CO2 Methanation Research Articles

High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate

AbstractStabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g−1 ⋅ h−1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x=12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

Core‐Shell Catalyst Pellets for CO2 Methanation in a Pilot‐Scale Fixed‐Bed Reactor

AbstractPower‐to‐methane (PtM) offers an efficient opportunity for surplus renewable energy storage, but heat management is a major challenge for conducting the highly exothermic methanation reaction. To address this challenge, this study presents the first successful demonstration of core‐shell catalyst pellets in a pilot‐scale reactor for CO2 methanation. Experiments in a wall‐cooled fixed‐bed reactor are conducted with diluted and undiluted reactant feed under systematic variation of cooling temperature and inlet gas flow rate. The results show that core‐shell catalyst pellets significantly reduce the hot‐spot temperature while maintaining comparable reactant conversions to uncoated catalyst pellets at the same conditions. Additionally, core‐shell catalyst pellets allow for undiluted reactant feed at comparably low hot‐spot temperatures (approx. 600 °C).

Formate and CO* Radicals Intermediated Atmospheric CO2 Conversion over Co-Ni Bimetallic Catalysts Assembled on Diatomite.

There exists an imperative exigency to ascertain catalysts of cost-effectiveness and energy efficiency for the facilitation of industrial CO2 methanation. In this area, the dual metal synergistic enhancement of the metal-support interaction emerges as a highly promising strategy. Here, Diatomite (Dt) was used as the support, and a series of CoyNi/Dt (Co as the first component and Ni as the second component) composite catalysts were constructed using an ultrasound-assisted coimpregnation method. Different Co/Ni molar ratios had a significant impact on the phase structure, chemical properties, morphological characteristics, and NiCo crystal structure of the xCoyNi/Dt materials. When the Co/Ni molar ratio was set to 2.0, a Ni-Co alloy was obtained, which is the key to improve the catalytic activity. Compared to the other xCoyNi/Dt catalysts, the bimetallic catalyst 2Co1Ni/Dt exhibited superior CO2 catalytic performance and stability, achieving a 76% CO2 conversion and 98% CH4 selectivity at 425 °C. The in situ DRIFTS results indicated that CO2 methanation over the 2Co1Ni/Dt catalyst followed the reaction pathway with formate and CO* radicals as the intermediates.

Investigation of CO methanation activities of ZSM-5 supported Ni catalysts using microchannel and conventional reactor

Investigation of CO methanation activities of ZSM-5 supported Ni catalysts using microchannel and conventional reactor

Band gap effect of TiO2 on supported Ru single-atom catalysts for CO2 methanation by DFT calculations

The influence of TiO2 band gap on structure and reactivity of the supported single ruthenium (Ru1) atom was studied by density functional theory calculations, utilizing Ru1/2L-TiO2 and Ru1/3L-TiO2 as model catalysts for CO2 methanation. The supports have band gaps of 2.39 eV and 1.48 eV, respectively. The band gap plays a significant role in electronic metal-support interactions (EMSIs) and the position of the d-band center of the Ru1 on the TiO2. The Ru1/3L-TiO2, the Ru1 catalyst supported on the 3L-TiO2 with a narrower band gap, shows enhanced EMSIs and a d-band center that is positioned farther from Fermi level, leading to lower charge density on the Ru1 and weaker adsorption of H2, CO2, and CO compared to the Ru1/2L-TiO2. CO2 methanation followed CO pathway, with the hydrogenation of CO* to HCO* identified as the rate-determining step on the Ru1/nL-TiO2. The Ru1 catalyst supported on TiO2 with a narrower band gap is more favorable kinetically and thermodynamically for CO2 methanation, despite the band gap not altering the reaction pathway. Enhanced hydrogen mobility and a pronounced promotional effect of hydrogen on CO adsorption, due to the narrower band gap support, are key factors facilitating the easier hydrogenation of CO* on the Ru1/3L-TiO2.

Optimizing reverse water gas shift catalysis: Minimizing metal loading and enhancing performance with Pt/ZrO2 catalysts through Rh incorporation

In this study, the optimization of catalysts for the reverse water gas shift reaction by minimizing metal loading and enhancing the performance of supported Pt catalysts through Rh incorporation was done. The catalysts were synthesized by the wet impregnation method, in which the metal noble load in bimetallic samples decreased by approximately one-third compared to the reference platinum catalyst, with varying Rh-Pt ratios. In all materials, m-ZrO2, obtained by the hydrothermal method, was used as support. In the catalytic tests in a continuous packed-bed flow reactor at atmospheric pressure, all samples were active to catalyze CO2 reduction between 200 and 300 °C. Bimetallic samples, particularly those with an Rh-Pt atomic ratio of 20–80, exhibited superior performance in the RWGS reaction despite their lower metal content. Based on the results of H2-TPR, FTIR in situ, and XPS, we propose that the enhanced CO production in bimetallic samples compared to Pt/ZrO2 catalysts can be attributed to Rh increasing the reduction extent of supported Pt. This enhancement facilitates the hydrogenation of bicarbonate species into formate species, which subsequently evolve into Pt0-CO and ultimately into CO. Additionally, Rh incorporation enables an alternative pathway for CO generation, where Pt0-carbonyls, known for their CO-producing capability, are formed via CO2 dissociation on the Pt0 surface. However, higher Rh concentrations favor the CO2 methanation rather than the RWGS reaction.

Very low Ru loadings boosting performance of Ni-based dual-function materials during the integrated CO2 capture and methanation process

Herein, the effect of the Ru:Ni bimetallic composition in dual-function materials (DFMs) for the integrated CO2 capture and methanation process (ICCU-Methanation) is systematically evaluated and combined with a thorough material characterization, as well as a mechanistic (in-situ diffuse reflectance infrared fourier-transform spectroscopy (in-situ DRIFTS)) and computational (computational fluid dynamics (CFD) modelling) investigation, in order to improve the performance of Ni-based DFMs. The bimetallic DFMs are comprised of a main Ni active metallic phase (20 wt%) and are modified with low Ru loadings in the 0.1–1 wt% range (to keep the material cost low), supported on Na2O/Al2O3. It is shown that the addition of even a very low Ru loading (0.1–0.2 wt%) can drastically improve the material reducibility, exposing a significantly higher amount of surface-active metallic sites, with Ru being highly dispersed over the support and the Ni phase, while also forming some small Ru particles. This manifests in a significant enhancement in the CH4 yield and the CH4 production kinetics during ICCU–Methanation (which mainly proceeds via formate intermediates), with 0.2 wt% Ru addition leading to the best results. This bimetallic DFM also shows high stability and a relatively good performance under an oxidizing CO2 capture atmosphere. The formation rate of CH4 during hydrogenation is then further validated via CFD modelling and the developed model is subsequently applied in the prediction of the effect of other parameters, including the H2 inlet concentration, inlet flow rate, dual-function material weight, and reactor internal diameter.

Novel application of Ru-based catalysts on MgAl oxides alkaline adsorbents for cyclic CO2 methanation

This study explores the performances of Ru-based catalysts with a low metal content (2 wt%) supported on MgO and Mg-Al Oxides (MgAl) for cyclic CO2 adsorption and methanation at atmospheric pressure. Adsorption and desorption tests demonstrated that MgAl-based catalysts are more promising for CO2 capture due to their larger surface area and better distribution of active sites (Mg2+–O2-). Moreover, doping the MgAl support with K2CO3 further improves surface alkalinity and, consequently, capture performance. During cyclic operations, all the catalysts proved effective and selective for methane production. To simulate realistic conditions, both dry and wet CO2 adsorptions were conducted before the methanation stage. The presence of moisture positively influenced gas carbonation for all catalysts, increasing the overall amount of CO2 captured. Specifically, Ru/MgAl exhibited the best performance in terms of adsorption and conversion to methane (approximately 85 % after dry adsorption and 79 % after wet adsorption), with a maximum methane production of 183 and 220 μmolCH4 g−1, respectively. The reaction yield was further enhanced with Ru-K/MgAl, achieving 327 μmolCH4 g−1 after dry adsorption and 333 μmolCH4 g−1 after wet adsorption. However, this catalyst displays different conversion kinetics, attributed to slowed carbonate migration, low Ru dispersion, limited specific surface area, and excessive carbonation strength. Operando FTIR tests revealed differences in reaction intermediates between Ru/MgAl and Ru-K/MgAl, by going deeper into the kinetic differences observed. The study concludes that Ru/MgAl materials are highly promising catalysts for CO2 adsorption and methane production, supporting the development of technologies for CO2 abatement and renewable energy utilisation.

Integrated capture and conversion of CO2 to methane using deep eutectic solvents under mild conditions

Addressing the issues of absorbent regeneration, CO2 compression and purification, and energy consumption during transportation in the integrated carbon capture and utilization (ICCU) process, an integrated technology for CO2 capture and hydrogenation conversion has been proposed. In this study, deep eutectic solvents (DESs) composed of tetramethylguanidine (TMG) and ethylene glycol (EG) were employed to capture and hydrogenate CO2. When a heterogeneous Ru-based catalyst and a TMG:EG DES were used as a catalytic system, CO2 methanation was achieved under mild conditions (170°C and 8 MPa H2 pressure), with a CH4 yield of up to 75 % and a conversion number (TON) of 148. Importantly, the structure of the DES remained unchanged before and after the reaction, and the catalytic system could be reused three times without significantly diminishing the effectiveness of CO2 hydrogenation. This method not only reduces desorption energy consumption but also benefits from the absorbent’s high specific heat capacity, enabling the absorbent to absorb the heat generated during CO2 hydrogenation and addressing issues such as carbon deposition and catalyst deactivation resulting from poor heat transfer.

Experimental and calculation investigations of the photocatalytic selective and performance for CO2 reduction by cobalt-doped Bi4O5Br2 nanosheets

This study delves into the photocatalytic process of an innovative Co-doped Bi4O5Br2 material synthesized through a straightforward process. Experimental and theoretical findings corroborate that cobalt doping remarkably enhances the CO2 reduction capability of Bi4O5Br2 catalysts under visible light. Findings indicate that Co-doped Bi4O5Br2 exhibits substantial advantages over its pristine counterpart in photocatalytic CO2 reduction. Notably, the catalyst with 4 at.% Co doping demonstrates the highest photocatalytic CO2 reduction efficiency, achieving CO and methane production activities of up to 9.46 and 0.20 μmol/g/h, respectively. Furthermore, the low activation energy for CO2 reduction in Co-doped Bi4O5Br2, as indicated by reaction pathways calculations, facilitates the process. Detailed experimental results reveal that Co incorporation does not alter the surface morphology or the crystalline phase of the photocatalyst. The superior efficiency of Co-doped Bi4O5Br2 is attributed to multiple factors: a narrow band gap, expanded visible light absorption spectrum, greater absorption intensity within the visible range, and enhanced separation efficiency of photogenerated electrons and holes compared to pristine Bi4O5Br2. This highlights the practical application of Co-doped Bi4O5Br2 for enhancing photocatalytic performance, supporting future advancements in solar energy utilization and the creation of high-value chemical products.

Cobalt Supported Nickel Silicate Nanotubes for Efficient CO2 Methanation

Cobalt Supported Nickel Silicate Nanotubes for Efficient CO2 Methanation

Isomorphously Substituted Cerium Induced Oxygen Vacancy and Medium Basicity in Ni/Fibrous Silica Catalyst for superior low-temperature CO2 Methanation

Isomorphously Substituted Cerium Induced Oxygen Vacancy and Medium Basicity in Ni/Fibrous Silica Catalyst for superior low-temperature CO2 Methanation

Ni–CaZrO3 with perovskite phase loaded on ZrO2 for CO2 methanation

CO2 methanation has emerged as a promising strategy for the greenhouse gas CO2 utilization and storage of hydrogen. However, achieving low temperature activity and high temperature stability remains challenging due to the sintering of Ni-based catalysts. To address these limitations, this study introduces a Ni–CaZrO3 catalyst featuring a perovskite phase supported on ZrO2, prepared via citrate complexation and impregnation methods. In this approach, a perovskite-type oxide (PTO) of CaZrO3 forms through a solid reaction on the surface of ZrO2 with impregnated CaO. The formation of CaZrO3 on Ni/ZrO2 restrains the ZrO2 support aggregation and reduces the particle size of Ni nanoparticles (NPs), thereby enhancing the activity for CO2 methanation. The interaction between Ni–CaZrO3, and ZrO2 effectively confines the Ni NPs and CaZrO3, enhancing the sintering resistance of Ni–CaZrO3. This leads to excellent stability of the resulting catalyst for CO2 methanation. The Ni–CaZrO3/ZrO2 catalyst achieves 85% CO2 conversion and maintains 100% methane selectivity at 300 °C, demonstrating the prolonged stability over 100 h at 550 °C. Notably, the loading of CaZrO3 in a perovskite phase on ZrO2 via solid surface reaction represents an interesting and valuable route, which could be extended to loading other PTOs for industrial applications.

CO2 methanation: a bibliometric analysis and review of activated carbon-based materials (2014–24)

Abstract This study highlights the significant potential of activated carbon (AC)-based materials in environmental remediation and energy production, particularly in converting carbon dioxide (CO2) and hydrogen (H2) into methane (CH4) and water (H2O) using transition metal-based catalysts. It emphasizes the role of porous AC in waste reduction and resource utilization, examining various applications of CO2 and evaluating environmental impacts. The research explores commercialization opportunities and specifically investigates CO2 methanation using AC-based materials. Using bibliometric analyses of 4196 articles from the Web of Science database, the study identifies a growing research interest in porous AC-related CO2 methanation from 2014 to 2024. The top three journals in this field are Environment Development and Sustainability, Biomass Conversion and Biorefinery, and Journal of Environment Science and Pollution. However, there is limited inter-institutional collaboration in this field, suggesting room for development towards commercializing sustainable CH4 production pathways. CH4 is highlighted as a crucial intermediate in industrial processes, and research directions are identified through co-occurring author keywords analysis. The study suggests the need for a comprehensive approach integrating AC materials into carbon-neutral energy processes while addressing the potential adverse effects of AC nanoparticles on biological and environmental factors. Ultimately, it clarifies the potential uses and commercialization prospects for porous AC materials, especially in conjunction with carbon capture and utilization technologies, promoting sustainable practices in energy production and environmental management.

Design and Development of Integrated Direct Air Capture and Methanation Processes

AbstractThe synergies from integrating direct air capture and CO2 methanation are assessed and quantified. Three direct air capture and methanation processes with different integration strategies are proposed: only heat integration, direct air capture sorbent regeneration with high‐pressure H2, and complete integration in a single unit. The heat integration study via pinch analysis evaluated the potential energy demand reduction. Overall autothermal operation is achievable, as the heat generated in methanation often exceeds that required for direct air capture sorbent regeneration. A novel process combining CO2 adsorption and methanation in one reactor provided the best productivity and energy demand results. However, this design requires complex cycles and strict demands on the sorbent and catalyst, requiring further development and experimental demonstration.

Environmental tradeoff on integrated carbon capture and in-situ methanation technology

Compared to conventional CO2 removal methods, carbon capture and in-situ conversion using dual function materials avoid compression and transportation of CO2, which is regarded as a promising technology. Although it brings additional economic benefits, the environmental impacts of CO2 capture and conversion remain unclear. A life cycle assessment of an integrated CO2 capture and methanation system using dual function materials is conducted to investigate its feasibility to reduce global warming. Life cycle inventory is obtained through construction, operation, and disposal process of the integrated system. A dynamic model of CO2 capture and methanation is developed to obtain the operating parameters. Results show that the optimal global warming potential is 0.706 kg CO2,eq per kilogram captured CO2, which indicates the advantages of using dual function materials for carbon mitigation. Global warming potential is a minor factor among the overall normalized environmental impacts, only accounting for 0.5 % of the total normalized impact, while the main factor marine aquatic ecotoxicity accounts for around 73 %, and fresh water aquatic ecotoxicity accounts for around 23 %. Global warming potential is the most affected by green hydrogen input, followed by dual function material input. Results reveal that the integrated CO2 capture and conversion using dual function materials is conducive to carbon mitigation but has significant other environmental impacts, such as marine aquatic ecotoxicity, and the main contributors to the environmental impacts are wind electricity, green hydrogen, refrigerator, and dual function material.

Identification of Deactivation Mechanisms by the Periodic Transient Kinetic Method

AbstractThe understanding of deactivation processes in heterogeneous catalysis is key for the development of new materials and exploration of new operation windows. In this contribution, the periodic transient kinetic method (PTK) is used to identify and separate catalyst deactivation processes for the first time. The PTK method is applied for a standard Ni/Al2O3 catalyst in CO and CO2 methanation for 24 h and compared to steady‐state experiments. For the example reactions, the study exhibits different deactivation behavior for CO and CO2 methanation. The results demonstrate that the PTK method delivers an insight into the deactivation process and furthermore gives evidence for the underlying mechanism.

Continuous Biological Ex Situ Methanation of CO2 and H2 in a Novel Inverse Membrane Reactor (IMR)

A promising approach for carbon dioxide (CO2) valorization and storing excess electricity is the biological methanation of hydrogen and carbon dioxide to methane. The primary challenge here is to supply sufficient quantities of dissolved hydrogen. The newly developed Inverse Membrane Reactor (IMR) allows for the spatial separation of the required reactant gases, hydrogen (H2) and carbon dioxide (CO2), and the degassing area for methane (CH4) output through commercially available ultrafiltration membranes, enabling a reactor design as a closed circuit for continuous methane production. In addition, the Inverse Membrane Reactor (IMR) facilitates the utilization of hydraulic pressure to enhance hydrogen (H2) input. One of the process’s advantages is the potential to utilize both carbon dioxide (CO2) from conventional biogas and CO2-rich industrial waste gas streams. An outstanding result from investigating the IMR revealed that, employing the membrane gassing concept, methane concentrations of over 90 vol.% could be consistently achieved through flexible gas input over a one-year test series. Following startup, only three supplemental nutrient additions were required in addition to hydrogen (H2) and carbon dioxide (CO2), which served as energy and carbon sources, respectively. The maximum achieved methane formation rate specific to membrane area was 87.7 LN of methane per m2 of membrane area per day at a product gas composition of 94 vol.% methane, 2 vol.% H2, and 4 vol.% CO2.

Abundant interfacial and intrinsic oxygen vacancies enabling small nickel/ceria nanocrystal efficient CO2 methanation

Smaller nano-sizes typically result in supported catalysts with abundant interfacial and intrinsic oxygen vacancies for better adsorption and activation of small molecules, including CO2, leading to improved efficiency of CO2 methanation. Here, Ni/CeO2-S with the smaller nano-size of around 4.2 nm is used to catalyze CO2 methanation, which exhibits significantly enhanced activity compared to larger nano-sized Ni/CeO2-L catalyst, even surpassing the most majority of previously reported catalysts using CeO2 as the support or Ni as the active metal. The coexistence of interfacial defects and intrinsic oxygen vacancies allows for enhanced adsorption and activation of CO2 molecules as well as H spillover, resulting in such improved CO2 methanation. In-situ DRIFTS demonstrate a nearly sole Formate pathway on Ni/CeO2-S for efficient CO2 hydrogenation. This research provides valuable insights into the reaction mechanism over a small nanosize supported catalyst.

Numerical simulation for subsidence control in CO2 storage and methane hydrate extraction

Gas hydrates are increasingly viewed as a promising alternative to traditional fossil fuels. However, their extraction process poses risks to structural integrity, potentially causing significant subsidence. In this study, we developed a Thermo-Hydro-Mechanical-Chemical (THMC) model to analyze the impact of gas hydrate extraction on seabed subsidence. Our investigation focused on the influence of bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity on subsidence during gas hydrate extraction via depressurization.The results show that seabed subsidence is affected by various factors such as bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity. It was noted that significant subsidence is associated with low initial hydrate concentration, high permeability, porosity, low gas saturation, low rock thermal conductivity, and a notable pressure drop of 79.31%.To address this issue, we propose a seabed subsidence mitigation strategy involving CO2 injection. This approach not only safeguards offshore infrastructure and coastal communities but also helps reduce CO2 emissions, aligning with global climate change mitigation efforts. In our model, CO2 injection occurs in the subsurface reservoir at the interface between the free water zone and hydrate-bearing formations. The CO2 hydrates formation process releases heat, which dissociates methane hydrates, allowing the methane to be replaced by CO2 molecules and move towards the production well.Our analysis reveals that increasing injection temperature and rate significantly reduces subsidence. Additionally, the range of investigated injection pressures, which included pressures equal to and more than double the initial reservoir pressure, showed inconsequential impacts on seabed subsidence.The effectiveness of subsidence reduction is significantly enhanced by injecting a CO2/N2 mixture compared to pure CO2 injection. The most substantial reduction in subsidence occurred when a mixture of CO2 and N2 in a 50/50 vol/vol ratio was injected at a high rate.These findings offer crucial insights for optimizing the efficiency and control of gas hydrate extraction methods. They emphasize the importance of employing balanced injection strategies to minimize environmental risks and ensure sustainable energy extraction.