous reaction mechanisms g 367–368 gas–liquid–liquid reactors 622 heterogeneous photocatalysis 216–228 gas–liquid–solid reactors 616 – case studies 220–228 gas–liquid systems 611–613 glycerolphosphate oxidase (GPO) 192 – – crystalline catalysts design 222–223 Gouy–Chapman diffuse double layer 206 – – energy conversion 222–225 Gouy–Chapman model 205 – – microreactors 227–228 Gouy–Chapman–Stern model 205 – – supported chromophores 223–225 ‘growing chain orientation’ mechanism 268 – – visible light-sensitive systems 223 – – water purification 220–222 – – Z-scheme process 224 h – photocatalysis 216–217 Haber–Bosch process 3, 291 – from surface chemistry to reactor design Hagen–Poiseuille law 593, 605 216–228 half-titanocene precatalyst structures 281 Hammett acidity function 154 Hevea brasiliensis (HbHNL) 189, 257 Hatta number (Ha) 103, 572 High Density PolyEthylene (HDPE) 262 heat balance 583 high-energy resolution fluorescence detected heat management in microstructured reactors (HERFD) X-ray Absorption Spectroscopy 622–624 (XAS) 497 heat transfer 85–96, See also mass and heat High Throughput Experimentation transfer effects (HTE) 280 Helmholtz model 205 Highest Occupied Molecular Orbital heterogeneous catalysis 4–7, 113–150, (HOMO) 217 273–278, See also kinetics of heterogeneous high-temperature catalysis 365–385 catalytic reactions; reducible oxides; solid – applications 372–378 acids and bases; transition metal catalysis – – formulation of an optimal control problem – catalyst preparation methods 7 375–378 634 Index

high-temperature catalysis (contd.) – – isolation of products and recovery and – – olefin production by high-temperature recycle of catalyst 153 oxidative dehydrogenation of alkanes – – ligands for 153–154 373–378 – – metal-catalyzed reactions 153 – – synthesis gas from natural gas by – – nature of compounds 152 high-temperature catalysis 373 – – reaction conditions 152 – – turbulent flow through channels with – – reactions mediated by transition metal radical interactions 372–373 complexes 153 – fundamentals 366–372 – – reactions phase 153 – – coupling of chemistry with mass and heat – enzyme catalysis 155 transport 369–370 – nucleophilic and electrophilic catalysis – heterogeneous chemistry role 365–385 154, 157–159 – homogeneous chemistry role 365–385 – – acid/base catalyzed RNA hydrolysis 155 – hydrogen production from logistic fuels by – organometallic complex catalysis 157–160 378–380 – transition metal-centered homogeneous catalysis 155, 159–169, See also – mathematical optimization of reactor individual entry conditions and catalyst loading 372 homogeneous chemistry, of high-temperature – radical chemistry role 365–385 catalysis 369 – in solid oxide fuel cells 380–385 Horvath–Kawazoe (HK) method 525–526 high-temperature Fischer–Tropsch synthesis hydantoinases 187–188 310–311 hydride transfer 141 high-temperature fuel cells 381 hydroaminomethylation reaction 238 high-throughput technologies in solid hydrocarbon/oxygen (C/O) ratio 377 catalysts development 456–459 hydrocarboxylation 240 – catalytic materials preparation 457 hydrocracking reaction, acid catalysis 309, – data analysis 458–459 325–332 – screening of catalytic materials 457 – cracking selectivity dependence 326–328 – testing of catalytic materials 457 – hydrocarbon chain length, activity on historic review 3–19 326–328 – development of catalytic processes 11–13 – symmetric versus asymmetric cracking – – history and future 11–13 patterns 328–332 – fundamental catalysis in practice 13 – – butylbranching mechanism 329 – history of catalysis science 3–12 – – pore size 328–332 – – chemical engineering 3 – – side-chain elongation mechanism 329 – – organic chemistry 3 – – stereo-selective behavior 330 – – nineteenth century 3 – – stereoselectivity 328–332 – – synthetic organic chemistry 4 – – topology dependence 328–332 – – hysical chemistry 4 hydrodenitrogenation 397 – – inorganic chemistry 3–4 hydrodesulfurization 390–398 – important scientific discoveries 9–11 – C-X bond-breaking mechanism 393 – – new industries/new catalytic processes – sulfidic catalyst, structure 393–397 10 – – DFT calculations 395–397 – process choice 17–19 – – Mo structure 393–394 – reactor choice 16–17 – – promoter structure 394–395 Hofmann-type β-hydrogen elimination 391 – surface sites determination 398 Hombikat UV 100, 220 hydroesterification 240 homogeneous catalysis 8–9, 152–169, hydroformylation 235–239 278–280, 465–490, See also acid/base – co-catalyzed carbonylation 241 catalysis; in-situ techniques for – rhodium-catalyzed hydroformylation homogeneous catalysis; kinetics in 236 homogeneous catalysis hydrogen cyanide (HCN) 171 – in biphasic fluid/fluid systems 103–108 hydrogen evolution reaction (HER) – characteristics 152 202 Index 635 hydrogenation 126–132 in situ characterization at a single catalyst – hydrogenolysis of isopentane, single-center particle level 501–510 route for 130 – single-molecule in-situ spectroscopy of a – mechanism of 126 catalytic solid 504–508 – route 392 in situ generation of organo-catalyst 42–44 hydrogenolysis of grafted in situ hydroformylation 238 hydrocarbyl-containing systems 409 in situ micro-spectroscopy of catalytic solid hydroisomerization 309, 327–328 501–504 hydrolases 182–188 in situ techniques 59, See also individual – acylases 185–186 entries – amidases 185–186 induction periods as catalyst activation – hydantoinases 187–188 59–60 – lipases 182 inhomogeneous site distribution 40–42 – nitrilases 186–187 inorganic chemistry 4 – nitrile hydratases 186–187 – inorganic solid chemistry 42 – peptidases 185–186 in-situ characterization of heterogeneous hydroxynitrile lyases (HNLs) 171, 188–190, catalysts 493–510 257 – applications 495–497 – dynamic conditions 494 i – gas chromatography (GC) 495 ibuprofen 246 – history 495–497 ideal continuously-operated stirred tank – mass spectrometer (MS) 495 reactor 591–592 – reactor loaded with catalytic solid 497–501 ideal plug flow reactor 591 – – Extended X-ray Absorption Fine Structure ideal polymerization model of FT synthesis (EXAFS) 499 313–322 ––in-situ HERFD-XAS approach 497 – alcohols in 316 – – probed by multiple characterization – alternative reactions on growth site 315 methods 499–501 – Anderson–Schulz–Flory curve 313 – – probed by one characterization method – branching 315–316 497–499 – chain growth 314–315 – – XANES 497 – desorption (olefins/paraffins) 316–319 – recent developments 495–497 – – primary reactions 317 – static conditions 494 – – secondary reactions 317 – ultra-high vacuum (UHV) conditions 494 – in situ catalyst formation 319–322 in-situ high-resolution transmission electron – – cobalt catalyst formation 321–322 microscopy (HRTEM) 296 – – iron catalyst formation 319–321 in-situ nano-spectroscopy of a catalytic solid – – self-organization of FT regime 319 509–510 ideal reactor modeling/heat management in-situ techniques for homogeneous catalysis 575–586 465–490, See also IR-spectroscopy; NMR – batchwise-operated stirred-tank reactors spectroscopy; UV/Vis spectroscopy 578–579 – gas consumption and gas formation – continuously operated ideal stirred tank 467–470 reactors (CSTR) 580–581 instantaneous or point selectivity 92 – ideal plug flow reactor 581–586 interfacial activation 183 – – heat balance 583 internal mass and heat transfer 85–96 – – highly exothermic reactions 586 – isothermal pellet 87–94 – – mass balance in 582 – non-isothermal pellet 94–96 – – parametric sensitivity 584 Internally Illuminated Monolith Reactor – – stability diagram 586 (IIMR) 227 – mass and energy balances 576–577 ion adsorption 423–424 in situ catalyst formation in FT synthesis iron 312–313 319–322 iron middle pressure synthesis 309 636 Index

irreversible reactions, catalyst deactivation l due to 65–64 lactate dehydrogenase (LDH) 194 IR-spectroscopy 481–485 laminar flow reactor 593–595 – hydroformylation 484–485 Langmuir adsorption isotherms 72–73 – in-situ FTIR spectroscopic study 483 Langmuir-Hinshelwood kinetics 74–75, 327 isomerization catalysis 141–143 Langmuir–Hinshelwood–Watson–Hougen isothermal pellet 78–84, 87–94 (LHWH) equation 6, 21, 25 – consecutive reactions 92 Langmuir isotherm 519–521 – external concentration profile 80 Laser Doppler Anemometry/Laser Doppler – instantaneous or point selectivity 92 velocimetry (LDA/LDV) 371 – isothermal yield and selectivity laser-induced fluorescence (LIF) 371 82–84, 91 lazabemide 247 – parallel reactions 91 Lennard–Jones potential (L–J potential) – porous catalysts, concentration profiles in 515–516 79 leucine dehydrogenase (Leu-DH) 178, 253 isothermal yield and selectivity 82–84, 91 Lewis acid–lewis base catalysis 132–143, – consecutive first-order reactions 82 332–333 – parallel reactions 84 – hydrocarbon activation 332–333 isotherms 71 ligand-accelerated catalysis (LAC) 167 Linum usitatissimum 189 lipases 182, 253–255 k lipitor building blocks synthesis 257–259 Kelvin equation 528–529 liquid–liquid systems 613–616 kinetic resolution 174–175 liquid–liquid–gas system 573 – dynamic kinetic resolution (DKR) 175 liquid loading (α) 107 kinetics 4–7, 68 lock and key model 27–30, 168 – microkinetics 7 – anti-lock and key model 28 – rate-limiting step 6 Low Density PolyEthylene (LDPE) 262–263 kinetics in homogeneous catalysis Low-Energy Electron Diffraction (LEED) 493 48–64 Lowest Unoccupied Molecular Orbital – activation and deactivation, catalyst (LUMO) 217 58–64 low-pressure oxo processes (LPO) 236 – – co-catalysts 59 lyases 188–193 ––in situ techniques 59 – aldolases 190–193 – – induction periods as catalyst activation – hydroxynitrile lyases 188–190 59–60 – pyruvate/phosphoenolpyruvate-dependent – – spectator ligands 59 aldolases 192–193 – catalyst activity 54–58 – kinetic description 48–54 m – principles of catalyst 48–54 major/minor concept 168, 479 kinetics of heterogeneous catalytic reactions Manihot esculenta 190 20–46 mass and heat transfer effects 77–103 – altered surface reactivity 38–39 – external and internal transfer resistances, – equivalence of electrocatalysis and combination 96–101 chemocatalysis 30–32 – external mass and heat transfer 78–85, See – materials gap 39–42 also internal mass and heat transfer – microkinetics, rate-determining step – isothermal pellet 78–84, See also individual 32–34 entry – physical chemical principles 20–27 – non-isothermal pellet 84–85 – – activation energy 26 – transport effects, estimation criteria for – – catalytic cycle 20–27 101–103 – – rate-limiting step 21 mass Biot number 97 – pressure gap 36–39 mass transfer implication on temperature – surface reconstruction 37–38 dependence 98–99 Index 637 materials gap 39–42 – – elemental analysis 401 – catalyst activation or deactivation 40 – – ESR spectroscopy 401 – inhomogeneous site distribution 40–42 – – IR (Raman) spectroscopy 401 – structure sensitivity 39 – – mass spectrometry 401 maximum rate (rmax)53 – – NMR spectroscopy 401 mercury porosimetry 533 – – UV spectroscopy 401 mesh microcontactor 619 – – X-ray crystallography 401 mesoporous materials characterization – single sites 527–532 – – on border between homogeneous and metal-organic frameworks (MOFs) heterogeneous catalysis 400–412 442–443 – taking homogeneous catalysis to methane reforming 120–125 heterogeneous phase 402–406, See also – activation energies and reaction energies single-site alkene metathesis catalysts 123 – toward new reactivity 408–411 – composition dependence 120–125 – – alkane metathesis 409 – mechanism of reaction 120 – – cross-metathesis of methane and higher – structure sensitivity 120–125 alkanes 409–410 methyl methacrylate (MMA) 240 – – H/D reaction of D2/H2 or D2/RH Michaelis–Menten equation 6, 27, 50–55, mixtures 409 166 – – hydrogenolysis of alkanes 409 micro packed beds 621 – – methanol-to-olefin (MTO) process 413 microkinetics 7 – – non-oxidative coupling of methane 410 – in catalysts development 448–453 – – titanium-substituted silicate-1 (TS-1) 413 – rate-determining step 32–34 monolithic catalysts 370–371 microporous materials characterization – DETCHEMMONOLITH 370–371 524–526 – shapes microreaction engineering 602–624, See also – – corrugated plate packing 570 three-phase reactors – – square-channel monolith 570 – criteria for reactor selection 602–604 monomer insertion 274 – fluid–fluid MSR 610–612 Monte Carlo methods 7 – fluid–solid MSR 607–610 Montsanto process 245 – gas–liquid systems 611–613 mordenite (MOR) 441 – heat management in microstructured most abundant surface intermediate (masi) reactors 622–624 approximation 75–76 – liquid–liquid systems 613–616 multinuclear complexes formation, catalyst – micro-structured catalytic wall reactor 608 deactivation due to 61–62 – residence time distribution 606–607 multinuclear NMR spectroscopy 470 – single-phase MSR 604–607 multitubular reactors 309, 569 – types of 604–610 microreactors 227–228 n micro-spectroscopic techniques 502 N-acetylneuraminate (NeuAc) 192 micro-structured reactors (MSRs) 564 natural gas-based ammonia plant 290–291 minimum fluidizing velocity (umf ) 571 – desulfurization 291 modern pertochemical route 18 – secondary reforming 291 molecular basis of catalysis 5 – steam reforming 291, 295–299 molecular vs surface chemistry 401 nicotinamide adenine dinucleotide – characterization tools 401 (phosphate)(NAD(P)H) 251 molecularly defined systems in heterogeneous nitrilases 186–187 catalysis 399–413 nitrile hydratases 186–187 – bridging the gap with classical NMR spectroscopy 470–480 heterogeneous systems 406–408 – carbon monoxide ethylene copolymer – molecular vs surface chemistry, formation 477 characterization tools 401 – hydridoalkyl intermediate formation 478 – – chemical characterization (reactivity) 401 – hydroformylation catalyst formation 474 638 Index

NMR spectroscopy (contd.) oxidoreductases 176–182, See also – Iridium catalyst 478 oxygenases – major/minor principle 479 – dehydrogenases 176–178 – multinuclear NMR spectroscopy 470 – – alcohols synthesis 176–177 – palladium-catalyzed oxo synthesis (hydroformylation) 103 hydroalkoxycarbonylation 476 oxygen reduction reaction (ORR) on Pt(111), non-isothermal pellet 84–85, 94–96 application 202, 207–212 – internal and external mass transport in – electrochemical ORR mechanisms 210 96–98 – HOOH pathway 209 nonlocal Density Functional Theory –O2 pathway 208 (NL–DFT) 530–532 – OOH pathway 209 non-oxidative coupling of methane 410 oxygenases 178–182 non-reactive complexes formation, catalyst – Baeyer-VilligerMonooxygenases (BVMOs) deactivation due to 61 180–181 non-specific adsorption 204 – P450 mono-oxygenases 179–180 nucleophilic/electrophilic catalysis 154, – P450 superfamily 180 157–159 – bimolecular reaction 158 p P450 mono-oxygenases 179–180 pairing reaction 45 o palladium-catalyzed carbonylation 242 olefin hydrogenation kinetics 126–127 parallel reactions 84, 91 olefin polymerization process technology parametric sensitivity 584 264–280, See also heterogeneous catalysis; Pareto plot 15–16 homogeneous catalysis Pauling valency concept 133 – ‘growing chain orientation’ mechanism Pausen-Khand reaction 244 268 Peclet´ number 597 – propene polymerization catalysts 266 Penicillin G amidase (PGA) 256 – reactivity 264–269 peptidases 185–186 – structure 264–269 phenyl alanine dehydrogenase (Phe-DH) Operando spectroscopy 465 178, 254 ordered mesoporous materials 442 photocatalysis 216–217, See also organo-catalyst, in situ generation of 42–44 heterogeneous photocatalysis organometallic complex catalysis 152, – applications of 219 157–160 – in practice, reactor considerations – major/minor concept 159 225–228 – ‘Reppe chemistry’ 157 – principle of 217–219 Ortho-F effect 282 physical adsorption 514–516 overall effectiveness factor 97 physical chemistry 4 oxidation reactions 148–150 pig liver esterase (PLE) 171 – propane ammoxidation mechanism 149 planar laser-induced fluorescence (PLIF) 371 – propane oxidation 150 plug flow reactors (PFRs) 546 – selective oxidation of propylene 148–150 Point of Zero Charge (PZC) 422–423, 436 oxidative addition 162–163 polyethylene glycol (PEG) 178 – in transition metal-centered homogeneous polymerase chain reaction (PCR) 253 catalysis 159–169 polymer-electrolyte (or proton-exchange) – – of non-polar addenda in apolar solvents membrane fuel cell (PEMFC) 207 171 polymerization 261–285 – – via radical chain mechanism 163–164 – kinetics oxidative coupling of methane (OCM) 448 – – active sites 269–273 – catalytic solid materials for OCM reaction – – ‘dormant’ sites 269–273 – – physico-chemical properties of 451 – – ‘triggered’ sites 269–273 – kinetics of 448–449 – latest breakthroughs 280–285 – reaction mechanism 448–449 – – half-titanocene precatalyst structures 281 Index 639

– olefin polymerization process technology – bimolecular catalytic reactions 76–77 264–273, See also individual entry – complex reaction 73 – polyolefins 262–264 – Langmuir–Hinshelwood model 74–75 – Ziegler–Natta-type olefin polymerizations – ‘masi’ approximation 75–76 261 – quasi-surface equilibrium approximation polyolefins 262–264 75 porcine pancreatic lipase (PPL) 184 reaction order 69 pore size distribution (PSD) 518 reaction rate 69 pore volume impregnation (PVI) 425 reactor choice 16–17 porous catalysts, concentration profiles in 79 reactor engineering, See catalytic reactor porous materials as catalysts and catalyst engineering supports 431–444, See also adsorption reactor performance (Lp) 578 methods for porous materials redox catalysis 333–335 characterization reducible oxides 143–150 – activated carbon supports 439 – heats of formation 145 –alumina(Al2O3) and other oxides 436–438 – oxidation reactions, mechanism 148–150 – carbon materials 438–440 – – propane ammoxidation mechanism 149 – fumed silica 433–436 – – propane oxidation 150 – general characteristics 431–433 – – selective oxidation of propylene 148–150 – ordered mesoporous materials 442 – relative stabilities, comparison 143–145 – shaping 443–444 – structure sensitivity 145–148 – sol-gel method of preparation of 433–436 residence time distribution (RTD) 587–602, ® ––Aerosil process 435 606–607 – zeolites 440–441 – experimental determination of 589–591 Prelog-rule 177 – – pulse function 590–591 pressure gap 36–39 – – step function 589–590 primary proton attachment 137 – residence time distribution in tubular Proactinomyces erythropolis 181 reactors, estimation 597–599 process choice 17–19 – RTD for ideal reactors 591–595 – classical chlorohydrin route 18 – – cascade of ideally stirred tanks 592–593 – modern pertochemical route 18 – – ideal continuously-operated stirred tank propane oxidation 150 reactor 591–592 propene polymerization catalysts 266 – – ideal plug flow reactor 591 proton activation by zeolites 135–139 – – laminar flow reactor 593–595 Pseudomonas chlororaphis B23 256 – RTD influence on performance of real Pseudomonas putida 181 reactors 599–602 pyruvate decarboxylase (PDC) 194 – RTD models for real reactors 595–597 pyruvate/phosphoenolpyruvate-dependent – – cell model 596–597 aldolases 192–193 – – dispersion model 595–596 reversible reaction 69 q rhodium-catalyzed carbonylation of methanol α-quartz 433 245 quasi-surface equilibrium approximation 75 rhodium-catalyzed hydroformylation 236 Rhodococcus rhodochrous 256 r Ruhrchemie/Rhone-Poulencˆ process 237 radical chemistry, of high-temperature ruthenium 312 catalysis 365–385 – experimental evaluation of models 371 s rate-controlling step or slow step 33 Sabatier Principle 21–23 rate-determining step 34 Sabatier’s catalytic reactivity principle 14 rate-limiting step 6, 21 Scanning Electron Microscopy (SEM) 494 reaction engineering principles, See catalytic Scanning Transmission X-ray Microscopy reactor engineering (STXM) 509 reaction mechanisms 70, 73–77 Schmidt number 85 640 Index

second Damkohler¨ number (DaII) specific adsorption 204 81–82, 98 specific surface area (A) 518 Second Harmonic Generation (SHG) 502 spectator ligands 59 secondary proton attachment 137 staged fixed-bed 569 segmented flow gas–liquid–solid reactors standard isotherms 522–523 620 steam reforming, in ammonia sysnthesis selection, catalyst 13–16 291, 295–299 – Brønsted–Evans–Polanyi (BEP) – catalysis 296–297 relationship 14 – secondary phenomena 297–299 – computational approach 13 – technology 295–296 – Sabatier’s catalytic reactivity principle 14 – tubular reformer 296 selective oxidation 333–335 stirred-tank reactor 564–567 selectivity 544 – heat transfer 567 shaping, porous material catalysts 443–444 – mixing 565 Shell Higher Olefin Process (SHOP) 103 structural defects 451–452 Sherwood number (NSh) 547 structured catalysts for multiphase reactions side-chain elongation mechanism 329 575 silica (SiO2) 433 sulfidic catalyst 393–397, See also under single-molecule in-situ spectroscopy of hydrodesulfurization catalytic solid 504–508 supported catalysts 453 single-phase MSR 604–607 – preparation 420–429 – mixing 604 – – deposition precipitation 427–428 single-phase reactors 564–568, See also – – drying 425–427 stirred-tank reactor – – impregnation 425–427 – tubular reactors 567–568 – – ion adsorption 423–424 single-site alkene metathesis catalysts – – outer-sphere complex formation 423 402–406 – – selected catalysts, applications 421 – enantioselective ring-closing metathesis – – selective removal 420 405 – – support surface chemistry 422–423 slurry-phase bubble column reactors 309 – – thermal treatment 428–429 slurry reactors 310 Supported Liquid-Phase Catalyst (SLPC) 106 slurry–suspension reactors 574–575 supported transition-metal hydrides sol-gel method 433–436 408–411 solid acids and bases 132–143, 440 surface oxygen species in methane conversion – Brønsted acid or base 132 449–450 – Lewis acid or base 132 surface reactions 34–36 – mechanistic considerations 139–143 – elementary rate constant expressions for – – direct alkane activation 139–141 34–36 – – hydride transfer 141 surface reconstruction 37–38 – – isomerization catalysis 141–143 suspension reactors 572 – primary proton attachment 137 symmetric versus asymmetric cracking – proton activation by zeolites 135–139 patterns 328–332 – secondary proton attachment 137 synthesis gas 311 – stereochemical effects 139 synthetic organic chemistry 4 – van der Waals interactions 139 solid oxide fuel cells (SOFC) t – high-temperature catalysis in 380–385 Temkin kinetic expression 118 solid-state properties, in catalysts Temkin Pyzhev kinetics 291–292 development 448–453 temperature-programmed reduction (TPR) solvent complexes 487 method 509 Sorghum bicolor 189–190 Temporal Analysis of Products reactor (TAP) space time 580, 583 451 space–time yield 545 Terrylene diimide (TDI) dye molecule 506 space velocity 580 Tetrahydrofuran (THF) 57, 176 Index 641 thermal reaction 216 – application of 556 thermal treatment 428–429 – criteria for 554 Thiele modulus 88, 95, 98, 547 – – axial mixing 554 Thomas chemistry 339 – – channeling 554 three-center (M-C-H) transition states – – isothermality 554 128 – – mass transfer 554 three-phase gas–liquid–solid systems – disadvantages 553 573–575 – input data 555 three-phase reactors 616–622 – laboratory scale versus industrial trickle-bed – continuous-phase contacting 616–618 reactors 557 – dispersed phase contacting 619–622 tubular reactors 567–565 – gas–liquid–solid 616 tubular reformer 296 – mesh microcontactor 619 turnover frequency (TOF) 55 – trickle-bed reactors 555, See also turnover number (TON) 54–55 individual entry Ti-catalyzed epoxidation 335–338 u Time-Resolved Microwave Conductivity UV Photoelectron Spectroscopy (TRMC) 220 (UPS) 493 t-method 522–523 UV/Vis spectroscopy 486–490 Topsøe radial flow converter 292 – principal component analysis 489 T-plot techniques 6 TPPTS (tris sodium salt of meta- v trisulfonated triphenylphosphine) 237 van der Waals interactions 139 transaminases (TAs) 193–194 visible light-sensitive systems, quest for 223 transition metal catalysis 114–132 – ammonia synthesis 114–119, See also w individual entry Washburn equation 533 – C–C bond cleavage 126–132 weight hourly space velocity (WHSV) – dehydrogenation 126–132 544 – ethane hydrogenolysis mechanism Weisz module 90, 102 127–132 Weisz’ window 545 – hydrogenation 126–132 wet impregnation 425 – methane reforming 120–125, See also white biotechnology 171 individual entry Wilkinson’s catalyst 166 transition metal-centered homogeneous catalysis 155, 159–169 x – hydrometalation of alkenes 165 xenon porosimetry 533–534 – kinetic activity 167 X-ray Absorption Near Edge Spectroscopy – ligand substitution (XANES) 497 – – associative pathway 160 x-ray absorption spectroscopy (XAS) 466 – – dissociative pathway 160 x-ray fluorescence spectroscopy (XAFS) 466 – – limiting mechanisms 160 X-ray Photoelectron Spectroscopy (XPS) 493 – migratory insertion 164–165 x-ray scattering techniques 6 – oxidative addition 162–163 – reductive elimination 164 y – substrates and reagents, activation yield 545 of 159 – Ziegler–Natta polymerization 164 z Transmission Electron Microscopy (TEM) zeolite catalysis 325–339 494 – framework-substituted redox ions transport effects, estimation criteria for 335–339 101–103 – hydrocracking reaction, acid catalysis trickle-bed reactors 552 325–332, See also individual entry – advantages 553 – Lewis acid–lewis base catalysis 332–333 642 Index

zeolite catalysis (contd.) zeolites 7, 28–30, 440–441 – redox catalysis 333–335 – proton activation by 135–139 – selective oxidation 333–335 Ziegler–Natta-type olefin polymerizations – single-site versus two-center Fe 164, 261–262, 266–267, 274–283 oxycations reactivity 334–335 Z-scheme process 224 – Thomas chemistry 339