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INDEX
Adsorbed layer of A g catalyst in oxidation of C2H4, characteriza tion 209-236 Adsorption behavior of C H 220, 224-226 C O over Pt-alumina 80 isotherms C H 226/ C0 228/ C O - P t system 88, 90/ Adsorption-desorption of C O on N i .. 10/ Adsorptive capacity of catalyst 1 Air-fuel ratio, C O concentration effect 70,71/ Air-fuel ratio, three-way catalyst, content, effect 72,73/ Ammonia formation with automotive three-way catalysts 146, 147/ Ammonia formation in N O reduction 109-139 Auger electron spectroscopy 8, 20/ Automobile exhaust, function of three-way catalysts 60 Automotive pollutants: N O , C O , and and hydrocarbons ( H C ) 143 Automotive three-way catalyst(s) ammonia formation 146, 147/ IR study 146 M o in 143-161 Mo-Pd 147/, 148 Mo-Pt 146, 147/, 148, 149 Mo-Rh 147/, 148 N O , C O , and H C conversions .146, 147/ selectivity 146-148 temperature programmed reduction 146, 152, 154/ 2
2
4
4
2
Carbon monoxide adsorption, integral-averaged C O coverage 91, 92/ intrapellet concentration 93, 94/ 0 pretreatment effect 97, 98/ transport resistances, stepresponse effects 93, 95/ air-fuel ratio effect on concentration 70, 71/ catalytic oxidation, transient low-pressure studies 33-56 chemisorption on Pt-alumina 79-101 chemisorption on P t - Μ ο / γ A 1 0 , IR spectra 157, 158/ concentrations at inlet and outlet of three-way catalytic converter 67, 69/ concentrations over pelleted Pt/Pd/Rh/Ce/Al 0 catalyst 70, 71/ conversion(s), automotive threeway catalysts 146, 147/ steady and cycled conditions .62, 65/ time-averaged 62, 64/ transient enhancement 66 desorption, integral-averaged C O . 9 1 , 92/ intrapellet concentration 93, 94/ Pt/Si0 21/, 22/ transport resistances, stepresponse effects 93, 95/ N i , adsorption-desorption 10/ N i interaction 8 Pt, oxidation 15/, 18-19 preadsorbed 0 reaction between 20/, 21/, 22/ system, adsorption isotherm ... 88, 90/ reaction over Fe, H 24 reaction rate resonance in concen tration cycling 267-274 removal, 0 effect 97, 98/ Carbon, surface, over reduced catalyst, hydrogénation 26/ Catalysis heterogeneous, electron spectroscopy study 8 gas-phase kinetics 2-4 IR measurements 5-8 transient method of study 1-29 Catalyst(s) adsorptive capacity 1 automotive three-way, dynamic behavior 59-76 2
2
3
2
3
2
2
2
Carbon-13, C O oxidation on Pt 53, 55/ Carbon dioxide adsorption isotherms 228/ adsorption on adsorbed Ο species .. 210 formation on Pt, rate 23/ pressure, variation during flash of Pd 35/, 37 production on Pt 41, 43/, 51, 52/ production on R h surface ...38, 39/, 40* transient adsorption behavior ...209-236
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Bell and Hegedus; Catalysis Under Transient Conditions ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
304
C A T A L Y S I S
Catalyst(s) (continued) automotive three-way, M o 143-161 Ce, cycled performance of RI1/AI2O3 effect 17/ C H epoxidation, A g 181 C H 3 O H oxidation, pulse reactor effect 246-250 monolithic, flow reactor use ...144, 1451 0 content measurement 72-74 0 content of pelleted Pt/Pd/Rh/Ce/Al 0 74, 75/, 76/ performance under cycled conditions 62, 63/ pulse technique 225 reduced, C H and H reaction 27/ reduced, surface C hydrogénation .. 26/ temperature programmed reduction study 144, 145i three-way, content, air-fuel ratio effect 72,73/ transition metals in C O oxidation 33-56 Catalytic C O oxidation, reaction rate resonance in concentration cycling 267-274 C O oxidation, transient lowpressure studies 33-56 three-way, converter, C O concentrations at inlet and outlet ... 67, 69/ Cerium, cycled performance of RI1-AI2O3 catalyst effect 17/ Chemisorption, on Pt-alumina, C O .79, 101 Concentration step-disturbance in packed bed reactor 280/ Conversion measurements, timeaveraged 60, 62 Cupric oxide catalyst, N 0 decomposition 163-179 Current effect on rates of epoxidation and deep oxidation ...192, 193/ Cycled feed as forcing function 12—14 Cycled performance of R h - A l 0 catalyst, Ce effect 17/ Cyclic operation, improving performance of catalytic reactor 267 2
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2
T R A N S I E N T
C O N D I T I O N S
Dynamic behavior of three-way automotive catalysts Dynamic behavior of three-way catalysts in engine exhaust, apparatus Dynamic gas-phase measurements
59-76
67, 68/ ...62-71
Ε Electrocatalytic C H epoxidation, vapor phase 181-207 Electrochemical Ο pumping, C H epoxidation rates effect 187, 188/ Electrode surface area, C H epoxidation effect 181 Electron spectroscopy, procedure for detecting surface species 41-55 Electron spectroscopy, heterogeneous catalysis study 8 Emission control system 61/ Epoxidation, vapor phase electrocatalytic C H 181-207 Ethylene, adsorption behavior 220,224-226 adsorption isotherms 226/ characterization of adsorbed layer of A g catalyst in oxidation 209-236 epoxidation, vapor phase electrocatalytic 131-207 and H on reduced catalyst 27/ Exhaust, automobile, three-way catalysts function 60 composition controlled by feedback control system 60, 61/ Ο sensor signal showing oscillation 60, 61/ oscillations, transients 60 Experimental methods, transient, heterogeneous catalysis study .... 1-29 External diffusion on kinetics of N 0 decomposition, effect 164 2
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D Decay of reactive Ο on Pt 42, 43/ Decomposition of N 0 163-179 with C u O catalyst 165-171 over metal oxides catalysts reaction 163 over N i O 11/ 0 effect on C u O 165, 168/ Desorption C O over Pt-alumina 80 C O from P t - S i 0 21/, 22/ Ο from catalyst surface 169, 170/ Diffusion-coupled C O chemisorption, transient 84 2
U N D E R
F Feed system, fast-response IR spectrophotometer 81, 83/ Ferric molybdate, M0O3 catalyst 241 Fischer-Tropsch reaction 4 Forced periodic operation, waveforms of concentration cycles 268/ Forcing function 9, 12-14
2
2
Galvanostatic response, oxidation and deep oxidation rates 195, 198/, 199 Galvanostatic transients, C H deep oxidation rate 187, 190/ 2
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305
I N D E X
Gas-phase composition, C H epoxidation effects 192, 195* fast-phase IR spectrophotometer, response 84, 85/ heterogeneous catalysis, kinetics .... 2-4 measurements, dynamic 62-71 2
4
H
Isotope (continued) kinetic, F e ( M o 0 ) / M o 0 , effect 242 N O reduction study I l l , 116, 117/, 118/, 132, 135/, 136/, 137/, 138/ 2
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3
3
Κ Kinetic (s) C 0 production of R h 40* C u O and M g O catalysts in N 0 decomposition studies 164 distributed catalytic systems 277-300 gas-phase, heterogeneous catalysis 2-4 isotope effect on F e ( M o 0 ) / M o 0 242* N O adsorption and reduction 121 N 0 decomposition, external diffusion effect 164 2
2
Heterogeneous catalysis, electron spectroscopy study gas-phase kinetics IR measurements transient conditions transient method of study Hydrocarbon conversions by automotive three-way catalysts 146, partial pressure effects on reduction of adsorbed NO I l l , 113/, 114/, pressure, N O reductions effect 132, 133/, reaction with C O over Fe reaction with C H over reduced catalyst temperature effect 152, Hydrogénation of surface C over reduced catalyst Hysteresis-free measurements in C O oxidation 2
8 2-4 5-8 277 1-29
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3
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M 115/
Magnesium oxide catalyst, N 0 decomposition 171,173-177 C u O comparison 163-179 C u O kinetic studies 164 Mass external, transfer coefficient of C O in fast-response IR system ... 88, 89/ intensities, time effect 244, 245/ steady-state, balance equation for reactor cell of fast-response IR system 88 Metal components, three-way catalysts 143 Metal oxides, catalysts in N 0 decomposition 163 Metals, noble, Pt-alumina catalyst in C O chemisorption 79-101 Metals, transition, substrates in C O oxidation 33-56 Methanol oxidation, pulse reactor, catalyst effect 246-250 on-line M S study 239-251 reaction mechanism 246, 250/ temperature effect 246, 247/ Mixing characteristics, fast-response IR spectrophotometer 84, 85/ Molybdenum automotive three-way catalysts .143-161 -Pd 147/, 148 -Pt 147/, 148, 149 -Rh 147/, 148 - P t ratio, selectivity effect 149, 150/ trioxide F e ( M o 0 ) catalyst 241 trioxide, vapor pressure 161* M S N O reduction study 106, 108/ 2
134/ 24 27/ 154/ 26/ 257
I
2
Integral-averaged C O coverage during C O adsorption-desorption 91, 92/ Intrapellet concentration during C O adsorption-desorption 93, 94/ IR automotive three-way catalysts 146 C O chemisorbed on Pt-Mo-y-Al 0 157, 158/ cell reactor 7/ diode laser, H C and C O concentrations in exhaust 66-67 fast-response 81 fast-response, C O chemisorption dynamics of Pt-alumina .79-101 heterogeneous catalysis measurements 5-8 N O reduction 106, 107/ optical system 6/ Iridium catalyst in titration of chemisorbed Ο 44, 47/, 48, 49/ Iron, catalyst in Η - C O reaction 24 Isothermal limit cycles 18 Isotope experiments, C O preadsorbed on Pt 53, 55/ 1 3
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147/
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Ν Nickel, C O adsorption-desorption ... Nickel, C O interaction
Bell and Hegedus; Catalysis Under Transient Conditions ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
10/ 8
306
C A T A L Y S I S
Nickel oxide, decomposition of N 0 .. 11/ Nitric oxide adsorption and reduction kinetics .. 121 conversion automative three-way catalysts, temperature effect 146, 147/, 149, 151/ conversions, time-averaged C O ... 62, 64/ exposure time effect on H 0 and N H production I l l , 112/ exposure time effects on IR band absorbance I l l , 112/ reduction, H pressure effect 132, 133/, 134/ Hover Rh 105-139 N O exposure time effect 128, 130/, 131/, 132, 133/ Nitrogen, formation in N O reduction 109-139 Nitrous oxide decomposition 163-179 C u O catalyst 164, 165-171, 168/ external diffusion effect on kinetics 164 metal oxides catalysts 163 M g O catalyst 164, 171, 173-177 N i 0 catalyst 11/ rate equations 171, 172/ N O reduction, formation 109-139 2
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U N D E R
T R A N S I E N T
C O N D I T I O N S
Oxygen (continued) catalyst surface, desorption 169, 170/ C O removal rate, effect 97, 98/ C O over Pt, surface reaction 20/ content of pelleted catalyst ...74, 75/, 76/ electrochemical, pumping on rates of C9H4 epoxidation, effect 187,188/ NoO decomposition on C u O , effect 165, 168/ preadsorbed, on Pd 53, 54/ on Pt reaction with C O 20/ on P t / S i 0 reaction with C O . 2 1 / , 22/ pressure, variation during flash of Pd 36/, 37 pretreatment effect on C O adsorption rate 97, 98/ pulse on steam-reforming activity, effect 152, 155/, 156/ reactive, on Pt, decay 42, 43/ sensor in automobile exhaust 60, 61/ transient behavior 212-217 2
2
Ο Oscillations, self-sustained 18 Oscillations, transients in exhaust composition 60 Overvoltage effect on C9H4 epoxidation rate .187, 191/, 192, 194/ Oxidation catalysis over Perovskite-type M n and Fe oxides, pulse reactor 253-265 C H 3 O H , pulse reactor with on-line M S analysis 239-251 C H , characterization adsorbed layer of a A g catalyst 209-236 CO on Pt 15/, 18-19 reaction rate resonance in con centration cycling 267-274 transient low-pressure studies ... 33-56 S0 , C H 149, 152, 153/ Oxygen adsorbed, reactivity 217-220, 222, 223 adsorbed, with H on R u , titration 48, 50/ catalyst, content measurement 72-74, 73/ chemisorption, on A g 48, 50/, 210 on Ir 44, 47/, 48, 49/ on Pt 42, 43/, 44, 45/ 2
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8
Palladium catalyst in titration of preadsorbed Ο 53, 54/ Palladium, automotive three-way catalysts 147/, 148 Perovskite-type oxides of M n and Fe, pulse reactor in oxidation catalysis 253-265 Perturbing function (see Forcing function) Platinum-alumina catalyst disc, properties 82/ Platinum-alumina catalyst in C O chemisorption, noble metals ...79-101 Platinum automotive three-way catalyst 146, 147/, 148, 149 catalyst C O oxidation 18-19 C O oxidation 53, 55/ C 0 production 41, 43/, 51, 52/ decay of reactive Ο 42, 43/ titration of chemisorbed Ο 42, 43/, 44, 45/, 46/ C O and preadsorbed Ο reaction . . . 20/ C 0 formation rate 23/ C O oxidation 15) Platinum silica, C O desorption 21/, 22/ Platinum silica, C O and surface Ο reaction 21/, 22/ Pollutants, automotive: N O , C O , and hydrocarbons ( H C ) 143 Pressure changes, transients induced by 41-55 1 3
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I N D E X
Propagation speed in wavefront analysis 281 Propane oxidation 149, 152, 153* Pulse reactor 242, 243/ on-line M S analysis to study oxida tion of C H O H 239-251 oxidation catalysis over Perovskitetype M n and Fe oxides 253-265 3
Silver catalyst(s) (continued) C H oxidation, adsorbed layer characterization 209-236 selectivity, freshly calcined 185, 186/ surface Ο activity, freshly calcined 185, 186/ titration of chemisorbed Ο 48, 50/ Sorption intermediates of C O and H 0 in shift reaction 286 Space relaxation equation in wavefront analysis 281 Steam-reforming activity, Ο pulse effect 152, 155*, 156* Sulfur dioxide oxidations 149, 152, 153* Surface area, A g catalyst 184, 185* A g catalyst-electrode, effect on cell relaxation time 195, 197/, 203 A g catalyst-electrode, effect on rates of epoxidation r i and deep oxidation 195, 196/ Ο activity of freshly calcined A g catalyst 185, 186/ species, electron spectroscopy 41-55 transients over Pt-alumina 97, 98/ 2
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R Rate adsorption of C O 86 coefficients to simulate transient response experiments 122, 123* desorption of adsorbed species from a surface 87 equations for N 0 decomposi tion 171,172/ Reaction decomposition of N 0 over metal oxides catalysts 163 mechanism for C H O H oxidation in pulse reactor 246, 250/ mechanism proposed for transient response experiments on N O reduction 119, 120/ rate resonance in concentration cycling catalytic C O oxidation ...267-274 Reactivity of adsorbed Ο 217-220, 222, 223 Reactor automotive three-way catalysts 144 cell in fast-response IR system 80 C H epoxidation 182, 183/ transient experiments, flow diagram 242,243/ transient response study of N O reduction 106, 107/, 108/ Rhodium A 1 0 catalyst, effect on cycled performance 17/ automotive three-way catalysts 147/, 148 catalyst in C 0 production ....38, 39/, 40* catalyst in N O reduction 105-139 Ruthenium catalyst in titration of adsorbed Ο with Η 48, 50/ 2
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S Selectivity automotive three-way catalysts 146-148, M o - P t ratio effect 149, Selectivity surface Ο activity of freshly calcined A g catalyst 185, Silver catalyst(s) C H epoxidation 2
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151* 150/
186/ 181
Temperature automotive three-way catalysts N O conversion, effect 149, 151* programmed reduction .146, 152, 154/ selectivity effect 151* changes, transients induced 34-41 C H O H oxidation in pulse reactor, effect 246, 247/ CH epoxidation, effect 181, 199, 200/, 203 H uptake, effect 152, 154/ Thermal desorption spectroscopy 34 Three-way catalysts, automobile exhaust, function 60 Time-averaged conversion measurements 60, 62 conversions, C O and N O 62, 64/ reaction rate as function of period 269,271/ Time relaxation equation in wavefront analysis 281 Titration adsorbed Ο with H on R u 48, 50/ Ο chemisorbed on A g 48, 50/ on Ir 44, 47/, 48, 49/ on Pt 42, 43/, 44, 45/ preadsorbed Ο on Pd 53, 54/ Transient behavior of catalyst 288 3
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C A T A L Y S I S
Transient (continued) of C 0 209-236 of Ο 212-217 difïusion-coupled C O chemisorption 84 enhancement in C O conversion .... 66 experiments, flow sheet 3/ inducing method 33 pressure changes 41-55 temperature changes 34-41 low-pressure studies of catalytic C O oxidation 33-56 method of study, heterogeneous catalysis 1-29 oscillations in exhaust composition 60 response experiments, rate coefficients used to simulate 122, 123/ N , N 0 , H 0 , and N H , during reduction of preadsorbed NO 109,110/ techniques to study N 0 reduction 105-139 Transition metal substrates in C O oxidation 33-56 Transport resistances 1 2
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U N D E R
T R A N S I E N T
C O N D I T I O N S
Transport resistances, effects on stepresponse of C O adsorption-desorption 93,95/
V Vapor phase electrocatalytic C H epoxidation 181-207 Vapor pressure of M o 0 161/ Voltage, C H epoxidation, effect 181 Voltage, C H epoxidation, response to constant current 187, 189/ 2
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W Water, formation in N O reduction .109-139 Water-gas shift reaction 277-300 Wavefront analysis 277-300
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X X-ray photoelectron spectroscopy ....
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Zirconia cells in electrocatalytic C H epoxidation 2
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Bell and Hegedus; Catalysis Under Transient Conditions ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
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