Periodic Reporting for period 1 - MesoSi-CO2 (Design of low-cost and carbon-resistant Ni-based mesoporous silicas for chemical CO2 utilization through tri-reforming of methane)
Reporting period: 2020-10-01 to 2022-09-30
The EU-funded Marie Skłodowska-Curie Individual Fellowship, MesoSi-CO2 project, aimed to design low-cost and carbon-resistant nickel-based mesoporous silicas for chemical CO2 utilization through tri-reforming of methane. This research targeted at developing an efficient synthesis route for KIT-6 mesoporous silica by taking advantage of renewable bio-sources, zero-cost waste, and microwave technology. Reforming of methane is one of the most vital industrial processes which converts natural gas into synthesis gas/syngas (a mixture of H2 and CO). Syngas is an important building block for transforming carbon-based feedstock into hydrocarbons and hydrogen for fuel cells.
The advantage of the studied process is the production of value-added products which is essential to complete the carbon cycle (from hydrocarbons to CO2, then back to carbon-containing chemicals). The usage of CO2 as a valuable resource will lead to creation of new economies with high potential of job creation, as well as business competitiveness for using and proposing clean energy sources. These aspects support the perspective that all sectors should employ low-pollution renewable energy with net “zero-emission” of CO2. Additionally, it is necessary to combat future CO2 emissions to prevent nature changes, such as global temperature increase, melting glaciers and extinction of animal species.
The overall aim of this MSCA-IF project was to design Ni-containing KIT-6 catalysts for tri-reforming of methane, leading to conversion of CO2 during electricity generation and production of value-added products, such as H2 and CO (synthesis gas).
The Scientific Objectives (SO) were:
SO1: Synthesis of catalysts with new properties for CO2 utilization: novel synthesis routes were proposed by involving industrial waste of rice husk ash and microwave usage.
SO2: Control of new properties by physicochemical characterization techniques: XRF, SAXS, XRD, N2 sorption, TPR-H2, TPD-CO2, TPD-NH3, H2 chemisorption, TGA/DSC-MS, SEM to determine the suitable conditions for preparation of the catalysts. In situ XAS-XRD was utilized to understand the course of reduction.
SO3: Evaluation of catalytic performance in reforming of methane reactions for CO2 transformation to synthesis gas: understanding of catalysts activation and obtained selectivity. In situ XAS-XRD analyses were carried out to investigate a possible cause of catalyst deactivation (carbon formation, sintering, oxidation of metallic nickel).
The advantage of the studied process is the production of value-added products which is essential to complete the carbon cycle (from hydrocarbons to CO2, then back to carbon-containing chemicals). The usage of CO2 as a valuable resource will lead to creation of new economies with high potential of job creation, as well as business competitiveness for using and proposing clean energy sources. These aspects support the perspective that all sectors should employ low-pollution renewable energy with net “zero-emission” of CO2. Additionally, it is necessary to combat future CO2 emissions to prevent nature changes, such as global temperature increase, melting glaciers and extinction of animal species.
The overall aim of this MSCA-IF project was to design Ni-containing KIT-6 catalysts for tri-reforming of methane, leading to conversion of CO2 during electricity generation and production of value-added products, such as H2 and CO (synthesis gas).
The Scientific Objectives (SO) were:
SO1: Synthesis of catalysts with new properties for CO2 utilization: novel synthesis routes were proposed by involving industrial waste of rice husk ash and microwave usage.
SO2: Control of new properties by physicochemical characterization techniques: XRF, SAXS, XRD, N2 sorption, TPR-H2, TPD-CO2, TPD-NH3, H2 chemisorption, TGA/DSC-MS, SEM to determine the suitable conditions for preparation of the catalysts. In situ XAS-XRD was utilized to understand the course of reduction.
SO3: Evaluation of catalytic performance in reforming of methane reactions for CO2 transformation to synthesis gas: understanding of catalysts activation and obtained selectivity. In situ XAS-XRD analyses were carried out to investigate a possible cause of catalyst deactivation (carbon formation, sintering, oxidation of metallic nickel).
The work was conducted within three work packages (WP1-WP3).
WP1 included different synthesis strategies of Ni-based mesoporous silicas. The researcher prepared novel Ni-containing silica catalysts assuming five different synthesis strategies: (i) Low loading of nickel in KIT-6 synthesized at pH of ca. 1, (ii) One-pot synthesis of KIT-6-Ni sample synthesized at pH of 9, (iii) conventional KIT-6 synthesis and wet impregnation with Ni and Y, (iv) rice husk used as a support of Ni-based catalysts for dry reforming of methane, (v) KIT-6-RHA-Ni synthesized from the silica extracted from rice husk ashes. WP2 comprised a detailed physicochemical characterization of the synthesized catalysts. It contained the application of well-established techniques in the Host lab and the Secondment lab. The Secondment involved two stays at the Sorbonne Université (SU), Campus St Cyr in Saint Cyr l’Ecole, France. During the Secondment, the catalytic runs for CO2 utilization were carried out and specific characterizations on the materials were performed (temperature-programmed reduction in H2, temperature-programmed desorption of CO2 or NH3, and Transmission Electron Microscopy). Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) was arranged by SU and performed at Institut de Chimie des Milieux et Matériaux de Poitiers in France. WP3 aimed to study catalytic performance in reforming of methane conditions. Different mixtures of the gases were assumed, involving stoichiometric reactions as well as an excess of one of the gaseous compounds. In situ XAS-XRD provided very meaningful understanding on the cause of the catalysts' deactivation. The measurements were performed at BM31 during beamtimes at the Swiss-Norwegian Beam Lines (SNBL) at European Synchrotron Radiation Facility in Grenoble, France.
The results of MesoSi-CO2 project are reported in: (i) one journal publication; with the researcher as a first author and corresponding author in Gold Open Access Journal (Energy&Fules, ACS Publications, https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.3c02994 ), (ii) forthcoming papers on different synthesis strategies of KIT-6 involving pH of ca. 1 and pH of 9, (iii) forthcoming paper on rice husk ash used as a support for dry reforming of methane, (iv) forthcoming paper on silica extracted form rice husk ashes, (v) six common journal publications with collaborators, (vi) oral presentation at North American Catalysis Society Meeting NAM 27 in New York, USA, (vii) oral presentation at the 19th Nordic Symposium on Catalysis in Espoo, Finland, (viii) poster presentation at the Catalysis at the Energy-Chemistry Nexus - 2022 Winter School in Aussois, France, (ix) poster presentation at Reaction Kinetics, Mechanisms and Catalysis organized online in Budapest, Hungary, (x) poster presentation within a collaboration at 15th International conference on materials chemistry (MC15) organized online by Royal Society of Chemistry.
A summary of the research activates have been presented in the attached image, including the oral presentation of the researcher at the 19th Nordic Symposium on Catalysis in Espoo; beamtimes at European Synchrotron Radiation Facility in Grenoble; Winter School in Aussois; Researchers’ Night organized at the Norwegian University of Science and Technology in Trondheim. The consent has been provided from people pictured in the attached image.
WP1 included different synthesis strategies of Ni-based mesoporous silicas. The researcher prepared novel Ni-containing silica catalysts assuming five different synthesis strategies: (i) Low loading of nickel in KIT-6 synthesized at pH of ca. 1, (ii) One-pot synthesis of KIT-6-Ni sample synthesized at pH of 9, (iii) conventional KIT-6 synthesis and wet impregnation with Ni and Y, (iv) rice husk used as a support of Ni-based catalysts for dry reforming of methane, (v) KIT-6-RHA-Ni synthesized from the silica extracted from rice husk ashes. WP2 comprised a detailed physicochemical characterization of the synthesized catalysts. It contained the application of well-established techniques in the Host lab and the Secondment lab. The Secondment involved two stays at the Sorbonne Université (SU), Campus St Cyr in Saint Cyr l’Ecole, France. During the Secondment, the catalytic runs for CO2 utilization were carried out and specific characterizations on the materials were performed (temperature-programmed reduction in H2, temperature-programmed desorption of CO2 or NH3, and Transmission Electron Microscopy). Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) was arranged by SU and performed at Institut de Chimie des Milieux et Matériaux de Poitiers in France. WP3 aimed to study catalytic performance in reforming of methane conditions. Different mixtures of the gases were assumed, involving stoichiometric reactions as well as an excess of one of the gaseous compounds. In situ XAS-XRD provided very meaningful understanding on the cause of the catalysts' deactivation. The measurements were performed at BM31 during beamtimes at the Swiss-Norwegian Beam Lines (SNBL) at European Synchrotron Radiation Facility in Grenoble, France.
The results of MesoSi-CO2 project are reported in: (i) one journal publication; with the researcher as a first author and corresponding author in Gold Open Access Journal (Energy&Fules, ACS Publications, https://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.3c02994 ), (ii) forthcoming papers on different synthesis strategies of KIT-6 involving pH of ca. 1 and pH of 9, (iii) forthcoming paper on rice husk ash used as a support for dry reforming of methane, (iv) forthcoming paper on silica extracted form rice husk ashes, (v) six common journal publications with collaborators, (vi) oral presentation at North American Catalysis Society Meeting NAM 27 in New York, USA, (vii) oral presentation at the 19th Nordic Symposium on Catalysis in Espoo, Finland, (viii) poster presentation at the Catalysis at the Energy-Chemistry Nexus - 2022 Winter School in Aussois, France, (ix) poster presentation at Reaction Kinetics, Mechanisms and Catalysis organized online in Budapest, Hungary, (x) poster presentation within a collaboration at 15th International conference on materials chemistry (MC15) organized online by Royal Society of Chemistry.
A summary of the research activates have been presented in the attached image, including the oral presentation of the researcher at the 19th Nordic Symposium on Catalysis in Espoo; beamtimes at European Synchrotron Radiation Facility in Grenoble; Winter School in Aussois; Researchers’ Night organized at the Norwegian University of Science and Technology in Trondheim. The consent has been provided from people pictured in the attached image.
The progress beyond state-of-the-art involves the synthesized catalysts within this MSCA-IF project: (i) dry reforming KIT-6-Ni catalyst produced through one-pot synthesis assuming pH of ca. 1 (low loading of nickel) and pH of 9 (allowed to introduce higher loading of nickel), (ii) rice husk ash (RHA) used as a support for dry reforming of methane, and (iii) an extraction of silica from rice husk for the synthesis of KIT-6-RHA-Ni. The scientific and technological quality of the results was expressed by the oral and poster presentations and the publication of scientific results, highlighting that: (i) pH adjustment method allows structural control and channel modification during the fabrication of KIT-6 mesoporous materials, and (ii and iii) that from waste material we are able to produce mesoporous supports for CO2 utilization.