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Index
aab initio calculation, theoretical background on– brief review of elementary quantum
chemistry 343–346– density functional theory 346ab initio density functional theory 343, 350ABO3 formula 480ABO3 perovskites 440, 454, 481, 632, 731– structure 456, 462, 870, 886– type oxides 440, 686–– crystal structure of 870abrasive materials 34absolute oxygen nonstoichiometry 818absorbing materials 5absorbing oxides 6acetaldehyde 543acetates 81, 126acetic acid 13, 74, 519, 530, 531, 532, 543acetone 5, 15, 16acetonitrile 16acetylacetonates 16acetylene 72– based flame 75, 76– based FSS 76acoustic waves 91acrolein 543actinides 239activated reactive synthesis 29activation energies 155, 183, 193, 291, 298,
302, 908– apparent 382–– the suprafacial and intrafacial
processes 377– barriers 597– for ionic solid-state diffusion 315– for permeation 888–– for O2/H2 314– Seebeck effect 193activation milling 29
activation of oxygen species, on perovskiteswith oxygen defects 393
actuators 37adiabatic flame temperature 395adsorbents 40adsorption 179– and oxidation of gaseous NO2 443advanced oxidation process (AOP) 479, 489aerosol droplets 105aerosol formation 105aerosol spray synthesis methods 69AFeO3 perovskite catalysts 482AFM images showing the surface morphology
of Ln2Ti2O7 thin films grown on 241, 243A/F oscillations 566agglomeration 29, 81, 83, 101, 873– hard 42– of particles 40aging 5, 12– time 99(AgNbO3)1�x(SrTiO3)x solutions 681agreement factors 275, 276Ag–SrTiO3 photocatalysts 681air 72– separation 767alcohols 42, 74, 401, 406, 530alcohol steam reforming (ESR) 539– reactions 540, 541–– reactions involved and thermodynamic
data 540–543– types of alcohols used 539aldehydes 401, 406Al–Fe-pillared clay catalysts 492Al3+ ion 283Al ions 200, 201aliovalent doping 182aliovalent substitutions 197alkali metals 233– doped perovskites 442
929
Perovskites and Related Mixed Oxides: Concepts and Applications, First Edition.Edited by Pascal Granger, Vasile I. Parvulescu, Serge Kaliaguine, and Wilfrid Prellier. 2016 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH & Co. KGaA.
BaNbyFe1�yO3�δ (BNF) 902band energy 280bandgap 143, 350, 478– excitations 478– formation 346– of a photovoltaic material 147band structures 346– YAP and energy of its defects 283Ba nitrate 85barium cobaltite Ba0.5Sr0.5Co0.8Fe0.2O3-δ
(BSCF) 175, 855– family perovskites 723– membrane 726– membranes 728, 895, 920– O2 permeation flux, reversibility of 903– oxygen fluxes 760– permeating O2 flow 758– properties of 722– vs. SFC–BSCF membranes 727barium cobaltite Ba0.5Sr0.5Co0.8Fe0.2O3-δ
(BSCF)/Ag (BSCF/Ag) 855barium titanate (BTO) 99, 216– based solid solution 216barium zirconate oxide 99BaRuO3 perovskites 439Ba salt precursor 85Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3�δ (BSCFNiO) 763Ba0.5Sr0.5Co0.8Fe0.2O3�δ membrane– SEM analysis 726Ba0.5Sr0.5Fe0.9Al0.1O3�δ (BSFA) 902Ba0.5Sr0.5Fe0.8Cu0.2O3�δ (BSFC)
formulation 902(Ba, Sr)(Fe, X)O3�δ series (BSFX) 902BaTiO3 mesocrystals 107BaTiO3 nanocrystals 103BaTiO3 nanoparticles 85, 103, 107BaTiO3 network 683BaTiO3 particles 85, 104BaTiO3 perovskite 39– structure of 683BaTi1�xNixO3�δ 502batteries 144Ba1�xSrxCo1�yFeyO3�δ (BSCF) 720BaZr0.3Ce0.6Y0.1 Zn0.05O3�δ (BZCYZn) 905BaZSM-5 membranes 885BCFNO membrane reactor 762BCFZ membrane 854bed-to-wall mass 741bed-to-wall mass transfer limitations 744,
oxidation 605Ca-stabilized zirconia membrane 850catalysts 37, 144, 543, 549– effect of the support 546– general assessement 549– in-shell configuration 741– noble metal catalysts 545– non-noble metal catalysts 545– perovskite-type catalysts as good
candidates 547– types of catalysts used 544catalytic activities 74, 130, 377– in CO oxidation 451– of 3DOM LaCoO3 131– monitoring 61– of prepared perovskites 41– for toluene combustion 131catalytic combustion, of chlorinated organic
compounds 426catalytic dry reforming of methane– drawback 510catalytic flameless combustion, of
methane 377catalytic membranes 488catalytic oxidation 476– of HC and CO 799– in liquid phase 475– of NO 443– reactions in liquid phase 475catalytic performances– with a Pt–Rh/Al2O3–CeO2 reference
catalyst 576– of perovskite-type catalysts, for H2
production from alcohols–– ethanol steam reforming 549, 550–– glycerol steam reforming 551, 552– of perovskite-type materials, in NO+CO
reaction 575catalytic studies 56–63
– chemical looping combustion 57, 58– dry reforming of methane 59–63– reduction of 57– total oxidation of methane 56– total oxidation of methanol 59catalytic system, toward reduction of NO by H2
in presence of oxygen 590catalyzed continuously regenerating trap
process 321, 325combustion, CO2 capture 6, 86, 290, 292, 376– Ce-containing perovskites 904– Ce-free formulations 909– dual-phase metal cerates–– cermets 905– at higher temperature 85– high-temperature membranes–– gasification systems combined with
combustion 890–– O2 separation and combustion 889
Index 935
–– perovskite membranes for O2
separation 889–– R&D membrane concepts 889– high-temperature membranes and
membrane reactors for gas separation882
– high-temperature membranes 885–888– membrane design, general criteria for
893– permeation 910– perovskite-containing membranes for CO2
separation 892– perovskite membranes for H2 separation and
295, 301, 317– vs. composition curves 294– diffusion coefficient 179– expressed as 315– of HIP LSGM 293– in perovskites 315– temperature characteristics–– comparison of 79– values 79–– comparison of 78conductors 289
configurations of a catalyst–ferroelectric hybridpacked 430
Co–Ni alloy 506CO2/N2 separation factors 885constant oxygen flow 854contamination 29, 34, 38– tolerated in final material composition 38continuously regenerating trap (CRT) 437, 802conventional ceramic method 5conventional cryogenic oxygen plants 753conventional rotary mills 32convergent beam electron diffraction
(CBED) 219conversion curves 404conversion data, expressed as T50 and T90 (°C)
of Pd/LaFe0.8Co0.2O3 andLaFe0.77Co0.17Pd0.06O3 577
representations for 912Coulomb correlations 349Coulomb energy 346Coulomb explosion 149coulombic attractions 299covalent/ionic character of the metal–oxygen
dipolar liquids 5dipolar polarization mechanism 100dipole moment 214dipole polarizability 274direct flame synthesis, of Y2O3 75direct MW irradiation of solid reactants 5direct piezoelectric effect 211– for compression and tensile stress 212disk-shaped dense membrane reactor 850disk-shaped perovskite membrane 850
dispersion-strengthened alloys 27displacement reaction 9distortions 1913DOM LaFeO3 perovskite– physicochemical properties of 132– syngas and hydrogen of 8483DOM La1�xKxCoO3 catalysts 4453DOM materials– applications 113– preparation 114–– colloidal crystal templates 114–– infiltration of precursors in voids of
templates 122–– removal of templates 122– structure (inverse opal structures) 1223DOM materials 113–1233DOM perovskite metal oxides– precursors, templates, calcination
temperatures, crystal phase properties, andapplications of 115–121
3DOM perovskite mixed metal oxides– preparation of–– characterization of 3DOM LaFeO3 134–– 3DOMLaFeO3withdifferent pore sizes 131–– formation mechanism 136–– precursor solution 123–– preparation of polymer spheres and
colloidal crystal templates 131–– synthesis of 3DOM LaFeO3 134– preparation of 123–138– selection of sphere templates 126– synthesis methods and applications of–– Eu1�xSrxFeO3 130– synthesis methods and applications of 131–– BaTiO3 127–– CaTiO3 and Yb- doped 127–– LaAlO3 131–– LaCoO3 and related oxides 131–– LaFeO3 and related oxides 129–– LaMnO3 and related oxides 128–– Li0.35La0.55TiO3 128–– LiNbO3 128–– Na0.5Bi0.5TiO3 128–– PbTiO3 and related oxides 127–– Sm0.5Sr0.5CoO3 1313DOM-structured materials 457dopant-induced metal support interactions
double mechanical alloying 29double-perovskite phase 143double perovskite structure 176downstream exhaust gas 890droplet reactor 77droplet size distribution 71droplet-to-particle mechanism 71drying 77dual-membrane reactor 523dual-phase membrane (DPM) 311, 730, 888– materials 755dual-phase perovskite membranes 902dual reactor concept 524dual site Langmuir–Hinshelwood model 380ductile material 29, 30, 31DyBa2Cu3O7 films 146Dy0.08W0.04Bi0.88O1.56 (DWSB) 874
eearth metal doping of photocatalysts 490EDTA–citrate sol–gel process 910effective cluster interaction (ECI) 355, 356effective coordination number (ECoN) 274,
318, 755, 896, 905, 914– by doping 895– of LSGM 901electronic conductor 177electronic contribution 176electronic density 198electronic disturbance 621electronic energy 344– levels 143electronic Hamiltonian 344electronic properties 79, 149, 311electronic/protonic conductivity 233electronic reconstructions 143electronic structure 349, 350electronic wave function 347electron migration 320electron paramagnetic resonance 82electron spin orientation (net spin) for Co
ions 350electron transport optimization 148electron transport properties 148electron vacancies 660
940 Index
electrostatic effects 246electrostatic errors 348electrostatic instability 150electrostatic interaction 348electrostatic potential 316, 317– gradient 316, 317electrostatic precipitators 81elemental composition (EDX) 651emerald crystals 17emulsions 773endothermic reaction 526, 540energy– barrier 597– computation using expression 888– consumption 396, 517– demand 881– efficiency 753– function 355– research 144– transfer 91enthalpy 6, 74, 77, 81, 527, 888– combustion 74– of formation of ABO3 and A2BO4
perovskites 371environmental catalysis 563epitaxial films 148– STO films 147epitaxial strain 896epitaxial thin films 145epoxidation reactions 475epoxide unlike multimetallosilicate
materials 478equilibrium composition– of gases, in reaction of ethanol with
steam 542, 543– of gases, in reaction of glycerol with
steam 544equilibrium-limited reaction systems 739equivalent electric circuit, corresponding to an
oxide ion conductor 174esters 401, 540ethane 523, 524ethane dehydrogenation
(BaCoxFeyZr1�x�yO3�δ membranes) 855ethanol 74, 77, 402, 539, 541, 545, 546– dehydration 544ethanol steam reforming– at high temperature 542ethanol steam reforming (ESR) 540ethanol synthesis 783ethylbenzene 417ethylene 399, 523, 524, 549– cracking processes for 523
– selectivity at a methane 519ethylene glycol 13, 69, 126, 127, 129, 130, 131,
134, 137, 138, 543ethylene oxide 779ET-specific surface areas 54EuFeO3 perovskite 419Eu2+ ions 196Eu3+ oxidation state 196European emission standards for gasoline
N)3 198eutectics 10EuTiO3 and related compounds 196–198evaporation 19, 122, 181evaporation-controlled (ECSA) 707evaporation temperature, of solvent 73excitation energies 193, 346exhaust emission control– application of perovskites in 569–578– application of perovskites in–– CO oxidation 572–– model reactions 572–– NO reduction by CO 573–– NO reduction by propene 575–– simulated exhaust conditions 576exhaust emissions 798exhaust gases 591– emissions 42exhaust gas recirculation (EGR) 801exhaust treatment technologies 800exothermicity 780exothermic reaction 540experimental apparatus– for ultrasonic spray pyrolysis system 106– for ultrasound-assisted sol–gel method 104external diffusion limitations 826external mass transfer limitations 751extrinsic defects 659
ffabrication, of devices by chemical sensor
materials integration 106face carbonate formation 727Faradaic flux 892Faradaic resistance 869Faraday constant 179Faraday resistance 871fasoline, European regulation 798fcc cell of cerium oxide with the fluorite
by 377flameless combustion, of methane 72flame-made compositions 79flame-made LSC 80flame-made materials 80– electronic properties 78flame-made titanates 79flame spray pyrolysis (FSP) 71, 395flame spray synthesis (FSS) 71–80– characterized by 72– perovskite-type oxides produced by
72
942 Index
flame synthesis 77– crucial parameters for outcome 73flame temperatures 73, 74, 76flexible piezoelectric composites 225floating zone method, for single crystals
238flow rates 71, 73, 77, 81– of oxygen carrier 73– of precursor 73flue gas recycling 891fluidized bed membrane reactor (FBMR) 740,
745, 762– with oxygen addition 747– schematic representation of 746fluidized bed reactors 746fluorinated compounds 235fluorite 313– space 660– structure 296flux 10, 177foil coatings of Pd/CeO2 783formaldehyde, synthesis 781formate species (HCOO�) 666formation, ammonia oxidation over
LaCoO3 831formic acid 530fossil carbon-containing raw materials 517fossil fuels 189, 865fossil hydrocarbons– partial oxidation of 539fourth generation TWCs 566fracturing 30free energy 219, 354freeze-drying 50, 510frequency 173F-T synthesis 645– hydrocarbons 647fuel burning, atomized droplets 801fuel cells 108, 539– anode/cathode off-gas surrogate 784– Nyquist plot 869– technology 773fuel processing techniques 865fuel production 781– biodiesel production 783– dimethyl ether, synthesis of 783– Fischer–Tropsch synthesis 782– hydrogen production 784–– ammonia decomposition 785–– hydrocarbon reforming 784–– methane, direct partial oxidation of 785–– methane reforming 784–– methanol/ethanol reforming 784
–– water-gas shift 785– methane to C1 oxygenates, direct partial
oxidation of 781– methanol and ethanol, synthesis of 783– total syngas methanation to synthetic natural
gas 782full width at half maximum (FWHM) 242fumed silica 71furnace 71, 82
green oxidants 479grinding 6, 25, 26, 77, 78grinding devices 26grinding energy 35grinding reactions 8Grotthus mechanism 888grow oxides 145growth factors 151growth process– real-time experiment during 151growth rates 93
hhafnia-based oxide systems 300half-Heusler compounds 190halides 26, 48halogenated compounds 413, 414halogenated hydrocarbons– total oxidation of 426–428halogenated metal perovskites 369halogenated organic compounds, total
(HT-WGS) 460high-throughput microreactors, uses 773H2O/CO2 splitting– hydrogen/CO production 855H2O/ethanol molar ratio 551H2O exhibits 727H2/O2 flame 81Hofmeister series 706– of anions 706H2O2 irradiation 488hollow fiber (HF) 845– configuration 743– dense membranes 850–– reactor, schematic diagram 853– LSCF system 731– membranes 724, 744–– reactors 744– robust porous substrate 723hollow particles 84homogeneity
– of final product 70homogeneous catalysts 540homogeneous gel 244homogeneous mixed oxide nanopowders 71homogeneous Ni–BaZr0.7Pr0.1Y0.2O3�δ (BZPY)
cermet membranes 909homogeneous precipitation 12homogenization 29homogenous elemental distribution– in flame-made titanate particles 79H2O2 permeance 488hot zone temperature(s) 85H2-permeable membranes 323, 324, 326, 905– Ce- and Zr-free formulations 910– equation for 324– within Ni 327– within perovskite membranes, equations for
modeling 323– properties, of perovskite membranes 906– schematic representation of 884H2 production 758, 855– from alcohols–– catalytic performances of perovskite-type
catalysts for 549–552– rate 855– by steam reforming of bioalcohols 539H2 purification-related CO oxidations 459H2-SCR catalytic system 588, 589, 590– selective ceramic membrane, uses 891H2 semipermeation, within dense Pd
membranes 324H2 separation, and purification 886H2 SOFCs, perovskite anode for 874H2 transport, permeance vs. permeability
representations 907H2 transport, within membranes 908huge oxygen permeability drop 730hybrid combustors 396hybrid composites 225hybridization 905hybrid solar cells, efficient 369hydride ions 888hydrocarbons (HCs) 169, 172, 376, 518, 524,
559– containing fuel 839– conversion, single catalytic membrane
reactor for 753– in gas streams 437– oxidation 568– radicals 559– synthesis, from syngas 652hydrochloric acid 402hydrochlorofluorocarbons 405
2� 407layered perovskite structures– and families 234– introduction and overview 233–235La2Zr2O7 872LBSM (La0.74Bi0.1Sr0.16MnO3�δ) 874leaching 42– of ZnO 41lead-free piezoelectrics– BaTiO3–CaTiO3–BaZrO3 solid
solutions 216–217– Na0.5Bi0.5TiO3 219–221– piezoelectric properties of BCT–BZT 218, 219– structural phase diagram of BZT–BCT 217,
218lead-free piezoelectrics 215–221lead zirconate titanate (PZT) films 107, 211lean-burn conditions 589, 591lean-burn DeNOx conditions 588– chemical processes 798– combustion of fossil fuels 797– diesel posttreatment (see diesel
posttreatment)– reduction 803– single brick solution 807lean-burn nitrogen oxides (NOx) 587lean NOx trap (LNT) 587, 591, 798lean NOx, after treatment of diesel engine
emissions 590–593Lewis acid 484Lewis acidic center 477Lewis acidity and conversion of cyclohexe 478Lewis acid sites 477Lewis acid TM sols 709ligand-assisted templating (LAT) 709light diffraction methods 31light-off curves for toluene on
nonsupported 422lignocellulosic biomass 540Li+ ion 128limestone 883LiNbO3 films 146
linear ME coefficient 227linear pseudo-piezomagnetism 228Li-O2 battery 103liqids, process involving– molecular self-assembling 14– other methods starting from liquid reactants
or solutions 15–– gel combustion method 15–– ionic liquids 15–– reverse microemulsion 15–– sonication 15– spray drying, and related methods–– freeze-drying 14–– spray–freeze-drying 14liquid crystal 14liquid droplet size 71liquid nitrogen 14liquid petroleum gas (LPG) 102liquid-phase catalytic oxidations– active sites and oxidants 476– environment-friendly processes 475– green oxidants 480–– mesoporous mixed oxide catalysts 486–– microporous mixed oxide catalysts 483–– perovskites catalysts 480– heterogeneous photo-fenton oxidation 488–– photo-fenton reactions 490, 491– photocatalytic ozonation reactions 492liquid-phase oxidations 476, 484liquid-phase selective oxidation 479– using hydrogen peroxide and heterogeneous
catalysts 479liquid-phase sintering 225liquids, processes involving 9– flux method 9– molten salt electrolysis 10– sol–gel 10–13– spray drying, and relatedmethodsquad;13, 14liquid stability 881– presence of O2 and SO2 881liquid–vapor surface tension 19lithium 289lithium-lanthanum-titanate (Li0.35La0.55TiO3,
mechanochemistry 25, 26– advantages 25– historical development 25–27mechanochemists, from ball milling 26mechanosynthesis 25, 28– synthesis of BiMnO3 via 38mechanosynthesis, of perovskites– increasing specific surface area 40– looking for an alternative route to synthesize
new compositions 38– lowering sintering temperature 38– reducing crystallite size and modifying
particle morphology 39mechanosynthesis, of perovskites 37–42mechanosynthesis process– acceleration of balls during milling 29– ball-to-powder mass ratio 29– brittle materials fracture under impact 31– crystal defects and internal residual stress 30– ductile material 30– evolution of diffraction patterns during the
synthesis of LaMnO3, 32– form new phases 31– fracturing of agglomerates 31– ignition–– occurs in-situ in mill 32– mass ratio 29– milled material comprised composed of
polycrystalline particles 30– milling times to achieve a full reaction 32– particle size, decreases rapidly 31– performed using high-energy ball- mill 29– progress of the reaction during ball
milling 32– reaction rate 31– re-agglomeration of fine particles 31– repeated collisions and plastic
deformations 30– stoichiometry of final product 29mechanosynthesis process 29–32mechanosynthesized Ba0.5Sr0.5Co0.5Fe0.5O3
perovskites 39ME coupling coefficient value 226melamine (C3H6N6) 806melt casting 225melting point 10membrane– design 885– exhibited a maximum CO2 flux 913– sealing 895– thickness 885membrane-assisted chemical looping
reforming (MA-CLR) 751
membrane-assisted fluidized bed reactor(MAFBR) 744
membrane-assisted fluidized bed reactors 745membrane housing 743membrane microreactor (MMR) 778membrane microstructure 728membrane permeability 894membrane reactor 103, 739– distributive feeding of reactant 740– drawbacks 747– embrane sealing 755–758– hydrogen production 739– methane conversion and C2 selectivity 767– O2 separation 753–758– reactors, types of 740–753– reactors, types of–– fluidized bed membrane reactors 744–– packed bed membrane reactor 740membrane reactor applications 885membrane reactor catalyst-in-tube 742membrane reactor concept– schematic representation 843membrane reactors 740, 891– feed gas traces 756– heating/cooling steps 757– leakage and back permeation 755– leakage of gas 757– for methane conversion 763– natural gas 764– with O2 membranes 758–768– syngas to ATR-MR 759– viscosity and rigidity 756membrane reduction surface 854membranes 18, 37– maintained their integrity 900– thickness 312, 821, 903membranes, impedance diagram of 334MeOH mixed solvent 130mesocrystals 103mesoporous ceria catalysts 424mesoporous LaCoO3 perovskites 53mesoporous manganese oxides– TEM images of 702mesoporous materials 51, 477– synthesis of 703mesoporous metal oxides 713mesoporous mixed oxides 52, 486mesoporous nickel–silicate membranes 488mesoporous nonsiliceous materials 52mesoporous oxides– formation mechanisms of 704– materials, formation of 704– synthesis of 702
952 Index
– thermal stability of 712mesoporous perovskites 48– reduction treatment of 63mesoporous SBA-15 silica host support 511mesoporous silicas 486, 487– materials 701– synthesis 703mesoporous TM oxides 701, 703– stability of 712– template removal 713mesoporous transition metal oxides 701, 707mesostructured carbon 63, 64mesostructured silica 63mesostructured solid template 63metal acetates 14metal–acidic clays 485metal agglomeration-resistant catalysts 579metal alkoxide precursors 126metal aluminate 546metal–aluminophosphates (APO) 485metal atoms 47, 546metal-based catalysts 507metal cations 10, 13, 72, 74, 328, 373metal–CeO2 interfacial sites 568metal citrate complex, as precursor 53metal complexes 107metal dispersion 550metal electrodes 228metal-exchanged zeolite systems 807metal films 19metal-fuel additives 437metal-hydroperoxy species 530metal–insulator (MI) 351metal ion–oxide bond 483metal ions 107, 200, 398metallic conductivity 199metallic element 47metallic natural elements 49metalloenzymes 528metal matrix composites 31metal nanoparticles 590metal nitrates 13, 53, 74, 130, 131– as precursors 53– salts 131metal organic chemical vapor deposition
521, 527, 883– catalytic oxidations over 593– complex 70– films 19
– precursors 69– reducible 521metal–oxygen bond 270, 276– distances 274metal–oxygen bonds 888metal particle size 549metal-perovskite catalysts– suppression of growth of precious metal
particles in 578metal precursors 71metals 29, 190, 886metal salts 396– precursors 69metal species 502metal-support interactions (MSI) 567metal–zeolites 485metastable monoclinic Y2O3 phase 75metastable particles 29metastable phases 18– stabilization of 7methane 72, 169, 373, 517, 531– to acetic acid 530–532– autothermal reforming of 758– combustion on metal oxides 72– combustion on, temperature dependence 56– conversion tomethanol, nondirect and direct
routes of 528– conversion to value-added products 517– dry reforming of 60– flameless combustion of 72– functionalization, noncommercialized routes
of 518– to methanol and its derivatives 527–530– oxidation, photocatalytic 530– oxidation to acetic acid, nondirect and direct
routes of 531– oxidation to methanol 519– oxidative coupling of 519, 765– oxidative transformations of 519– to produce liquid hydrocarbons directly
from 526– products from 518– resistant to chemical reactions 518– sources of 518– steam reforming of 518– total combustion of 63methane (fuel) 16methane-based flames 81methane combustion 72, 82, 101, 749methane combustion, kinetics of– approaches 378methane combustion, kinetics of 378–385– first-order kinetics 379–383
Index 953
– power law kinetics 383–385– Rideal–Eley kinetics 379– two term kinetics 385methane combustion, mechanism of 376–378methane conversion 744– degree of 382methane cracking reaction 501methane, dry reforming of 502methane, dry reforming of– carbon dioxide 501– LaNiO3 as catalyst precursor 502– lanthanum in perovskite La1�xAxNi1�yByO3,
507– nickel in perovskite LaNi1�yByO3, 506– perovskite as support of active sites 510– supported perovskite 510methane flame 72, 75methane monooxygenase (MMO) 528methane oxidation 53, 82, 86, 129– intrafacial (lattice) and suprafacial (surface)
reactions 386– temperature profile 827methane oxidization 856methane partial oxidation 753methane steam microreformer 784methane steam reforming 750methane, temperature and molar fractions
of 789methanol 15, 63, 74, 129, 137, 138, 518, 528,
529, 530, 531, 539, 540, 543– selectivity 529methanol combustion 129methanol oxidation 61– conversion profiles as a function of
microwave-assisted processes– of a La–Co citrate complex 100– in synthesis of perovskite materials 94microwave chemistry– basic concepts of 92, 93microwave coupling 97microwave-derived samples 101microwave excitation, of molecules 100microwave heating 93, 100– advantages over conventional heating 93– in area of synthetic organic chemistry 93– in combination with traditional synthesis
methods 93–99– vs. conventional heating 93microwave heating technique 92microwave irradiation 91, 100– frequency 99– time 101microwave methodology 92–101microwave operating powers 101microwave power 101microwave-prepared GdFeO3 nanocrystalline
891, 915– carbon dioxide on oxygen permeation of 729– for cost-effective oxygen separation 753– plant design of autothermal process 760MIEC performance 731– as electrode for SOFC or SOEC 173MIEC perovskite membranes 753MIEC properties, of perovskites 889MIEC systems 725milling devices 27, 28milling facilities– attrition mills 35– planetary mills 34– Spex mills 32– Zoz mills 36milling media 29, 38milling process 29, 30milling time 26, 32, 41, 42, 43– on process 38millistructured reactors 778
– applications/possible scale-up 778–– ammonia oxidation 779–– benzene hydrogenation to
cyclohexene 780–– cyclohexene, hydrogenation 780–– dehydrogenation of alkanes 781–– dehydrogenation of cyclohexane 780–– dehydrogenation of
methanol 781– challenges 773– currents and operational conditions,
summary 788– gas phase 776–– catalytic wall microreactors 777–– micropacked bed reactors 776– synthesis gas production 781–– partial oxidation of methane 781–– steam methane reforming 781– three-phase reaction 777–– catalytic system 777–– configurations 778mills, disadvantage of 37mineralization– into CO2 and inorganic compounds
475mineralizer-free YAP 280mineralizers 279, 280, 281– on Cr–YAP, effect of 282minimum energy path (MEP) 351mini-scale fuel cell, natural gas 784miscut angle 145mixed growth mode 158mixed ionic–electronic conductive
(MIEC) 311, 739, 853, 886mixed ionic–electronic conductor 176mixed metal oxides 47mixed oxide 6, 7, 13mixed oxide materials– synthesis of 53mixed oxides 7, 10, 143, 289mixed oxides as electrolytes and mixed
conductors– applications of 303–306mixed oxides electrolytes– synthesis methods and properties of
290–293
Index 955
– synthesis methods and properties of 290mixed oxides with ionic conductivity– solid electrolytes based on CeO2 298–300– solid electrolytes based on ZrO2 296–298mixed oxides, with ionic conductivity 295–300mixed oxides with mixed conductivity
301–303mixed oxide systems 390, 414, 841mixed solids 8mixed valences, in perovskites– mixed valences due to anion deficiencies 371– mixed valences due to isostructural
substitution of cations 373mixed valences, in perovskites 371–373Mn-based oxygen carriers 841Mn cations 12Mn ions 12Mn/Na2WO4/SiO2 catalysts 766Mn4+ species, in nanocast LaMnO3 54Mn system 182mobile ions 289mobile oxygen 144– species 466, 620mobility 290modeling O2 permeation within perovskite
membranes, equations for 319modified phase diagram of BCZT– showing phase convergence region and 218molar ratios 7, 297molecular beam epitaxy 19molecular beam epitaxy, growth chamber
of 146molecular oxygen dissociation 728molecular oxygen flux 756molecular sieves 883molecular weight 74molten carbonate (MC) 888molten carbonate fuel cell (MCFC) 865molten salts 9molybdenum 191momentum transfer 154Mo–Mn–Al mixed oxides 621monoatomic oxygen flux 180monoclinic distortions 48monoclinic La2Ti2O7 oxide 236monoclinic structure of Ln2Ti2O7 237monovalent halogen 369Monsanto technology 532Monte Carlo (MC) simulations 356morphology of perovskites– investigated for total oxidation of
VOCs 395–397morphotropic phase boundary (MPB) 216
motor vehicles, exhaust systems of 797Mott’s adiabatic small-polaron conduction
model 193MoV0.8Te0.23Ox perovskite 483MRT sealing 747MSR/heat exchanger configurations 779Mössbauer spectra recorded on EuFeO3 419Mössbauer spectroscopy 374, 422, 666, 726muffle furnace 42multianvil press 8multicomponent catalysts 527multicomponent oxide systems 483multiferrocity, in BiFeO3 144multiferroic materials 226, 227multiferroics 226multifunctional composites 211multifunctionality 226– in ceramics 226multifunctional piezoelectric composites
226–229multilayers 149multiple impregnations 54multiple reactions 28multiple roles of CeO2, in three-way catalytic
nNano BaTiO3 683nanocasting 61, 63, 397, 702– series of perovskite-structured mixed metal
oxides with 54nanocasting (hard templating) 48nanocasting, general principles of 51nanocasting, of perovskites– H2-TPR studies 53nanocasting, of perovskites 52–54nanocasting process, using ordered
Nb2O5–SiO2 system 485Nb-substituted sample 198NBT ceramics 221– captured in an oscilloscope–– response of 221– for external mechanical stimuli–– response of 221N2, dimensionless (Z) transient isotopic
response curves of 596Nd0.6Sr0.4FeO3�δ–60 wt% Ce0.9Nd0.1O2�δ
(40NSF-60CN) dual-phase membrane914
Nd2Ti2O7 thin film grown on (110)-SrTiO3
substrate 246NEB-derived energy 353NEB energy profiles 353– for an oxygen atom 353NEB method, schematic illustration 351nebulization 81– of precursor salt solution 82nebulizer 81nebulizer/atomizer 71– geometry 71N-electron wave function 345neodymium orthogallates 276neodymium oxide 302neodymium perovskite system 276Nernst–Einstein equation 176, 179, 315Nernst–Planck equations 316net current density 317net zero electricity consumption 753neutral ambipolar diffusion 178new compounds 3– improved properties 3N2 formation and N2O formation– integral reaction rate 595NG, oxy-combustion of 8906 NH3 conversion 828NH3 molecule 806NH4OH in aqueous solution 661NH3–O2 pump–probe experiment– NO, N2, and O2 pulse responses 831NH3-SCR applications 806NH3-SCR, location of current 589NH3-SCR process technology 587NH3-SCR technology 587, 591(NH4)2SO4 678NH3 under oxygen-rich conditions
oxygen 34, 72, 170, 273, 289– carrier gas through a nozzle 71– chemical potential gradients 753– content 357– defects 150– deficiency 196, 199– exchange from 72– exchange kinetics 821– flow rate 73– insertion 832– ion conductors 354– ions/molecules 755– ion transport 458– isotopic exchange experiments 819– linear velocity of 73– loss 191, 192, 846– membrane separation process 863– migration energy barrier 353– into milling reactor 40– mobility 51, 75, 182, 377, 398, 465– movement, from an octahedral site into 352– nonstoichiometry 303– overstoichiometry 427– permeability 39– -permeable membrane reactors 762– permeation cubic phase 348– permeation flux 728– permselective membranes 748– pressures 150, 151, 152, 160– radicals 491– sensor 305– sensors 289, 562– separation 765– separation from air 754– stoichiometry 845– storage capacity 42, 377, 843– storage capacity (OSC) 564, 566, 567, 660– storage properties 415– tracer diffusion coefficient 178– transfer–– within ionic and redox switchable
materials 883– transfer coefficient 176– transfer reactions 477– transport 175, 182, 183, 290– transport membrane 855– transport parameters 178– transport, in perovskite oxides 180– transport properties 170– vacancies 888– vacancies, genesis of 888β-oxygen 462oxygen anion-conducting electrolytes 864
splitting 842oxygen concentration– in GdO (CoO2) layer 358– gradient 864oxygen conductivity– of perovskites 393oxygen-deficient species (CeO2�x) 670oxygen-depleted air 841oxygen diffusion 79, 175, 180, 181, 355– coefficient 182– in cubic perovskite 183oxygen exchange 34, 822– experiments 820, 822– parameters 822– rate 150oxygen exchange materials– for solar thermochemical splitting 844oxygen flux 180, 722, 726, 730, 754– analytical expression 821oxygen interaction 817– case study 820– isotopic exchange techniques 819– mixed ionic and electronic conductor
(MIEC) 820– nonstoichiometry 818
Index 961
– secondary ion mass spectrometry 819– steady-state isotopic transient oxygen
exchange 819oxygen ion 289, 354– -conducting membrane separating 843oxygen ion conduction 149, 295, 323– in oxidizing conditions 298oxygen nonstoichiometry 818, 821– window 842oxygen partial pressure 178, 180– conditions 182oxygen reduction reaction (ORR) 874oxygen-selective membranes 741, 754– for membrane reactors 754– reactors 762, 764oxygen-selective membranes in membrane
reactors 755β-oxygen species 462oxygen transport kinetics, in MIEC material– factors governing 176oxygen vacancies 130, 150, 160, 182, 198, 202,
281, 282, 296, 352, 355, 462, 602, 719– arrangement 358– configuration of oxygen sites in the GdO
layer 359– creating 182– determining role in 183– gradient 854– ordering 896– suppression of 895oxygen variation 149– and epitaxial relation 150oxynitrides 48, 198, 235ozonation 492, 493ozone 405, 430, 559ozonization processes 483
ppacked-bed discharges– geometries for 429packed bed membrane reactor (PBMR) 740packed bed membrane reactors 741– limitations 744palladium 423– in total oxidation of toluene 423parabolic rate law 4paramagnetic species 430parameterizing energy function 355partial density of states (PDOS) 350partial doping 896partial oxidation 400, 882– of hydrocarbon 400– of methane (POM) 720, 741
partial pressures 16, 894partial reduction, of NO 560partial substitution 49– of La3+ with Ce4+ 373– of La3+ with Sr2+ 373particle agglomerations 101particle, average size 6particle formation– in flame 73– heterogeneous 75– mechanism–– in flame-assisted methods 72particle morphology 71, 77particle size 3, 27, 29, 30, 39, 71, 73, 74, 77, 81,
2,4-pentadione 238periodic boundary condition 347permeabilities 885, 886, 894– of membrane, steady-state 904permeance–permeability plots 905permeance vs. permeability 907– plots for dual-phase perovskite–carbonate
materials 910permeation 910– fluxes 893– of molecules (PIMs) 884– of oxygen 180– process 313– properties 885permittivities 316perovskite– -structured mixed metal oxides 47–– methods used for synthesis of 50– structure, under tensile stress 215perovskite compounds, with REE inside site A
– H2 permeation of properties 906– membrane scientist for developing
efficient 894– O2 permeation of properties 897– optical micrographs 757– for partial oxidation of methane 763Perovskite Membranes for Selective O2
Permeation– Co-Containing PeroCo-containing
perovskites 895perovskite pigments 259– black 263– blue 263– brown to light brown 262– described, according to chemical
composition 259– magenta to pink 263– red and orange 261perovskite-related materials– epitaxially integrated 144perovskites 25, 29, 34, 47, 170– ABO3 502– activity 483– as a diverse and active class of materials 369–– structural diversity, tolerance factor, and
thermodynamic stability 370– applications, in diesel engine de-NOx
conductivity 170– –fluorite DPMs encompasses systems 902– formation 54– formulations 35, 41, 42– hybridized with metal phases 314– LaNi0.8Fe0.2O3 506– LaNiO3 506– La2Ni2O5 372– LaNiO3 502– –LaSrMnO4 616– lattice 393– -like K2NiF4 oxide 507– material 178, 183, 754, 817–– GbBaCo2O5.5 (GBCO) 350–– providing mobile oxygen 888–– and related compounds oxygen transport
parameters 180– via mechanosynthesis 43– membrane 314, 889–– reactors 755, 763– as mixed ionic–electronic conductors 170– mixed metal oxides 123–– three-dimensionally ordered macroporous
(3DOM) 113– morphology 845– nanocast 54– nonstoichiometry 719– oxides 47, 442, 572, 604, 632–– substituted with Pd or Cu 47– and oxygen vacancy 414–416
Index 963
– and perovskite membrane, compilation of O2
and H2 diffusion and surface exchangecoefficients in 332
– phases 29, 38, 42–– proposed as pigments 260– porosity-to-tortuosity ratios 328– as powders, forced reduction 847– as powders, solar reduction 851– preparation 25– semiconductor gas sensors 102– sheets 235– SrTiO3 678– stable 49– structure 47, 171, 721, 888–– by doping 727–– ideal 48, 49–– lattices with lower t values 48– structure 48, 49– surface area/porosity of 480– systems, investigated for NO reduction by
CO 574– titanates 215– using porous silica xerogel as hard
template 53perovskite structure LaNixFe1�xO3 506perovskite symmetry– cubic 895perovskite synthesis 32, 37– evolution of 49–– compatibility of support with desired
phase 50––method advantage of providing high surface
concentration 51–– resistance to SO2 poisoning 50–– sintering of particles 49–– specific surface areas of final products 50–– surface area 49–– thermal energy required for the
crystallization replaced by 50perovskite-type calcium manganates
photo-Fenton cycle 492photo-Fenton efficiency in degradation of
rhodamine B 490photo-Fenton oxidation of acetic acid 490, 688photo-Fenton oxidation of 4-chlorophenol
onto Al–Fe clay 492photo-Fenton processes on iron oxide 489photogenerated electron–hole pairs 682photoinduced electron–hole pairs 676photoluminescence 233photoluminescence properties 98photoluminescent emission 98photooxidation of isopropanol over 407photo-oxidative degradation of toxic organic
pollutants 478photosynthesis 539photosystem II, in plants 371photovoltaics 108physical vapor deposition methods 145piezo- and ferroelectric properties of Ln2Ti2O7
thin films– experimental setup 244– Ln2Ti2O7 (Ln = La, Pr, and Nd) thin films
grown on (100)-oriented SrTiO3
substrates 247– Ln2Ti2O7 (Ln = La, Pr, and Nd) thin films
grown on (110)-oriented SrTiO3
substrates 246– metastable Ln2Ti2O7 (Ln = Sm, Eu, and Gd)
thin films grown on (110)-oriented SrTiO3
substrates 249
piezo- and ferroelectric properties of Ln2Ti2O7
thin films 244–250piezoceramics 223piezoelectric-based flexible transducers 225piezoelectric ceramic (PZT) 221, 225, 228– vs. polymers 223piezoelectric charge constant 39piezoelectric coefficient 213, 214, 217, 221, 228– enhanced 216piezoelectric composites 224piezoelectric composites 223, 224piezoelectric constants 228piezoelectric devices 37piezoelectric domains 245, 247piezoelectric effects 212, 213piezoelectricity 212–215– intrinsic 215piezoelectric materials 212, 214, 215, 228– an overview 214– research, major breakthrough 212– and their comparison 214piezoelectric phenomena 215piezoelectric polymers 224– polyvinylidene fluoride 222piezoelectric polymers 221, 222piezoelectric properties 239piezoelectric voltage coefficient 214piezo-/ferroelectric properties 235piezoloops 246, 247, 248piezomagnetic coefficient 228piezoresponse 228– signals 246pigments, based on perovskite 259piston–cylinder press 8planar fiber robust porous substrate 723planetary, and vibrating mills 26planetary mills 27, 34plant-derived materials 517plasma activation conditions in gas, total
oxidation under 404–406plasma-driven catalysis for total oxidation of
hydrocarbons, mechanism for 431plasma emission 149plasma enhanced chemical vapor deposition
ssalt-assisted spray synthesis 70salt-assistedultrasonicspraysynthesis(SASP) 85salt-assisted USP 82salt concentration 73sapphire 17SBA10 resist– to sintering 512sb initio calculations 198scanning electron microscopy images for the
vanadium 423scanning tunneling microscopy 18schematic of composite with 0–x201E;3
connectivity 224
968 Index
schematic of experimental setup used for thetime-resolved imaging analysis by fastphotography technique 161
schematic representations of FSS, FH, and USSprocesses 70
Schottky junctions 682Schrödinger equation 343, 344, 345SDAs formed, by a single molecule or ion 14sealing application technique 756, 757secondary ion mass spectrometry (SIMS) 31,
semi-rigid solid 12SEM micrographs of LaMnO3+δ perovskites
prepared by combustion method 395SEM micrographs of pellets sintered at 299SEM pictures of PrCoO3 396sensitivity– to CO adsorption 42sensor operation temperature 306sensors 37, 39, 91, 97, 108, 144separation factor 894sequential deposition of SrO and TiO2
layers 158SFC2 films 854SFN-coated membrane 729shaking mills 27– mechanosynthesis in laboratory scale 27shear stress 28, 34shell-and-tube configuration 742shell structure 122, 123Sherwood number 826shrinkage 126Si/Al ratios 885SiC DPF– for soot removal in diesel exhausts 438SiC monoliths 824S–I interactions with pros 708Silica Aerosil 200 54silica MCM-41, 14silica mesoporous materials 701silica template, removal– by treating with aqueous NaOH solution
54silica xerogel 18silicon 147silicon oxide (SiO2) 114silicon wafer microchannel walls 780silver 75silver paste 756simulation model construction 346–348single-base metal oxides 398single crystals 3, 10, 16– accelerated crucible rotating technique
membranes 900SrCO3 formation 728SrCoO3�δ and related phases 199, 200SrCO3 phase 508Sr dopant, segregates to 416Sr, Fe, and Nb oxides (SFN) 729SrFeCo0.5Ox (SFC2) 853SrFeOx compounds 372SrFeO3 phase 374SrFeO3 structure 901Sr2+ ions 392SrRuO3 perovskite 101Sr substitution, in LaCoO3 and LaMnO3
perovskites 47SrTi0.1Fe0.9O3�x synthesized 687SrTiO3 (STO)– intensity RHEED monitoring of growth of
three molecular layers of 159SrTiO3 films 106SrTiO3 (STO), films 147SrTiO3 heteronanostructures 679SrTiO3 nanoparticles 681SrTiO3 nanopowders 680SrTiO3 perovskites 441, 442SrTiO3 photocatalysts 681SrTiO3 surface 679Sr1�xKxTiO3 perovskites 444Sr1�yBayCoO3�δ family 481stability– explained by 244– of F-phase 302– of La0.6Sr0.4CoO3�((LSC) membranes 899– long-term 893– of LSC membranes 914– of the metastable phase 244– m-ZrO2–α-Fe2O3 system 660– obtaining with Ca 550– under reforming conditions 62stack-like reactors 778state-of-the-art material 725state-of-the-art modular instrumentations 149
materials 707surfactant micellization 705, 707surfactant molecules 14surfactants 30, 42, 292– cooperative self-assembly 51– exhibits a strong influence on sintering
behavior 292
972 Index
Suzuki coupling reactions 776sweep gas 750symmetry– of CaTiO3 170synchrotron radiation facility 151synergistic effects 493syngas 632, 641, 762, 765. see also synthesis gas
(syngas)syngas generation, from methane 844synthesis gas (syngas) 659, 890synthesis, of metals– grinding of halides 26Szegvari attritors 36Szegvari mills 28, 35, 36, 37, 42– configuration 35
tTammann temperature 712tantalum 191tantalum oxynitrides 415TAP experiments 832TAP measurements 621TAP reactor 830TAP-2 reactor 830tartaric acid 82TE efficiency 190teflon 7, 34TEG– conversion efficiency of 203TEM images– of Co3O4 nanocasted oxides 398– of 3DOM LaFeO3 137– of LaFeO3 421TEM microphotograph– of Ce0.78Gd0.2Sr0.02O2≏ grounded powder
prepared by Pechini sol-gel 291– of sintered electrolyte material with fluorite
structure 294temperature 15– of calcination 50– densification 290– dependence of methane combustion on 56– flame 82– gradient 7, 17– profiles of reaction rate of methane
– of H2 54temperature-programmed superficial reaction
(TPSR) 659temperature-related oxygen
nonstoichiometry 80temperatures 289– for reactions 4templates 14, 18– crucial role 51– hard 63– hard, as precursors 52– pores 51, 54– three-dimensional structure, to maintain
51terfenol-D 228– magnetostriction value of 228ternary CeO2-ZrO2-MO systems 297ternary oxides 290Tessellation in space for the
Ba1�xSrxCo1�yFeyO3�δ (BSCF) 349tetraethyl lead 559tetrafluoromethane 405tetragonal distortions 48tetragonal zirconia-based phases 295tetrahedral fluorine 123tetraline 4171-tetralone 481tetra-n-butyl titanate 15tetraselmis suecica 677TGA approach 822TGA experiments 822theoretical background on Ab initio
calculation 343–346theoretical density 296thermal conditions 72thermal conductivity 190, 191, 196, 197, 203– lattice 190thermal conductivity and figure of merit ZT of
the series CaMn1�xMxO3�δ 195thermal destruction 613thermal diffusivity of the cubic phase 196thermal energy 50, 588thermal evaporation 290thermal expansion coefficient (TEC) 169,
389– in ambient air undergo 389– biogenic 389– chlorinated 389– complete mineralization of 390– concentrations at ground level 390– distributions of 390– health risks for each 389– from industrial or other sources 390– major source of 389– negative effect of 389– oxidation 405– perovskites for total oxidation of 391, 394– pollution with 390– sensing properties, of sensors 106– total oxidation of 390– toxic 389volatile precursors 16, 81volatility 74Volkenstein mechanism 419VO4 species 483
wWagner equation 180, 320, 324Wagner hydration 323water– acting as a pressure transmitter 7water/acetic ratios 15water/alkoxide ratio 12water-gas shift (WGS) 451, 459, 577, 670, 751,
synthesis 86xerogel 12xerogel film 12xhaust emission control– application of perovskites in, model reactions–– N2O decomposition 573XPS analyses 454XPS characterization, decreasing the
lanthanum content 399XPS data, interpretation 87X-ray absorption near edge structure
– incorporation of a second rare earth oxidedopant in 302
ZrO2-Me2O3 systems 295ZrO2-MO systems 295ZrO2-Sc2O3 system 295ZrO2-Yb2O3-Y2O3 system– synergetic effects reported 297Z-scheme principle 683Z-STEM images of the BZY film 153ZT values 190