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      Chemical imaging of Fischer-Tropsch catalysts under operating conditions

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          Abstract

          Multimodal x-ray imaging techniques reveal insight into the structure-function relationships in cobalt Fischer-Tropsch catalysts.

          Abstract

          Although we often understand empirically what constitutes an active catalyst, there is still much to be understood fundamentally about how catalytic performance is influenced by formulation. Catalysts are often designed to have a microstructure and nanostructure that can influence performance but that is rarely considered when correlating structure with function. Fischer-Tropsch synthesis (FTS) is a well-known and potentially sustainable technology for converting synthetic natural gas (“syngas”: CO + H 2) into functional hydrocarbons, such as sulfur- and aromatic-free fuel and high-value wax products. FTS catalysts typically contain Co or Fe nanoparticles, which are often optimized in terms of size/composition for a particular catalytic performance. We use a novel, “multimodal” tomographic approach to studying active Co-based catalysts under operando conditions, revealing how a simple parameter, such as the order of addition of metal precursors and promoters, affects the spatial distribution of the elements as well as their physicochemical properties, that is, crystalline phase and crystallite size during catalyst activation and operation. We show in particular how the order of addition affects the crystallinity of the TiO 2 anatase phase, which in turn leads to the formation of highly intergrown cubic close-packed/hexagonal close-packed Co nanoparticles that are very reactive, exhibiting high CO conversion. This work highlights the importance of operando microtomography to understand the evolution of chemical species and their spatial distribution before any concrete understanding of impact on catalytic performance can be realized.

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          Most cited references61

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          Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

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            Cobalt particle size effects in the Fischer-Tropsch reaction studied with carbon nanofiber supported catalysts.

            The influence of cobalt particle size in the range of 2.6-27 nm on the performance in Fischer-Tropsch synthesis has been investigated for the first time using well-defined catalysts based on an inert carbon nanofibers support material. X-ray absorption spectroscopy revealed that cobalt was metallic, even for small particle sizes, after the in situ reduction treatment, which is a prerequisite for catalytic operation and is difficult to achieve using traditional oxidic supports. The turnover frequency (TOF) for CO hydrogenation was independent of cobalt particle size for catalysts with sizes larger than 6 nm (1 bar) or 8 nm (35 bar), while both the selectivity and the activity changed for catalysts with smaller particles. At 35 bar, the TOF decreased from 23 x 10(-3) to 1.4 x 10(-3) s(-1), while the C5+ selectivity decreased from 85 to 51 wt % when the cobalt particle size was reduced from 16 to 2.6 nm. This demonstrates that the minimal required cobalt particle size for Fischer-Tropsch catalysis is larger (6-8 nm) than can be explained by classical structure sensitivity. Other explanations raised in the literature, such as formation of CoO or Co carbide species on small particles during catalytic testing, were not substantiated by experimental evidence from X-ray absorption spectroscopy. Interestingly, we found with EXAFS a decrease of the cobalt coordination number under reaction conditions, which points to reconstruction of the cobalt particles. It is argued that the cobalt particle size effects can be attributed to nonclassical structure sensitivity in combination with CO-induced surface reconstruction. The profound influences of particle size may be important for the design of new Fischer-Tropsch catalysts.
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              Cobalt carbide nanoprisms for direct production of lower olefins from syngas.

              Lower olefins-generally referring to ethylene, propylene and butylene-are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The 'Fischer-Tropsch to olefins' (FTO) process has long offered a way of producing lower olefins directly from syngas-a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.
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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                March 2017
                17 March 2017
                : 3
                : 3
                : e1602838
                Affiliations
                [1 ]Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, U.K.
                [2 ]Research Complex at Harwell, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0FA, U.K.
                [3 ]Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K.
                [4 ]ISIS Facility, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire OX11 0QX, U.K.
                [5 ]Finden Limited, The Workstation Merchant House, 5 East St. Helen Street, Abingdon, Oxfordshire OX14 5EG, U.K.
                [6 ]School of Earth and Environmental Sciences, University of Manchester, Manchester M13 9PL, U.K.
                Author notes
                [* ]Corresponding author. Email: stephen.price@ 123456diamond.ac.uk (S.W.T.P.); andrew.beale@ 123456ucl.ac.uk (A.M.B.)
                Author information
                http://orcid.org/0000-0001-5601-6296
                http://orcid.org/0000-0002-9578-0374
                http://orcid.org/0000-0002-0923-1433
                http://orcid.org/0000-0001-6473-2743
                Article
                1602838
                10.1126/sciadv.1602838
                5357128
                8bba1c92-26c1-403e-9fd6-c6c0765619a8
                Copyright © 2017, The Authors

                This is an open-access article distributed under the terms of the Creative Commons Attribution license, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                : 18 November 2016
                : 01 February 2017
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/501100000266, Engineering and Physical Sciences Research Council;
                Award ID: ID0E31AI14940
                Award ID: EP/K007467/1
                Award Recipient :
                Categories
                Research Article
                Research Articles
                SciAdv r-articles
                Nanoparticles
                Custom metadata
                Justin Noriel

                operando,multimodal tomography,xrd-ct,xrf-ct,fischer-tropsch,cobalt,intergrowth

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