Abstract
The term operando was coined at the beginning of this century to gather the growing efforts devoted to establish structure-activity relationships by simultaneously characterizing a catalyst performance and the relevant surface chemistry during genuine catalytic operation. This approach is now widespread and consolidated; it has become an increasingly complex but efficient junction where spectroscopy, materials science, catalysis and engineering meet. While for some characterization techniques kinetically relevant reactor cells with good resolution are recently developing, the knowledge gained with magnetic resonance and X-ray and vibrational spectroscopy studies is already huge and the scope of operando methodology with these techniques is recently expanding from studies with small amounts of powdered solids to more industrially relevant catalytic systems. Engineering catalysis implies larger physical domains, and thus all sort of gradients. Space- and time-resolved multi-technique characterization of both the solid and fluid phases involved in heterogeneous catalytic reactions (including temperature data) is key to map processes from different perspectives, which allows taking into account existing heterogeneities at different scales and facing up- and down-scaling for applications ranging from microstructured reactors to industrial-like macroreactors (operating with shaped catalytic bodies and/or in integral regime). This work reviews how operando methodology is evolving toward engineered reaction systems.
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Mitchell S, Michels N L, Pérez-Ramírez J. From powder to technical body: the undervalued science of catalyst scale up. Chemical Society Reviews, 2013, 42(14): 6094–6112
Boger T, Heibel A K, Sorensen C M. Monolithic catalysts for the chemical industry. Industrial & Engineering Chemistry Research, 2004, 43(16): 4602–4611
Scheffler F, Claus P, Schimpf S, Lucas M, Scheffler M. Heterogeneously catalyzed processes with porous cellular ceramic monoliths. Cellular ceramics. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2006, 454–483
Tronconi E, Groppi G, Visconti C G. Structured catalysts for nonadiabatic applications. Current Opinion in Chemical Engineering, 2014, 5: 55–67
Kreutzer M T, Kapteijn F, Moulijn J A, Heiszwolf J J. Multiphase monolith reactors: Chemical reaction engineering of segmented flow in microchannels. Chemical Engineering Science, 2005, 60 (22): 5895–5916
Twigg M V, Richardson J T. Fundamentals and applications of structured ceramic foam catalysts. Industrial & Engineering Chemistry Research, 2007, 46(12): 4166–4177
Jähnisch K, Hessel V, Löwe H, Baerns M. Chemistry in microstructured reactors. Angewandte Chemie International Edition, 2004, 43(4): 406–446
Yue J, Schouten J C, Nijhuis T A. Integration of microreactors with spectroscopic detection for online reaction monitoring and catalyst characterization. Industrial & Engineering Chemistry Research, 2012, 51(45): 14583–14609
Kestenbaum H, Lange de Oliveira A, Schmidt W, Schüth F, Ehrfeld W, Gebauer K, Löwe H, Richter T, Lebiedz D, Untiedt I, Züchner H. Silver-catalyzed oxidation of ethylene to ethylene oxide in a microreaction system. Industrial & Engineering Chemistry Research, 2002, 41(4): 710–719
Inoue T, Schmidt M A, Jensen K F. Microfabricated multiphase reactors for the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Industrial & Engineering Chemistry Research, 2007, 46(4): 1153–1160
Yoshida J, Nagaki A, Iwasaki T, Suga S. Enhancement of chemical selectivity by microreactors. Chemical Engineering & Technology, 2005, 28(3): 259–266
Al-Rifai N, Cao E, Dua V, Gavriilidis A. Microreaction technology aided catalytic process design. Current Opinion in Chemical Engineering, 2013, 2(3): 338–345
Ufer A, Sudhoff D, Mescher A, Agar D W. Suspension catalysis in a liquid-liquid capillary microreactor. Chemical Engineering Journal, 2011, 167(2): 468–474
Martin A J, Mitchell S, Kunze K, Weston K C, Pérez-Ramírez J. Visualising compositional heterogeneity during the scale up of multicomponent zeolite bodies. Materials Horizons, 2017, 4(5): 857–861
Rasmussen S B, López-Medina R, Portela R, Mikolajska E, Daturi M, Avila P, Bañares M A. Shaping up operando spectroscopy: Raman characterization of a working honeycomb monolith. Catalysis Science & Technology, 2015, 5(11): 4942–4945
Hunger M, Weitkamp J. In situ IR, NMR, EPR, and UV/Vis spectroscopy: Tools for new insight into the mechanisms of heterogeneous catalysis. Angewandte Chemie International Edition, 2001, 40(16): 2954–2971
Urakawa A. Trends and advances in operando methodology. Current Opinion in Chemical Engineering, 2016, 12: 31–36
Urakawa A, Maeda N, Baiker A. Space-and time-resolved combined DRIFT and Raman spectroscopy: Monitoring dynamic surface and bulk processes during NOx storage reduction. Angewandte Chemie International Edition, 2008, 47(48): 9256–9259
Burch R. In situ methods in catalysis—Proceedings of the surface reactivity and catalysis group meeting of the royal society of chemistry. Catalysis Today, 1991, 9(1–2)
Clausen B S, Topsøe H, Frahm R. Application of combined X-ray diffraction and absorption techniques for in situ catalyst characterization. In: Eley D D, Haag W O, Gates B, Knözinger H, eds. Advances in Catalysis. Massachusetts: Academic Press, 1998, 315–344
Dumesic J A, Topsøe H. Mössbauer Spectroscopy Applications to Heterogeneous Catalysis. In: Eley D D, Pines H, Weisz P B, eds. Advances in Catalysis. Massachusetts: Academic Press, 1977, 121–246
Bañares M A. Operando spectroscopy: The knowledge bridge to assessing structure–performance relationships in catalyst nanoparticles. Advanced Materials, 2011, 23(44): 5293–5301
Topsøe H. Developments in operando studies and in situ characterization of heterogeneous catalysts. Journal of Catalysis, 2003, 216(1–2): 155–164
Topsøe H. In situ characterization of catalysts. In: Corma A, Melo F V, Mendioroz S, Fierro J L G, eds. 12th International Congress on Catalysis, Proceedings of the 12th ICC. Amsterdam: Elsevier, 2000, 1–21
Meunier F C. The design and testing of kinetically-appropriate operando spectroscopic cells for investigating heterogeneous catalytic reactions. Chemical Society Reviews, 2010, 39(12): 4602–4614
Weckhuysen B M. Preface: Recent advances in the in-situ characterization of heterogeneous catalysts. Chemical Society Reviews, 2010, 39(12): 4557–4559
Weckhuysen B M. Snapshots of a working catalyst: Possibilities and limitations of in situ spectroscopy in the field of heterogeneous catalysis. Chemical Communications, 2002, 2(2): 97–110
Bañares M A, Guerrero-Pérez M O, Fierro J L G, Garcia Cortez G. Raman spectroscopy during catalytic operations with on-line activity measurement (operando spectroscopy): A method for understanding the active centres of cations supported on porous materials. Journal of Materials Chemistry, 2002, 12(11): 3337–3342
Calvino-Casilda V, Banares M A. Recent advances in imaging and monitoring of heterogeneous catalysts with Raman spectroscopy. Catalysis, 2012, 24: 1–47
Banares M A. In situ to operando spectroscopy: From proof of concept to industrial application. Topics in Catalysis, 2009, 52(10): 1301–1302
Niemantsverdriet J W. Spectroscopy In Catalysis: An Introduction. 3rd ed. New Jersey: Wiley, 2007
Somorjai G A. In situ surface science studies of catalytic reactions. CATTech, 1999, 3(1): 84–97
Bennici S M, Vogelaar B M, Nijhuis T A, Weckhuysen B M. Realtime control of a catalytic solid in a fixed-bed reactor based on in situ spectroscopy. Angewandte Chemie International Edition, 2007, 46(28): 5412–5416
Brückner A, Kondratenko E. Simultaneous operando EPR/UV-vis/laser-Raman spectroscopy—A powerful tool for monitoring transition metal oxide catalysts during reaction. Catalysis Today, 2006, 113(1–2): 16–24
Bañares M A, Mestl G. Structural characterization of catalysts by operando Raman spectroscopy. In-situ Characterization of Heterogeneous Catalysts, 2013, 267–292
Balboni M L. Process analytical technology: Concepts and principles. Pharmaceutical Technology, 2003, 27(10): 54
Vogt C, Weckhuysen B M, Ruiz-Martínez J. Effect of feedstock and catalyst impurities on the methanol-to-olefin reaction over HSAPO-34. ChemCatChem, 2017, 9(1): 183–194
Jentoft F C. Chapter 3. Ultraviolet-visible-near infrared spectroscopy in catalysis: Theory, experiment, analysis, and application under reaction conditions. Advances in Catalysis, 2009, 52: 129–211
Rasmussen S B, Bañares M A, Bazin P, Due-Hansen J, Ávila P, Daturi M. Monitoring catalysts at work in their final form: Spectroscopic investigations on a monolithic catalyst. Physical Chemistry Chemical Physics, 2012, 14(7): 2171–2177
Ferraro J R, Nakamoto K, Brown C W. Introductory Raman spectroscopy. In: Nakamoto K, Brown C W, eds. Introductory Raman spectroscopy. 2nd ed. Massachusetts: Academic Press, 2003, 1–434
Brückner A. Electron paramagnetic resonance: A powerful tool for monitoring working catalysts. Advances in Catalysis, 2007, 51: 265–308
Ivanova I I, Kolyagin Y G. Impact of in situ MAS NMR techniques to the understanding of the mechanisms of zeolite catalyzed reactions. Chemical Society Reviews, 2010, 39(12): 5018–5050
Blasco T. Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy. Chemical Society Reviews, 2010, 39(12): 4685–4702
Beale A M, Jacques S D M, Weckhuysen B M. Chemical imaging of catalytic solids with synchrotron radiation. Chemical Society Reviews, 2010, 39(12): 4656–4672
Newton M A, van Beek W. Combining synchrotron-based X-ray techniques with vibrational spectroscopies for the in situ study of heterogeneous catalysts: A view from a bridge. Chemical Society Reviews, 2010, 39(12): 4845–4863
Senyshyn A, Mühlbauer M J, Nikolowski K, Pirling T, Ehrenberg H. “In-operando” neutron scattering studies on Li-ion batteries. Journal of Power Sources, 2012, 203: 126–129
Lennon D, Parker S F. Inelastic neutron scattering studies of methyl chloride synthesis over alumina. Accounts of Chemical Research, 2014, 47(4): 1220–1227
Frenken J, Groot I. Operando Research in Heterogeneous Catalysis. Berlin: Springer International Publishing, 2017
Han B, Stoerzinger K A, Tileli V, Gamalski A D, Stach E A, Shao-Horn Y. Nanoscale structural oscillations in perovskite oxides induced by oxygen evolution. Nature Materials, 2017, 16(1): 121–126
Stavitski E, Weckhuysen B M. Infrared and Raman imaging of heterogeneous catalysts. Chemical Society Reviews, 2010, 39(12): 4615–4625
Weckhuysen B M. Chemical imaging of spatial heterogeneities in catalytic solids at different length and time scales. Angewandte Chemie International Edition, 2009, 48(27): 4910–4943
Buurmans I L C, Weckhuysen B M. Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy. Nature Chemistry, 2012, 4(11): 873–886
Morgan K, Touitou J, Choi J S, Coney C, Hardacre C, Pihl J A, Stere C E, Kim M Y, Stewart C, Goguet A, Partridge W P. Evolution and enabling capabilities of spatially resolved techniques for the characterization of heterogeneously catalyzed reactions. ACS Catalysis, 2016, 6(2): 1356–1381
Sattler J J H B, Mens A M, Weckhuysen B M. Real-time quantitative operando raman spectroscopy of a CrOx/Al2O3 propane dehydrogenation catalyst in a pilot-scale reactor. Chem-CatChem, 2014, 6(11): 3139–3145
Guerrero-Pérez M O, Bañares M A. Operando Raman study of alumina-supported Sb-V-O catalyst during propane ammoxidation to acrylonitrile with on-line activity measurement. Chemical Communications, 2002, 12(12): 1292–1293
Bañares M A, Wachs I E. Molecular structures of supported metal oxide catalysts under different environments. Journal of Raman Spectroscopy, 2002, 33(5): 359–380
Wachs I E. International congress on operando spectroscopy: Fundamental and technical aspects of spectroscopy of catalysts under working conditions. Catalysis Communications, 2003, 4 (11): 567–570
Chakrabarti A, Ford M E, Gregory D, Hu R, Keturakis C J, Lwin S, Tang Y, Yang Z, Zhu M, Bañares M A, Wachs I E. A decade+ of operando spectroscopy studies. Catalysis Today, 2017, 283: 27–53
Thomas S, Marie O, Bazin P, Lietti L, Visconti C G, Corbetta M, Manenti F, Daturi M. Modelling a reactor cell for operando IR studies: From qualitative to fully quantitative kinetic investigations. Catalysis Today, 2017, 283: 176–184
Thibault-Starzyk F, Seguin E, Thomas S, Daturi M, Arnolds H, King D A. Real-time infrared detection of cyanide flip on silver-alumina NOx removal catalyst. Science, 2009, 324(5930): 1048–1051
Krivanek O L, Lovejoy T C, Dellby N, Aoki T, Carpenter R W, Rez P, Soignard E, Zhu J, Batson P E, Lagos M J, Egerton R F, Crozier P A. Vibrational spectroscopy in the electron microscope. Nature, 2014, 514(7521): 209–212
Choi J S, Partridge W P, Daw C S. Spatially resolved in situ measurements of transient species breakthrough during cyclic, low-temperature regeneration of a monolithic Pt/K/Al2O3 NOx storage-reduction catalyst. Applied Catalysis A: General, 2005, 293(1–2): 24–40
Nguyen H, Peng P Y, Luss D, Harold M P. Assessing intrusion by the capillary during spatially resolved mass spectrometry measurement. Chemical Engineering Journal, 2017, 307: 845–859
Bentrup U. Combining in situ characterization methods in one setup: Looking with more eyes into the intricate chemistry of the synthesis and working of heterogeneous catalysts. Chemical Society Reviews, 2010, 39(12): 4718–4730
Wachs I E, Routray K. Catalysis science of bulk mixed oxides. ACS Catalysis, 2012, 2(6): 1235–1246
Wachs I E. Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials. Catalysis Today, 2005, 100 (1): 79–94
Tran L, Bañares M A, Rallo R. Modelling the Toxicity of Nanoparticles. Berlin: Springer International Publishing, 2017
Guerrero-Pérez M O, Bañares M A. From conventional in situ to operando studies in Raman spectroscopy. Catalysis Today, 2006, 113(1–2): 48–57
Bañares M A, Khatib S J. Structure-activity relationships in alumina-supported molybdena-vanadia catalysts for propane oxidative dehydrogenation. Catalysis Today, 2004, 96(4): 251–257
Martínez-Huerta M V, Deo G, Fierro J L G, Bañares M A. Operando Raman-GC study on the structure-activity relationships in V5+/CeO2 catalyst for ethane oxidative dehydrogenation: The formation of CeVO4. Journal of Physical Chemistry C, 2008, 112 (30): 11441–11447
Banares M A, Dauphin L, Calvoperez V, Fehlner T P, Wolf E E. Activity and characterization of self-supported model catalysts derived from cobalt-based clusters of clusters: Hydrogenation of 1,3-butadiene. Journal of Catalysis, 1995, 152(2): 396–409
Bañares M A, Dauphin L, Lei X, Cen W, Shang M, Wolf E E, Fehlner T P. Effect of precursor core structure on the hydrogenation of 1,3-butadiene catalyzed by cluster-derived model catalysts. Chemistry of Materials, 1995, 7(3): 553–561
Bañares M, Patil A N, Fehlner T P, Wolf E E. Novel clusterderived catalysts for the selective hydrogenation of crotonaldehyde. Catalysis Letters, 1995, 34(3–4): 251–258
Deutschmann O, Schwiedemoch R, Maier L I, Chatterjee D. Natural gas conversion in monolithic catalysts: Interaction of chemical reactions and transport phenomena. In: Iglesia E, Spivey J J, Fleisch T H, eds. Studies in Surface Science and Catalysis. Amsterdam: Elsevier, 2001, 251–258
Meunier F, Reid D, Goguet A, Shekhtman S, Hardacre C, Burch R, Deng W, Flytzanistephanopoulos M. Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water-gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates. Journal of Catalysis, 2007, 247(2): 277–287
Rivallan M, Seguin E, Thomas S, Lepage M, Takagi N, Hirata H, Thibault-Starzyk F. Platinum sintering on H-ZSM-5 followed by chemometrics of CO adsorption and 2D pressure-jump IR spectroscopy of adsorbed species. Angewandte Chemie International Edition, 2010, 49(4): 785–789
Bare S R, Ressler T. Characterization of catalysts in reactive atmospheres by X-ray absorption spectroscopy. In: Gates B, Knoezinger H, Jentoft F, eds. Advances in Catalysis. Massachusetts: Academic Press, 2009, 339–465
Doronkin D E, Lichtenberg H, Grunwaldt J D. Cell designs for in situ and operando studies. In: Iwasawa Y, Asakura K, Tada M, eds. XAFS Techniques for Catalysts, Nanomaterials, and Surfaces Techniques for Catalysts, Nanomaterials, and Surfaces. Berlin: Springer International Publishing, 2017, 75–89
Carías-Henriquez A, Pietrzyk S, Dujardin C. Modelling and optimization of IR cell devoted to in situ and operando characterization of catalysts. Catalysis Today, 2013, 205(Supp. C): 134–140
Burcham L J, Badlani M, Wachs I E. The origin of the ligand effect in metal oxide catalysts: Novel fixed-bed in situ infrared and kinetic studies during methanol oxidation. Journal of Catalysis, 2001, 203(1): 104–121
Rasmussen S B, Perez-Ferreras S, Bañares M A, Bazin P, Daturi M. Does pelletizing catalysts influence the efficiency number of activity measurements? Spectrochemical engineering considerations for an accurate operando study. ACS Catalysis, 2012, 3(1): 86–94
Lisi L, Pirone R, Russo G, Stanzione V. Cu-ZSM5 based monolith reactors for NO decomposition. Chemical Engineering Journal, 2009, 154(1): 341–347
Gibson E K, Zandbergen MW, Jacques S D M, Biao C, Cernik R J, O’Brien M G, Di Michiel M, Weckhuysen B M, Beale A M. Noninvasive spatiotemporal profiling of the processes of impregnation and drying within mMo/Al2O3 catalyst bodies by a combination of X-ray absorption tomography and diagonal offset Raman spectroscopy. ACS Catalysis, 2013, 3(3): 339–347
Ferri D, Elsener M, Kröcher O. Methane oxidation over a honeycomb Pd-only three-way catalyst under static and periodic operation. Applied Catalysis B: Environmental, 2018, 220: 67–77
Malpartida I, Marie O, Bazin P, Daturi M, Jeandel X. An operando IR study of the unburnt HC effect on the activity of a commercial automotive catalyst for NH3-SCR. Applied Catalysis B: Environmental, 2011, 102(1): 190–200
Ávila P, Montes M, Miró E E. Monolithic reactors for environmental applications: A review on preparation technologies. Chemical Engineering Journal, 2005, 109(1): 11–36
Chen J, Yang H, Wang N, Ring Z, Dabros T. Mathematical modeling of monolith catalysts and reactors for gas phase reactions. Applied Catalysis A: General, 2008, 345(1): 1–11
Grunwaldt J D, Wagner J B, Dunin-Borkowski R E. Imaging catalysts at work: A hierarchical approach from the macro-to the meso-and nano-scale. ChemCatChem, 2013, 5(1): 62–80
Goguet A, Stewart C, Touitou J, Morgan K. In situ spatially resolved techniques for the investigation of packed bed catalytic reactors: Current status and future outlook of Spaci-FB. Advances in Chemical Engineering, 2017, 50: 131–160
Rasmussen S B, Portela R, Bazin P, Ávila P, Bañares M A, Daturi M. Transient operando study on the NH3/NH4 + interplay in VSCR monolithic catalysts. Applied Catalysis B: Environmental, 2018, 224: 109–115
Grunwaldt J D, Kimmerle B, Baiker A, Boye P, Schroer C G, Glatzel P, Borca C N, Beckmann F. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy. Catalysis Today, 2009, 145(3–4): 267–278
van de Water L G A, Bergwerff J A, Nijhuis T A, de Jong K P, Weckhuysen B M. UV-Vis microspectroscopy: probing the initial stages of supported metal oxide catalyst preparation. Journal of the American Chemical Society, 2005, 127(14): 5024–5025
Fait MJ G, Abdallah R, Linke D, Kondratenko E V, Rodemerck U. A novel multi-channel reactor system combined with operando UV/vis diffuse reflectance spectroscopy: Proof of principle. Catalysis Today, 2009, 142(3–4): 196–201
García-Casado M, Prieto J, Vico-Ruiz E, Lozano-Diz E, Goberna-Selma C, Bañares M A. High-throughput operando Ramanquadrupole mass spectrometer (QMS) system to screen catalytic systems. Applied Spectroscopy, 2014, 68(1): 69–78
Zandbergen M W, Jacques S D M, Weckhuysen B M, Beale A M. Chemical probing within catalyst bodies by diagonal offset Raman spectroscopy. Angewandte Chemie International Edition, 2012, 51 (4): 957–960
van Schrojenstein Lantman E M, Deckert-Gaudig T, Mank A J G, Deckert V, Weckhuysen B M. Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nature Nanotechnology, 2012, 7(9): 583–586
Li G, Hu D, Xia G, White J M, Zhang C. High throughput operando studies using Fourier transform infrared imaging and Raman spectroscopy. Review of Scientific Instruments, 2008, 79 (7): 074101
Grunwaldt J D, Schroer C G. Hard and soft X-ray microscopy and tomography in catalysis: Bridging the different time and length scales. Chemical Society Reviews, 2010, 39(12): 4741–4753
Jacques S D, Di Michiel M, Kimber S A, Yang X, Cernik R J, Beale A M, Billinge S J. Pair distribution function computed tomography. Nature Communications, 2013, 4(1): 2536
Beale A M, Jacques S D M, Gibson E K, Di Michiel M. Progress towards five dimensional diffraction imaging of functional materials under process conditions. Coordination Chemistry Reviews, 2014, 277–278: 208–223
Vila F D, Rehr J J, Kelly S D, Bare S R. Operando effects on the structure and dynamics of PtnSnm/g-Al2O3 from ab initio molecular dynamics and X-ray absorption spectra. Journal of Physical Chemistry C, 2013, 117(24): 12446–12457
O’Brien M G, Jacques S D M, Di Michiel M, Barnes P, Weckhuysen B M, Beale A M. Active phase evolution in single Ni/Al2O3 methanation catalyst bodies studied in real time using combined μ-XRD-CT and μ-absorption-CT. Chemical Science, 2012, 3(2): 509–523
Senecal P, Jacques S D M, Di Michiel M, Kimber S A J, Vamvakeros A, Odarchenko Y, Lezcano-Gonzalez I, Paterson J, Ferguson E, Beale A M. Real-time scattering-contrast imaging of a supported cobalt-based catalyst body during activation and Fischer-Tropsch synthesis revealing spatial dependence of particle size and phase on catalytic properties. ACS Catalysis, 2017, 7(4): 2284–2293
Ngo C, Dzara M J, Shulda S, Pylypenko S.Spectroscopy and Microscopy for Characterization of Fuel Cell Catalysts. Electrocatalysts for Low Temperature Fuel Cells. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2017, 443–466
Zhang C, Gustafson J, Merte L R, Evertsson J, Norén K, Carlson S, Svensson H, Carlsson P A. An in situ sample environment reaction cell for spatially resolved X-ray absorption spectroscopy studies of powders and small structured reactors. Review of Scientific Instruments, 2015, 86(3): 033112
Alrwashdeh S S, Manke I, Markötter H, Klages M, Göbel M, Haußmann J, Scholta J, Banhart J. In operando quantification of three-dimensional water distribution in nanoporous carbon-based layers in polymer electrolyte membrane fuel cells. ACS Nano, 2017, 11(6): 5944–5949
Yang Y, Risse S, Mei S, Jafta C J, Lu Y, Stöcklein C, Kardjilov N, Manke I, Gong J, Kochovski Z, Ballauff M. Binder-free carbon monolith cathode material for operando investigation of high performance lithium-sulfur batteries with X-ray radiography. Energy Storage Materials, 2017, 9: 96–104
Sezen H, Rockett A A, Suzer S. XPS investigation of a CdS-based photoresistor under working conditions: Operando-XPS. Analytical Chemistry, 2012, 84(6): 2990–2994
Polcari D, Dauphin-Ducharme P, Mauzeroll J. Scanning electrochemical microscopy: A comprehensive review of experimental parameters from 1989 to 2015. Chemical Reviews, 2016, 116(22): 13234–13278
Li F, Ciani I, Bertoncello P, Unwin P R, Zhao J, Bradbury C R, Fermin D J. Scanning electrochemical microscopy of redoxmediated hydrogen evolution catalyzed by two-dimensional assemblies of palladium nanoparticles. Journal of Physical Chemistry C, 2008, 112(26): 9686–9694
Sá J, Fernandes D L A, Aiouache F, Goguet A, Hardacre C, Lundie D, Naeem W, Partridge WP, Stere C, Spaci MS. SpaciMS: Spatial and temporal operando resolution of reactions within catalytic monoliths. Analyst, 2010, 135(9): 2260–2272
Bosco M, Vogel F. Optically accessible channel reactor for the kinetic investigation of hydrocarbon reforming reactions. Catalysis Today, 2006, 116(3): 348–353
Horn R, Williams K A, Degenstein N J, Bitsch-Larsen A, Dalle Nogare D, Tupy S A, Schmidt L D. Methane catalytic partial oxidation on autothermal Rh and Pt foam catalysts: Oxidation and reforming zones, transport effects, and approach to thermodynamic equilibrium. Journal of Catalysis, 2007, 249(2): 380–393
Luo J Y, Hou X, Wijayakoon P, Schmieg S J, Li W, Epling W S. Spatially resolving SCR reactions over a Fe/zeolite catalyst. Applied Catalysis B: Environmental, 2011, 102(1–2): 110–119
Kopyscinski J, Schildhauer T J, Vogel F, Biollaz S M A, Wokaun A. Applying spatially resolved concentration and temperature measurements in a catalytic plate reactor for the kinetic study of CO methanation. Journal of Catalysis, 2010, 271(2): 262–279
Geske M, Korup O, Horn R. Resolving kinetics and dynamics of a catalytic reaction inside a fixed bed reactor by combined kinetic and spectroscopic profiling. Catalysis Science & Technology, 2013, 3(1): 169–175
Korup O, Mavlyankariev S, Geske M, Goldsmith C F, Horn R. Measurement and analysis of spatial reactor profiles in high temperature catalysis research. Chemical Engineering and Processing: Process Intensification, 2011, 50(10): 998–1009
Gladden L F, Mantle M D, Sederman A J. Magnetic Resonance Imaging of Catalysts and Catalytic Processes. In: Gates B C, Knzinger H, eds. Advances in Catalysis. Massachusetts: Academic Press, 2006, 1–75
Lysova A A, Koptyug I V. Magnetic resonance imaging methods for in situ studies in heterogeneous catalysis. Chemical Society Reviews, 2010, 39(12): 4585–4601
Barskiy D A, Coffey A M, Nikolaou P, Mikhaylov D M, Goodson B M, Branca R T, Lu G J, Shapiro M G, Telkki V V, Zhivonitko V V, Koptyug I V, Salnikov O G, Kovtunov K V, Bukhtiyarov V I, Rosen M S, Barlow M J, Safavi S, Hall I P, Schröder L, Chekmenev E Y. NMR hyperpolarization techniques of gases. Chemistry, 2017, 23(4): 725–751
Kovtunov K V, Barskiy D A, Shchepin R V, Coffey A M, Waddell K W, Koptyug I V, Chekmenev E Y. Demonstration of heterogeneous parahydrogen induced polarization using hyperpolarized agent migration from dissolved Rh(I) complex to gas phase. Analytical Chemistry, 2014, 86(13): 6192–6196
Telkki V V, Zhivonitko V V, Selent A, Scotti G, Leppäniemi J, Franssila S, Koptyug I V. Lab-on-a-chip reactor imaging with unprecedented chemical resolution by Hadamard-encoded remote detection NMR. Angewandte Chemie International Edition, 2014, 53(42): 11289–11293
Gladden L F, Buckley C, Chow P S, Davidson J F, Mantle M D, Sederman A J. ‘Looking into’ chemical products and processes. Current Applied Physics, 2004, 4(2): 93–97
Gladden L F, Mantle M D, Sederman A J. Magnetic resonance imaging of catalysts and catalytic processes. Advances in Catalysis, 2006, 50: 1–75
Cattaneo A S, Villa D C, Angioni S, Ferrara C, Melzi R, Quartarone E, Mustarelli P. Operando electrochemical NMR microscopy of polymer fuel cells. Energy & Environmental Science, 2015, 8(8): 2383–2388
Britton M M, Sederman A J, Taylor A F, Scott S K, Gladden L F. Magnetic resonance imaging of flow-distributed oscillations. Journal of Physical Chemistry A, 2005, 109(37): 8306–8313
Ulpts J, Dreher W, Kiewidt L, Schubert M, Thöming J. In situ analysis of gas phase reaction processes within monolithic catalyst supports by applying NMR imaging methods. Catalysis Today, 2016, 273: 91–98
Ulpts J, Kiewidt L, Dreher W, Thöming J. 3D characterization of gas phase reactors with regularly and irregularly structured monolithic catalysts by NMR imaging and modeling. Catalysis Today, 2018, 310: 176–186
Zheng Q, Russo-Abegao F J, Sederman A J, Gladden L F. Operando determination of the liquid-solid mass transfer coefficient during 1-octene hydrogenation. Chemical Engineering Science, 2017, 171: 614–624
Li H, Rivallan M, Thibault-Starzyk F, Travert A, Meunier F C. Effective bulk and surface temperatures of the catalyst bed of FTIR cells used for in situ and operando studies. Physical Chemistry Chemical Physics, 2013, 15(19): 7321–7327
Kellow J C, Wolf E E. Infrared thermography and FTIR studies of catalyst preparation effects on surface reaction dynamics during CO and ethylene oxidation on Rh/SiO2 catalysts. Chemical Engineering Science, 1990, 45(8): 2597–2602
Kellow J, Wolf E E. In-situ IR thermography studies of reaction dynamics during CO oxidation on Rh-SiO2 catalysts. Catalysis Today, 1991, 9(1): 47–51
Kellow J C, Wolf E E. Propagation of oscillations during ethylene oxidation on a Rh/SiO2 catalyst. AIChE Journal. American Institute of Chemical Engineers, 1991, 37(12): 1844–1848
Koptyug I V, Khomichev A V, Lysova A A, Sagdeev R Z. Spatially resolved NMR thermometry of an operating fixed-bed catalytic reactor. Journal of the American Chemical Society, 2008, 130(32): 10452–10453
Lysova A A, Kulikov A V, Parmon V N, Sagdeev R Z, Koptyug I V. Quantitative temperature mapping within an operating catalyst by spatially resolved 27Al NMR. Chemical Communications, 2012, 48(46): 5763–5765
Kimmerle B, Grunwaldt J D, Baiker A, Glatzel P, Boye P, Stephan S, Schroer C G. Visualizing a catalyst at work during the ignition of the catalytic partial oxidation of methane. Journal of Physical Chemistry C, 2009, 113(8): 3037–3040
Cao E, Firth S, McMillan P F, Gavriilidis A. Application of microfabricated reactors for operando Raman studies of catalytic oxidation of methanol to formaldehyde on silver. Catalysis Today, 2007, 126(1–2): 119–126
Gänzler A M, Casapu M, Boubnov A, Müller O, Conrad S, Lichtenberg H, Frahm R, Grunwaldt J D. Operando spatially and time-resolved X-ray absorption spectroscopy and infrared thermography during oscillatory CO oxidation. Journal of Catalysis, 2015, 328: 216–224
Hannemann S, Grunwaldt J D, van Vegten N, Baiker A, Boye P, Schroer C G. Distinct spatial changes of the catalyst structure inside a fixed-bed microreactor during the partial oxidation of methane over Rh/Al2O3. Catalysis Today, 2007, 126(1–2): 54–63
Grunwaldt J D, Baiker A. Axial variation of the oxidation state of Pt-Rh/Al2O3 during partial methane oxidation in a fixed-bed reactor: An in situ X-ray absorption spectroscopy study. Catalysis Letters, 2005, 99(1): 5–12
Fletcher P D I, Haswell S J, Zhang X. Monitoring of chemical reactions within microreactors using an inverted Raman microscopic spectrometer. Electrophoresis, 2003, 24(18): 3239–3245
Acknowledgements
This work was supported by Spanish Ministry grants CTQ2014-57578-R ‘LT-NOx’ and CTM2017-82335-R ‘RIEN2O’; and Comunidad de Madrid programme 2013/MAE2985 ‘ALCCONES.’
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Prof. Miguel A. BAÑARES, Granada (Spain), 1965, PhD 1992. Research Professor at CSIC, Institute for Catalysis and Associate Editor, Catalysis Today. Doctor Honoris Causa by the Univerisity of Caen, Normandy, France. He has been Deputy Vice-President of CSIC (Spanish National Research Council), Vice-Chairman, COST ACTION TD1204, MODENA and Chairman of COST Action D36. Co-founder of Advanced Dispersed Particles (ADParticles, https://doi.org/www.adparticles.com) in 2011, 1, a CSIC spin-off company. Advisory Board Member for The Catalyst Group Review and editorial board member of several journals (Top. Catal., Catal. Letter).
Bañares was distinguished by the Otto Mønsted Visiting Professorship at DTU University, Lyngby, Denmark in 2014; and he has also been granted the FEDER-Region de Normandie, “chaire d’excellence” at CNRS Caen, France, during 2013–2015. He has more than 200 publications in international journals and an ‘h’ factor 41 with more than 30 plenary/keynote lectures. Bañares objective is to understand structure-reactivity relationships in oxide catalysts at a molecular level by combining in situ and operando analyses with computational description of the structure, spectra and reactivity of the catalysts. He coined the term ‘operando’ to identify this advanced in situ spectroscopy, his new term is widely used in literature now. The ultimate goal is to implement fundamental operando knowledge into real working industrial processes.
Dr. Raquel Portela (Ph.D in Chemical Engineering, Ciemat/University of Santiago de Compostela, 2008) has made numerous stays in recognized research centers, such as UBA, LBNL, Institut de Recherches sur la Catalyze et l’Environnement de Lyon, IRCELYON-CNRS or ENSICAEN-CNRS-Laboratoire de Catalyze et Spectrochimie, and since 2011 investigates at ICP-CSIC.
She has broad experience in air pollution control by (photo) catalysis and adsorption, and recently also in reactions of industrial interest. Her approach combines chemistry and engineering, and her activities comprise synthesis, shaping and characterization of monolithic catalysts, including in situ and operando spectroscopy; and activity tests at laboratory and pilot plant scale and new set-ups. She has authored 36 papers in SCI journals of high impact index.
Dr. Susana Perez-Ferreras. Ph.D. in Organic Chemistry in 2006 in Organometallic complexes (Ru, Pd, Au) synthesis and heterogeneous catalysts immobilized on silica gel, ordered mesoporous silica (MCM-41), and delaminated zeolite (ITQ-2). Application in metathesis of olefins reaction, hydrogenation of alkenes and Suzuki cross-coupling reaction.
She works on the development of new metal catalysts for elimination of harmful gases (NOx) and greenhouse gases (N2O) using Operando methodology in the study. Skilled in NLDFT studies of microporous carbon monoliths used as supercapacitors. Development of a new methodology of O2 chemisorption in Cermets Ni/(Ce0.9Ln-0.1O1.95) (Ln = lanthanide) for hydrogen production by partial oxidation of methane. Textural studies of meso-micro-porous materials used as catalyst for aromatic compounds oxidation.
Dr. Ana Serrano-Lotina conducted her doctoral research at Hydrogen and Fuel Cells Group (Instituto de Catálisis y Petroleoquímica-ICP-CSIC-). She obtained her PhD in Physical Chemistry in 2012 and she worked as a postdoctoral researcher until 2015 when she moved to her current position. Her research was based on hydrogen production from biogas and bioethanol and for its purification. Nowadays, she works at Spectroscopy and Industrial Catalysis Group (ICP-CSIC) and her work is focused on the abatement of industrial emissions, i.e. NOx, N2O or NH3. Synthesis of catalysts including its conformation by extrusion, characterization of materials and gas-phase catalytic tests at laboratory and pilot plant scale are among her expertise.
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Portela, R., Perez-Ferreras, S., Serrano-Lotina, A. et al. Engineering operando methodology: Understanding catalysis in time and space. Front. Chem. Sci. Eng. 12, 509–536 (2018). https://doi.org/10.1007/s11705-018-1740-9
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DOI: https://doi.org/10.1007/s11705-018-1740-9