The influence of chromium and aluminium doping on the over-reduction during activation of iron-oxide-based water-gas shift catalysts was investigated using Mössbauer spectroscopy for the first time. In situ Mössbauer spectra of catalysts exposed to industrially relevant gas compositions were recorded with increasingly reducing R factors R = [CO]*[H₂]/[CO₂]*[H₂O]. Whereas α-Fe and cementite formed during exposure of a non-doped iron-oxide catalyst to process conditions with an R factor of 2.09, such phases were only observed at R = 4.60 for a chromium-doped catalyst, showing that chromium stabilizes the catalyst. Over-reduction was enhanced to R = 2.88 in a chromium-copper co-doped catalyst. α-Fe was already observed at R = 1.64 in an aluminium-doped catalyst, while cementite formation occurred at R = 2.09, showing that over-reduction was enhanced, the presence of aluminium delaying carburization. Co-doping copper in the aluminium-doped catalyst showed cementite formation at R = 2.09, the same as a non-doped catalyst.

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Hydrogen gas is an essential reagent in numerous industrial processes including ammonia synthesis. Ammonia is a key intermediate in the synthesis of nitrogen-based fertilisers, e.g. nitrates and urea. According to recent estimates (2008), approximately half of the world population is fed by nitrogen-based fertilisers of synthetic origin. Therefore, statistically speaking, every other person reading this sentence owes their existence to ammonia synthesis. Nowadays, most hydrogen gas is produced from natural gas via steam reforming followed by a dual stage water-gas shift reaction. The catalyst used in high-temperature water-gas shift (HTS) is chromium/copper promoted iron oxide. Chromium is known to stabilise the active iron-oxide phase magnetite (Fe3O4) from sintering and over-reduction to α-Fe and Fe-carbides, while copper enhances the activity by providing additional active sites. The chromium stabiliser has been used for over a century, because it provides excellent stability and its low cost. Chromium is added to the catalyst precursor via a co-precipitation/calcination route. An unintended side effect of calcination is that some of the chromium can oxidise to chromium-6, which is prone to strict handling and partial bans. The active magnetite phase has an inverse spinel structure composed of a 1:1:1 mixture of; tetrahedral Fe3+, octahedral Fe3+, and octahedral Fe2+, resulting in an octahedral Fe3+/Fe2+ redox couple. The active sites of the bulk magnetite catalyst are the surface octahedral Fe3+/Fe2+ redox couple. Rational design of catalysts with alternative dopants to chromium is severely hindered because of a poor understanding of chromium incorporation into the inverse spinel magnetite structure. Accordingly, the position of chromium and its effect on the magnetite structure and the octahedral Fe3+/Fe2+ redox couple was investigated in detail.....@en

A set of doped iron oxides (chromium, aluminum, gallium, indium, manganese, zinc, niobium) were prepared by a one-step coprecipitation/calcination approach evaluated for their WGS activity under industrially relevant conditions and characterized in detail. The WGS activity after ageing the doped catalyst for 4 days at 25 bar follows the order chromium ≈ aluminum > gallium > indium > manganese > zinc > niobium for copper-codoped catalysts. The activated catalysts predominantly consist of magnetite, irrespective of the dopant. Mössbauer spectra of aged catalysts showed that aluminum and zinc occupy both tetrahedral and octahedral sites of magnetite, while chromium, gallium, indium, manganese, and niobium preferentially substitute octahedral iron. The incorporation of trivalent metal ions of similar size to octahedral Fe3+ (i.e., chromium, aluminum, gallium) results in moderate to high CO conversion, irrespective of incorporation in tetrahedral or octahedral sites. The substitution of Fe2+ with Mn2+ results in an increased Fe3+/Fe2+ ratio. Incorporation of Zn2+ in tetrahedral sites (replacing Fe3+ ions) leads to a complex structure where the charge balance is compensated from the octahedral sites. Separate dopant metal oxide phases were observed in indium- and niobium-doped catalysts. XPS shows that copper is present as a separate phase in activated copper-codoped catalysts. Aluminum is identified as the most promising promoter for substituting chromium in commercial high-temperature WGS catalysts on the basis of their similar high CO conversion although incorporation of these dopants into the magnetite structure differed substantially.

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Copper promotion of chromium-doped iron oxide prepared via co-precipitation for high-temperature water–gas shift (WGS) catalysis is investigated. Low-temperature Mössbauer spectra demonstrate that copper doping delays hematite (α-Fe₂O₃) formation in the fresh catalyst, favoring the formation of small crystallites of ferrihydrite (Fe₅HO₈∙4 H₂O). Catalysts are treated under industrial WGS conditions at 360 °C (activity evaluation) and 450 °C (ageing) at 2 and 25 bar. Mössbauer spectra show that chromium is incorporated in octahedral sites of the active magnetite (Fe₃O₄) phase, resulting in a partially oxidized structure. Copper doping did not affect the bulk magnetite structure of the activated catalyst, which points to the presence of a separate copper phase. Near-ambient pressure XPS shows that copper is in the metallic state. XPS of discharged catalysts evidenced that reaction at elevated pressure resulted in the surface reduction of Fe³⁺ to Fe²⁺. Copper promotion enhances CO conversion under high-temperature WGS conditions.

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Chromium promotion of iron oxide based water-gas shift (WGS) catalysts prepared via co-precipitation/calcination was investigated. Mössbauer spectroscopy and XRD evidence that chromium is incorporated in the calcined hematite (α-Fe₂O₃) precursor irrespective of the doping level (0−12 wt.%). CO-TPR shows chromium delays the reduction of hematite and the active magnetite (Fe₃O₄) phase. WGS activity was evaluated under realistic conditions for 4 days. Enhanced CO conversion was observed with increased chromium doping. Mössbauer spectra indicate that chromium incorporates into octahedral sites of magnetite and prevents reduction of Fe³⁺ to Fe²⁺ during formation of the active phase, leading to an increased Fe³⁺/Fe²⁺ ratio in octahedral sites. The higher Fe³⁺/Fe²⁺ ratio did not affect the high CO conversion associated with the structural stabilization mechanism of Cr-doping. Interpretation of the Mössbauer spectra was supported by computational modelling of various chromium and vacancy-doped magnetite structures. The bulk structure of an in situ prepared chromium-doped high-temperature WGS catalyst is best described as a partially oxidized chromium-doped magnetite phase. No surface effects of Cr-doping were found.

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