Operando X-ray absorption spectroscopy study of the Fischer-Tropsch reaction with a Co catalyst.

This article describes the setting up of a facility on the energy-scanning EXAFS beamline (BL-09) at RRCAT, Indore, India, for operando studies of structure-activity correlation during a catalytic reaction. The setup was tested by operando X-ray absorption spectroscopy (XAS) studies performed on a Co-based catalyst during the Fischer-Tropsch reaction to obtain information regarding structural changes in the catalyst during the reaction. Simultaneous gas chromatography (GC) measurements during the reaction facilitate monitoring of the product gases, which in turn gives information regarding the activity of the catalyst. The combination of XAS and GC techniques was used to correlate the structural changes with the activity of the catalyst at different reaction temperatures. The oxide catalyst was reduced to the metallic phase by heating at 400°C for 5 h under H2 at ambient pressure and subsequently the catalytic reaction was studied at four different temperatures of 240, 260, 280 and 320°C. The catalyst was studied for 10 h at 320°C and an attempt has been made to understand the process of its deactivation from the XANES and EXAFS results.

[1]  C. Santilli,et al.  Correlation of Sol–Gel Alumina‐Supported Cobalt Catalyst Processing to Cobalt Speciation, Ethanol Steam Reforming Activity, and Stability , 2017 .

[2]  E. Hensen,et al.  The effect of organic additives and phosphoric acid on sulfidation and activity of (Co)Mo/Al2O3 hydrodesulfurization catalysts , 2017 .

[3]  I. Arčon,et al.  Correlations between photocatalytic activity and chemical structure of Cu-modified TiO2–SiO2 nanoparticle composites , 2017 .

[4]  D. Dimitrov,et al.  Structure–reactivity relationship in Co3O4 promoted Au/CeO2 catalysts for the CH3OH oxidation reaction revealed by in situ FTIR and operando EXAFS studies , 2017 .

[5]  N. K. Sahoo,et al.  Augmentation of the step-by-step Energy-Scanning EXAFS beamline BL-09 to continuous-scan EXAFS mode at INDUS-2 SRS. , 2016, Journal of synchrotron radiation.

[6]  A. Beale,et al.  X-ray spectroscopic and scattering methods applied to the characterisation of cobalt-based Fischer–Tropsch synthesis catalysts , 2016 .

[7]  Oliver Müller,et al.  Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution , 2016, Journal of synchrotron radiation.

[8]  B. Ravel,et al.  Analysis of Soils and Minerals Using X‐ray Absorption Spectroscopy , 2015 .

[9]  D. Bhattacharyya,et al.  Correlation of Mo dopant and photocatalytic properties of Mo incorporated TiO2: an EXAFS and photocatalytic study , 2015 .

[10]  H. Emerich,et al.  The state and location of Re in Co–Re/Al2O3 catalysts during Fischer–Tropsch synthesis: Exploring high-energy XAFS for in situ catalysts characterisation , 2014 .

[11]  C. Santilli,et al.  Effect of the balance between Co(II) and Co(0) oxidation states on the catalytic activity of cobalt catalysts for Ethanol Steam Reforming , 2014 .

[12]  S. R. Kane,et al.  Commissioning and first results of scanning type EXAFS beamline (BL-09) at INDUS-2 synchrotron source , 2014 .

[13]  N. K. Sahoo,et al.  A comprehensive facility for EXAFS measurements at the INDUS-2 synchrotron source at RRCAT, Indore, India , 2014 .

[14]  Sivakumar R. Challa,et al.  In situ Transmission Electron Microscopy of Catalyst Sintering , 2013 .

[15]  V. Briois,et al.  Quick-XAS and Raman operando characterisation of a cobalt alumina-supported catalyst under realistic Fischer–Tropsch reaction conditions , 2013 .

[16]  M. Rønning,et al.  Fischer–Tropsch synthesis: An XAS/XRPD combined in situ study from catalyst activation to deactivation , 2012 .

[17]  P. Roussel,et al.  Identification of the active species in the working alumina-supported cobalt catalyst under various conditions of Fischer–Tropsch synthesis , 2011 .

[18]  P. Roussel,et al.  Structure and catalytic performance of Pt-promoted alumina-supported cobalt catalysts under realistic conditions of Fischer–Tropsch synthesis , 2011 .

[19]  Grant Bunker,et al.  Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy , 2010 .

[20]  A. Khodakov,et al.  Fischer-Tropsch synthesis: Relations between structure of cobalt catalysts and their catalytic performance , 2009 .

[21]  A. Datye,et al.  Carbon deposition as a deactivation mechanism of cobalt-based Fischer-Tropsch synthesis catalysts under realistic conditions , 2009 .

[22]  Yuming Dong,et al.  A facile route to controlled synthesis of Co3O4 nanoparticles and their environmental catalytic properties , 2007 .

[23]  Arturo Martínez-Arias,et al.  Dynamic in situ observation of rapid size and shape change of supported Pd nanoparticles during CO/NO cycling. , 2007, Nature materials.

[24]  G. Hutchings,et al.  Effect of the addition of Au on Co/TiO2 catalyst for the Fischer–Tropsch reaction , 2007 .

[25]  C. Hardacre,et al.  DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: identification of the nature of the active form of gold. , 2005, The journal of physical chemistry. B.

[26]  B. Weckhuysen,et al.  Synchrotron radiation effects on catalytic systems as probed with a combined in-situ UV-vis/XAFS spectroscopic setup. , 2005, The journal of physical chemistry. B.

[27]  A. Dent,et al.  Synchronous, time resolved, diffuse reflectance FT-IR, energy dispersive EXAFS (EDE) and mass spectrometric investigation of the behaviour of Rh catalysts during NO reduction by CO. , 2004, Chemical Communications.

[28]  G. Jacobs,et al.  Fischer–Tropsch synthesis: study of the promotion of Re on the reduction property of Co/Al2O3 catalysts by in situ EXAFS/XANES of Co K and Re LIII edges and XPS , 2004 .

[29]  H. Topsøe,et al.  Developments in operando studies and in situ characterization of heterogeneous catalysts , 2003 .

[30]  A. Dent,et al.  Bringing time resolution to EXAFS: recent developments and application to chemical systems. , 2002, Chemical Society reviews.

[31]  B. Weckhuysen,et al.  Snapshots of a working catalyst: possibilities and limitations of in situ spectroscopy in the field of heterogeneous catalysis. , 2002, Chemical communications.

[32]  J. Weitkamp,et al.  In situ IR, NMR, EPR, and UV/Vis Spectroscopy: Tools for New Insight into the Mechanisms of Heterogeneous Catalysis. , 2001, Angewandte Chemie.

[33]  Thomas,et al.  Design, Synthesis, and In Situ Characterization of New Solid Catalysts. , 1999, Angewandte Chemie.

[34]  D. Koningsberger,et al.  Deactivation processes of homogeneous Pd catalysts using in situ time resolved spectroscopic techniques. , 2003, Chemical communications.

[35]  A. Dent Development of Time-Resolved XAFS Instrumentation for Quick EXAFS and Energy-Dispersive EXAFS Measurements on Catalyst Systems , 2002 .

[36]  J. Grunwaldt,et al.  Combining XRD and EXAFS with on-Line Catalytic Studies for in situ Characterization of Catalysts , 2002 .

[37]  D. Koningsberger,et al.  X-ray absorption : principles, applications, techniques of EXAFS, SEXAFS and XANES , 1988 .