Operando DRIFTS-MS Study of WGS and rWGS Reaction on Biochar-Based Pt Catalysts: The Promotional Effect of Na

Biochar-based Pt catalysts, unpromoted and Na-promoted, were prepared by an incipient wetness impregnation method and characterised by Inductively coupled plasma mass spoectrometry (ICP-MS) analysis, X-ray diffraction, N2 adsorption and transmission, and scanning electron microscopy. It was demonstrated that a sodium promoter modifies the acid-base properties of the support, altering the Pt-support interaction. An operando Diffuse reflectance infrared fourier transform spectroscopy-mass spectrometry (DRIFTS-MS) study was performed to gain insights into the reaction pathways and the mechanism of the Water-Gass-Shift (WGS) and the Reverse Water-Gass-Shift (rWGS) reactions. It was demonstrated that the addition of Na enhances the catalytic performance due to the changes induced by the alkali in the electronic structure of the Pt active sites. This effect favours the activation of H2O molecules during the WGS reaction and the dissociation of CO2 during the rWGS reaction, although it may also favour the consecutive CO methanation pathway.Ministerio de Economía y Competitividad ENE2013-47880-C3-2-R, ENE2017-82451-C3-3R, BES-2014-06824

Promoting effect of Sn on supported Ni catalyst during steam reforming of glycerol

The promoting effect of Sn on the catalytic performance of supported Ni catalyst in the reaction of glycerol steam reforming was studied. The physico-chemical properties of the prepared samples were investigated by X-ray fluorescence (XRF), BET surface area, in situ X-ray diffraction (XRD), laser Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and temperature-programmed oxidation (TPO) techniques. The characterization results of the samples after reduction treatment (in the same conditions than the activation before catalytic activity measurements) revealed the formation of Ni-Sn alloy. The Sn-doped catalyst exhibited a high activity and it was demonstrated that the Sn addition increase the catalyst stability and durability by decreasing the coke deposition.Ministerio de Economía y Competitividad ENE2009-14522-C05-0

Intensifying glycerol steam reforming on a monolith catalyst: a reaction kinetic model

In this work, a structured monolithic catalyst has been tested under a wide range of conditions (partial pressure, residence time, temperature and time-on-stream), with the aim of modeling its kinetic behavior and assessing its economic and upscaling potential. We have developed a sequential model to help us interpret both main trends and salient features. Unexpected behavior was found for certain parameter values, which led us to consider kinetic parasitic effects such as mass or heat transfer limitations. By independently invoking these effects, a conciliatory view of the results observed could not be reached. A combined explanation may prove successful, although overfitting could not be ruled out at this point. More importantly, however, the observed salient features of this stable and selective monolith catalyst may hold potential for process intensification of glycerol steam reforming, thus contributing to a more sustainable industry.Ministerio de Economía y Competitividad ENE2013-47880-C3-2-R, ENE2015-66975-C3-2-

Elucidation of water promoter effect of proton conductor in wgs reaction over pt-based catalyst: An operando drifts study

A conventional Pt/CeO2/Al2O3 catalyst physically mixed with an ionic conductor (Mo-or Eu-doped ZrO2) was tested at high space velocity (20,000 h−1 and 80 L h−1 gcat−1) under model conditions (only with CO and H2O) and industrial conditions, with a realistic feed. The promoted system with the ionic conductor physically mixed showed better catalytic activity associated with better water dissociation and mobility, considered as a rate-determining step. The water activation was assessed by operando diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS) studies under reaction conditions and the Mo-containing ionic conductor exhibited the presence of both dissociated (3724 cm−1) and physisorbed (5239 cm−1) water on the Eu-doped ZrO2 solid solution, which supports the appearance of proton conductivity by Grotthuss mechanism. Moreover, the band at 3633 cm−1 ascribed to hydrated Mo oxide, which increases with the temperature, explains the increase of catalytic activity when the physical mixture was used in a water gas shift (WGS) reaction.Ministerio de Ciencia, Innovación y Universidades ENE2015-66975-C3-2-R, RTI2018-096294-B-C

Monitoring the Reaction Mechanism in Model Biogas Reforming by In Situ Transient and Steady-State DRIFTS Measurements

In this work, the reforming of model biogas was investigated on a Rh/MgAlO catalyst. In situ transient and steady-state diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were used to gain insight into the reaction mechanism involved in the activation of CH and CO. It was found that the reaction proceeds through of an initial pathway in which methane and CO are both dissociated on Rh metallic sites and additionally a bifunctional mechanism in which methane is activated on Rh sites and CO is activated on the basic sites of the support surface via a formate intermediate by H-assisted CO decomposition. Moreover, this plausible mechanism is able to explain why the observed apparent activation energy of CO is much lower than that of CH. Our results suggest that CO dissociation facilitates CH activation, because the oxygen-adsorbed species formed in the decomposition of CO are capable of reacting with the CH species derived from methane decomposition.Ministerio de Economía y Competitividad ENE2013-47880-C3-2-R, ENE2015-66975-C3-2-RJunta de Andalucía TEP-819

Hydrogen production by methanol steam reforming on NiSn/MgO-Al 2O3 catalysts: The role of MgO addition

The effect of the magnesia loading on the surface structure and catalytic properties of NiSn/MgO-Al2O3 catalysts for hydrogen production by methanol steam reforming has been investigated. The catalysts have been obtained by impregnation of γ-Al2O3 by the incipient wetness method, with variation of the MgO content. X-ray diffraction (XRD), BET surface area and H2-temperature programmed reduction (TPR) have been used to characterise the prepared catalysts. From this, it has been concluded that the incorporation of MgO results in the formation of MgAl 2O4 spinel, which modifies the acid-base properties of the catalysts. The formation of Ni-Sn alloys after the reductive pre-treatment has also been evidenced. The influence of the temperature of reaction and of the MgO loading on the hydrogen production by reforming of methanol has been established. Moreover, tests of catalytic stability have been carried out for more than 20 h. The carbonaceous deposits have been examined by temperature-programmed oxidation (TPO). The analysis of the catalysts after reaction has confirmed the low level of carbon formation on these catalysts. In no case, carbon nanotubes have been detected on the solids.Junta de Andalucía TEP106Ministerio de Ciencia e Innovación ENE2009-14522-C05-0

Promoting effect of CeO2, ZrO2 and Ce/Zr mixed oxides on Co/Γ-Al2O3 catalyst for Fischer-Tropsch synthesis

A series of cobalt-based catalysts have been synthesized using as support γ-Al2O3 promoted by ceria/zirconia mixed oxides with a variable Ce/Zr molar ratio. The obtained catalysts demonstrated oxide promotion results in the protection of the major textural properties, especially for Zr-rich solids. Reducibility of cobalt species was enhanced by the presence of mixed oxides. The chemical composition of the oxide promoter influenced not only physicochemical properties of final catalysts but also determined their performance during the reaction. In this sense, Zr-rich systems presented a superior catalytic performance both in total conversion and in selectivity towards long chain hydrocarbons. The observed Zr-promotion effect could be explained by two significant contributions: firstly, the partial inhibition of Co–Al spinel compound formation by the presence of Zr-rich phases which enhances the availability of Co actives site and secondly, Zr-associate acidic sites promote higher hydrocarbons selectivity.Ministerio de Economía y Competitividad ENE2012-374301-C03-01, ENE2015-66975-C3-2-

H2-rich syngas production from biogas reforming: overcoming coking and sintering using bimetallic Ni-based catalysts

Dry reforming of methane is a very appealing catalytic route biogas (mainly composed by greenhouse gases: carbon dioxide and methane) conversion into added value syngas, which could be further upgraded to produce liquid fuels and added value chemicals. However, the major culprits of this reaction are coking and active phase sintering that result in catalysts deactivation. Herein we have developed a highly stable bimetallic Ni–Rh catalyst supported on mixed CeO2–Al2O3 oxide using low-noble metal loadings. The addition of small amounts of rhodium to nickel catalysts prevents coke formation and improves sintering resistance, achieving high conversions over extended reaction times hence resulting in promising catalysts for biogas upgrading. © 2023 The Author(s)Ministerio de Ciencia e Innovación (MICIN). España PLEC2021-008086, RYC2018- 024387-I, PID2019-108502RJ-I00European Commission (EC) BIOALL project (Grant Agreement: 101008058

Evidence of new Ni-O-K catalytic sites with superior stability for methane dry reforming

Liquid fuels produced via Fischer-Tropsch synthesis from biomass-derived syngas constitute an attractive and sustainable energy vector for the transportation sector. This study focuses on the role of potassium as a promoter in Ni-based catalysts for reducing coke deposition during catalytic dry reforming. The study provides a new structural link between catalytic performance and physicochemical properties. We identify new Ni-O-K chemical states associated with high stability in the reforming process, evidenced by different characterization techniques. The nickel particles form a core surrounded by a Ni-O-K phase layer (Ni@Ni-O-K) during the reduction of the catalyst. This phase likely presents an alkali-nickelate-type structure, in which nickel is stabilized in oxidation state + 3. The Ni-O-K formation induces essential changes in the electronic, physical, structural, and morphological properties of the catalysts, notably enhancing their long-term stability in dry reforming. This work thus provides new directions for designing more efficient catalysts for sustainable gas-to-liquids processes.Ministerio de Economía y Competitividad RTI2018-096294-B-C33Universidad de Sevilla US-126328

Recent advances on gas-phase CO2 conversion: Catalysis design and chemical processes to close the carbon cycle

Chemical CO2 recycling in the gas phase constitutes a straightforward approach for effective CO2 conversion to added-value products like syngas or synthetic methane. In this scenario, some traditional processes such as the dry and bi-reforming of methane, the CO2 methanation and the reverse water-gas shift have gained a renewed interest from the CO2 utilisation perspective. Indeed, these reactions represent flexible routes to upgrade CO2 and their application at an industrial scale could substantially reduce CO2 emissions. The bottleneck for the implementation of these processes at the commercial level is the development of highly active and robust heterogeneous catalysts able to overcome CO2 activation and deliver sufficient amounts of the upgrading products (i.e. syngas or synthetic natural gas) at the desired operating conditions. This review paper gathers the most recent advances in the design of new catalytic formulations for chemical CO2 recycling in the gas phase and constitutes an overview for experts and newcomers in the field to get fundamental insights into this emerging branch of low-carbon technologies.Ministerio de Ciencia, Innovación y Universidades RTI2018-096294-B-C33, PID2019-108502RJ-I00, IJC2019- 040560-I, RYC2018-024387-IJunta de Andalucía US-1263288, P20-00667European Union (UE).H2020 10100805