Performance For CO Methanation Research Articles

Comparative Study of Porous High‐Entropy Oxides as Low‐Temperature Catalysts for CO2 Methanation

AbstractHigh‐entropy oxides (HEOs) are an emerging class of materials whose compositional complexity has garnered attention because of their tailorable chemistries and unique properties arising from extreme configurational entropy. Solid‐state methods are often employed to synthesize HEOs, but such methods result in poor material properties for catalytic processes, leaving HEOs less studied for catalysis. Here we utilize different wet‐synthesis strategies to produce porous HEOs and investigate their performance in heterogeneous CO2 hydrogenation to methane. Specifically, HEOs were synthesized using hydrothermal, co‐precipitation, and solvothermal methods, resulting in different morphologies like platelets or spheres. Of the tested materials, HEOs with 2‐D platelets derived from hydrothermally‐synthesized high‐entropy layered double hydroxides had superior catalytic performance, especially in low‐temperature regimes (<300 °C). K‐edge XANES indicated that metallic sites (Ni0‐Co0) were formed during the reaction, and these metallic sites are dispersed into the HEO matrix which is confirmed by STEM/elemental mapping. This facile synthesis approach allows for realized synergy between the metallic sites and the HEO support, leading to superior performance for CO2 methanation compared to low‐entropy counterparts. Finally, this study illustrates how HEOs offer new avenues of tailorability in terms of the interplay between support, active site and reaction temperatures for heterogeneous catalysis.

Insight and comprehensive study of Ni-based catalysts supported on various metal oxides for CO2 methanation

In this study, nickel supported on various metal oxides were prepared by simple impregnation and the performance for CO2 methanation was tested. The oxide supports were all prepared by thermal decomposition of metal salts to provide comparable oxide properties such as surface area. Among the investigated oxides, nickel supported on CeO2 and Y2O3 showed the highest CO2 conversion of 90% at 320 °C with highest CH4 selectivity of 99%. The order of catalyst activity (XCO2@320°C) was reported: Ni/CeO2 ~ Ni/Y2O3 > > Ni/La2O3 > Ni/ZrO2 > Ni/Al2O3 > Ni/MgO > Ni/CaO > > Ni/MnO. The physicochemical properties of the catalysts were analyzed by TEM, BET, XRD, ICP, H2-TPR, CO2-TPD, H2 chemisorption, TGA, Raman, and XPS. From the characterization results, the catalyst activity was independent to specific surface area of catalyst and crystallite size of Ni. The amount of oxygen vacancies and weak-to-medium basic sites exhibited major roles for enhancing catalyst activity. The CeO2 and Y2O3 as reducible oxide supports not only provided abundant oxygen vacancies / basic sites, but also promoted Ni dispersion with appropriate interaction between metal and support, resulting in higher reducibility at low temperature. The reduction of catalyst at high temperature can significantly improve the performance of Ni supported on non-reducible MgO. However, the Ni/CeO2 and Ni/Y2O3 reduced at high temperature suffered from coalescence of CeO2 and Y2O3, though Ni crystallite sizes are well preserved from sintering.

A detailed characterization study of Ni/CeO2 catalysts identifies Ni availability as the primary factor affecting CO2 methanation performance

The structure of a catalyst has a strong impact on its performance. Here we investigate the physicochemical properties of Ni/CeO2 in an attempt to draw structure–activity relationships for CO2 methanation. A combination of characterisation methods (X-ray diffraction (XRD), 4D Scanning Transmission Electron Microscopy (4D-STEM), CO chemisorption and oxygen storage capacity study etc.) clearly demonstrates the effect of Ni crystallite size, Ni availability (i.e. catalytically accessible Ni) and oxygen vacancies at the Ni-CeO2 interface in Ni/CeO2 during CO2 methanation. Among them, the role of exposed Ni active sites is highlighted, and two possible optimisation schemes i.e. changing the support calcination temperature and the final calcination atmosphere are proposed to obtain a better dispersal of Ni NPs (nanoparticles) on CeO2. Both modification methods do not affect the reaction route, and the activity differences of Ni/CeO2 can be explained by the various hydrogenation rate of formate species, as confirmed by in situ diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) measurements.

Boosting Photocatalytic CO2 Methanation through Interface Fusion over CdS Quantum Dot Aerogels.

In the field of photocatalytic CO2 reduction, quantum dot (QD) assemblies have emerged as promising candidate photocatalysts due to their superior light absorption and better substrate adsorption. However, the poor contacts within QD assemblies lead to low interfacial charge transfer efficiency, making QD assemblies suffer from unsatisfactory photocatalytic performance. Herein, a novel approach is presented involving the construction of strongly interfacial fused CdS QD assemblies (CdS QD gel) for CO2 reduction. The novel CdS QD gel demonstrates outstanding photocatalytic performance for CO2 methanation, achieving a CH4 generation rate of ≈296 µmol g-1 h-1, with a selectivity surpassing 76% and an apparent quantum yield (AQY) of 1.4%. Further investigations reveal that the robust interfacial fusion in these CdS QDs not only boosts their ability to absorb visible light but also significantly promotes charge separation. The present work paves the way for utilizing QD gel photocatalysts in realizing efficient CO2 reduction and highlights the critical role of interfacial engineering in photocatalysts.

Enhancing low-temperature CO2 methanation performance by selectively covering Ni with CeO2 to form Ni-O-Ce interface active sites

The methanation of CO2 is crucial for resource utilization, however, achieving excellent CO2 methanation performance with Ni-based catalysts at low temperatures remains highly challenging. In this study, a high-performance 10Ni-0.1Ce/Al catalyst was synthesized using a simple and efficient one-pot combustion method. Unlike other catalysts with the same components, this catalyst exhibits a unique feature where a small amount of the CeO2 promoter is dispersed on the support, while the majority selectively binds to and coats the Ni nanoparticles. This distinctive structure allows it to achieve approximately 80 % CO2 conversion and 99.9 % CH4 selectivity under conditions of 260 °C, 0.1 MPa, and a GHSV of 48,000 mL·g−1·h−1. The high catalytic performance is attributed to the unique structure of Ni nanoparticles and CeO2, which promotes the formation of numerous Ni-O-Ce interface active sites. These Ni-O-Ce interfaces enhance the reducibility and increase the content of weak basic sites in the catalyst. The combination of in-situ DRIFTS and TPSR reveals that the decomposition of bridged HCOO– to *CO is the rate-determining step. The presence of Ni-O-Ce interface active sites in the 10Ni-0.1Ce/Al catalyst facilitates the generation of abundant bridged HCOO– intermediates with higher activity than the 10Ni/Al catalyst, leading to a substantial enhancement in catalytic performance.

RuCo/ZrO2 Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO2 Methanation.

Photothermal CO2 methanation reaction represents a promising strategy for addressing CO2-related environmental issues. The presence of efficient tandem catalytic sites with a localized high-temperature is an effective pathway to enhance the performance of CO2 methanation. Here the bimetallic RuCo nanoparticles anchored on ZrO2 fiber cotton (RuCo/ZrO2) as a photothermal catalyst for CO2 methanation are prepared. A significant photothermal CO2 methanation performance with optimal CH4 selectivity (99%) and rate (169.93mmol gcat -1 h-1) is achieved. The photothermal energy of the RuCo bimetallic nanoparticles, confined by the infrared insulation and low thermal conductivity of the ZrO2 fiber cotton (ZrO2 FC), provides a localized high-temperature. In situ spectroscopic experiments on RuCo/ZrO2, Ru/ZrO2, and Co/ZrO2 indicate that the construction of tandem catalytic sites, where the Co site favors CO2 conversion to CO while incorporating Ru enhances CO* adsorption for subsequent hydrogenation, results in a higher selectivity toward CH4. This work opens a new insight into designing tandem catalysts with a photothermal confinement effect in CO2 methanation reaction.

Highly Stable and Selective Ni/ZrO2 Nanofiber Catalysts for Efficient CO2 Methanation.

Ni-based oxides are promising catalysts for CO2 methanation. However, Ni-based catalysts also have some unresolved issues and drawbacks in practical applications. The activity and selectivity of Ni-based catalysts in CO2 methanation at low temperatures still need to be improved. Here, Ni/ZrO2 nanofibers with high surface areas (up to 101.2 m2/g) were prepared by electrospinning methods. The Ni/ZrO2-ES (also named as 66Ni/ZrO2) catalyst showed excellent catalytic performance in CO2 methanation (the CO2 conversion = 81% and CH4 selectivity = 99% at 350 °C) and excellent stability for 100 h, which was better than most reported Ni/ZrO2 catalysts. However, the comparison sample Ni/ZrO2-CP prepared by the coprecipitation method had poor catalytic performance (the CO2 conversion = 54% and CH4 selectivity = 90% at 350 °C). Within 100 h, the CO2 conversion decreased to 30% and the CH4 selectivity decreased to 52%. Both EPR and O1S XPS confirmed that Ni/ZrO2 nanofibers can form more reactive oxygen species vacancies, and CO2-TPD confirmed that nanofibers had more CO2 adsorption sites compared with the control sample Ni/ZrO2-CP. In situ DRIFTS analysis showed that bidentate carbonate and monodentate carbonate were key intermediates in CO2 methanation. The catalytic performance of Ni/ZrO2 nanofiber catalysts would be attributed to higher dispersion of Ni species on the surface of nanofibers, high specific surface area (101.2 m2/g), more oxygen vacancies, more CO2 adsorption sites, and the synergistic effect between Ni nanoparticles and ZrO2 nanofibers. This work may inspire the rational design of Ni/ZrO2 nanofiber catalysts with rich oxygen vacancies for low-temperature CO2 methanation.

Boosting CO2 methanation activity by tuning Ni crystal plane and oxygen vacancy in Ni/CeO2 catalyst

It is challenging to boost CO2 methanation activity over Ni-based catalysts, and new findings that decipher the relationship between the essential laws of catalysts and their catalytic performance will be transformative. Herein, three kinds of Ni/CeO2 catalysts with different Ni crystal facets and oxygen vacancy are developed by varied preparation methods, which show significant differences in catalytic performance for CO2 methanation, and these catalysts are taken as a case study for the investigation of the crystal plane and oxygen vacancy effects in CO2 methanation as well. It is observed that the activity of Ni/CeO2-SG catalyst with abundant oxygen vacancies and principally exposed Ni (111) crystal facet is highly active for CO2 methanation reaction, which is 1–3 times than that of Ni/CeO2 catalysts with poor oxygen vacancy and/or Ni (111) crystal face. In addition, the former one cannot suffer from deactivation even in operation 130 h at 300 °C. Both structural investigations and catalytic evaluations indicate that the adsorption and activating ability of H2 and CO2 can be controlled by adjusting the Ni-exposed crystal face and oxygen vacancy concentration, respectively. It is also verified that the synergistic contribution of the Ni crystal facets and the oxygen vacancy play a crucial role in boosting the catalytic activity of the Ni/CeO2 catalysts by affecting the adsorption and activation of reactants. The Ni/CeO2 catalysts exposed Ni (111) crystal plane facilitate the catalytic activity by strengthing the H2 adsorption/dissociation capacity, while the abundantly available oxygen vacancies maximize the activity via acting as CO2 activation sites. Furthermore, the in situ DRIFT experiments reveal that the direct formate hydrogenation pathway is involved in the CO2 methanation process over the Ni/CeO2-SG catalyst.

Tailoring metal-support interactions via spatial confinement of Ni/CeO2 interfaces on h-BN for efficient CO2 methanation

Modulating metal-support interactions is critical for improving catalytic activity and product selectivity for CO2 hydrogenation. Such modulation can be achieved by modifying the metal nanoparticles as well as the supports. Here, we prepared a novel catalyst, in which Ni nanoparticles were dispersed on CeO2 and hexagonal boron nitride (h-BN) hybrid supports. The introduction of h-BN to Ni/CeO2-BN effectively improves the dispersion of Ni nanoparticles. More importantly, the abundant Ni-CeO2 interfacial sites with enriched oxygen vacancies are formed over h-BN edge sites. The dispersed Ni species are anchored on CeO2 via a unique interfacial structure, with electron-rich Ni (Niδ−) species. At the interfacial sites on Ni/CeO2-BN, the synergy between oxygen vacancies and Niδ−, which enhances CO2 activation and H2 dissociation, respectively, renders superior catalytic performance for CO2 methanation. In situ DRIFTS suggests formate as key rate-limiting intermediates on Ni-CeO2 sites, while the formation of B-H bonds further promotes hydrogen activation and subsequently the catalytic performance. The modulation of metal-support interactions by spatial confinement effect by BN offers a new paradigm for designing metal/oxide catalysts for chemical transformations that requires bifunctionality as CO2 hydrogenation.

Incorporation of atomic Fe-oxide triggers a quantum leap in the CO2 methanation performance of Ni-hydroxide

The heterogeneous catalytic conversion of carbon dioxide (CO2) to methane (CH4) via CO2 methanation offers a promising avenue for establishing the closed carbon loop. Nevertheless, the lack of effective catalysts limits its industrial applications. Considering this, we developed a novel heterogeneous catalyst comprising oxygen vacancies enriched atomic Fe-oxide clusters confined in the TiO2-supported Ni-hydroxide (denoted as NiFe-TiO2) via wet chemical reduction method. This material delivers an unprecedently high CH4 productivity of ∼24,358 mmol g-1h−1 in CO2 methanation at 300 °C, surpassing the Ni-TiO2 (12,481 mmol g-1h−1) by ∼ 95 %. On top of that, the high structural reliability of the Fe-oxide atomic clusters endows the NiFe-TiO2 catalyst with outstanding durability, where it achieves an optimum CH4 productivity of ∼ 36,399 mmol g-1h−1 after 116 cycles (155 h) with CH4 selectivity of 90.5 % and retains the pristine performance up to 220 cycles (330 h) in the stability test. With evidence from in-situ X-ray absorption and ambient pressure X-ray photoelectron spectroscopy studies, the performance descriptors and reaction pathways were unveiled, where the oxygen vacancies in the atomic Fe-oxide clusters and the adjacent Ni-hydroxide domains synergistically boost the CO2 activation and the H2 dissociation, respectively. Such a potential synergy enables the simultaneous operation of all intermediate steps for enhanced CO2 methanation kinetics on the NiFe-TiO2 surface. Most importantly, these findings not only unravel the merits of oxygen vacancies in transition metals for CO2 methanation but mark a step ahead for the rational design of heterogeneous catalysts in various catalytic applications.

Identifying the key structural features of Ni-based catalysts for the CO2 methanation reaction

Identifying the parameters influencing the selectivity of products is prominently significant for fabricating efficient catalysts. However, little progress has been made in describing the regulation rule of CH4 selectivity toward the CO2 methanation reaction, which is considered a vital process for CO2 emission and conversion. Herein, we disclosed the integral role of the electronegativity of M atoms in Ni-MOx supported catalysts to producing CH4 molecules, which the satisfactory catalytic performance stemmed from the regulated ability to capture CO2 molecules and CO intermediates. More importantly, alongside the extensively studied descriptor of particle size, we uncovered a strong correlation between the electronegativity of M atom and CH4 selectivity, in which the CO/CO2 adsorption capacity upon the Ni/NiOx/MOx interfaces exhibited a volcanic trend based on the electronegativity of M atoms in MOx supports. The screened Ni-Y2O3 composite catalysts demonstrated excellent CO2 methanation performance, suggesting the powerful practicability of the electronegativity of M atoms in MOx supports as a descriptor. These findings not only shed fundamental insight into the reaction pathway but also paved the way for the rational design of Ni-based catalysts based on the simple descriptor of electronegativity.

Mechanism study on dissociation of hydrogen and carbon dioxide towards carbon dioxide methanation

The study of carbon dioxide (CO2) methanation mechanisms widely argues on the nature and formation of intermediates. How reactants dissociate is still poorly understood. To gain deeper knowledge on its mechanism, we focused on studying reactants dissociation. After H2 dissociation and diffusion, the spillover H atom was observed, as well as the confirmation of H cluster formation on metal through aggregation by simulation and experiment. This H cluster facilitated C-O bond scission to easily form H ligand cobonded to metal, and thus resulted in high CO2 methanation performance. Four driving forces could dissociate CO2, three of them came from supports and metals, and another one was atomic H on metal as the strongest force. This simple and convenient method has wide adaptability and can be developed as an effective standard method for studying CO2 dissociation. The facile dissociation study of reactants would be very helpful in understanding the CO2 hydrogenation mechanism.

Space confinement effect of carbon nanotube-alumina strip support on the Cu-Co catalysts for CO2 methanation

The present work reported the space confinement effect of carbon nanotube-alumina strip (CAS) support on the Cu-Co bimetallic catalyst or the single Cu, Co catalysts for the CO2 methanation. CAS, made by extrusion of nanotubes and Al-based sol and high temperature calcination, was a macroscopic support with sufficient mesopores and hydrophobic property. Cu-Co/CAS catalysts exhibited high catalytic activity for methanation of CO2 (H2/CO2=3:1), where CO2 conversion was 49.62% and CH4 selectivity was 95.98% at temperature as low as 250 ℃ and 1.5 MPa, and showed advantage significantly over those with the supports of individual nanotube or pure Alumina support. The comparison suggested the hydrophobicity of carbon nanotubes can effectively remove water from the metal active sites, enhancing the equilibrium of reverse water gas shift and CO methanation reactions, as compared to alumina support. Additionally, CAS support had a spatial confinement effect that increased the contact time of CO2 or intermediates with the active sites, compared with individual nanotube support. XPS and Raman spectroscopy validated the presence of oxygen vacancies of CAS, promoting the CO2 methanation. H2-TPR results, in combination with DFT calculations, confirmed that the CAS supports enabled the Cu-Co active phase by changing their electronic structures, to possess a strong adsorption activation capacity for H2 at low temperatures with high performance for CO2 methanation.

Rapid construction of nickel phyllosilicate with ultrathin layers and high performance for CO2 methanation

The traditional techniques for the synthesis of nickel phyllosilicates usually time-consuming and energy-intensive, which often lead to the formation of layers with excessive thickness due to uncontrolled crystal growth. In order to overcome these challenges, this work introduces a microwave-assisted synthesis strategy to facilitate the synthesis of Ni-phyllosilicate-based catalysts within an exceptionally short duration of only five minutes, attaining a peak temperature of merely 102 °C. To enhance the specific surface area and to increase the exposure of active sites, an investigation was conducted involving three surfactants. The employment of hexadecyl trimethyl ammonium bromide (CTAB) has yielded remarkable results, with an ultrahigh specific surface area reaching 535 m2 g−1 and an ultrathin lamellar thickness of 1.43 nm. The catalyst exhibited an impressive CO2 conversion of 81.7 % at 400 °C, 60 L g−1 h−1, 0.1 MPa. It also demonstrated a substantial turnover frequency for CO2 (TOFCO2) of 5.4 ± 0.1 × 10−2 s−1, alongside a relatively low activation energy (Ea) of 80.74 kJ·mol−1. Moreover, the catalyst maintained its high stability over a period of 100 h and displayed high resistance to sintering. To further elucidate growth temperature gradient of the catalyst and concentration gradient of the materials involved, COMSOL Multiphysics (COMSOL) simulations were effectively utilized. In conclusion, this work breaks the limitation associated with traditional, laborious synthesis methods for Ni-phyllosilicates, which can produce materials with high surface area and thin-layer characteristics.

Ruthenium-Cobalt Solid-Solution Alloy Nanoparticles for Enhanced Photopromoted Thermocatalytic CO2 Hydrogenation to Methane.

Bimetallic alloy nanoparticles have garnered substantial attention for diverse catalytic applications owing to their abundant active sites and tunable electronic structures, whereas the synthesis of ultrafine alloy nanoparticles with atomic-level homogeneity for bulk-state immiscible couples remains a formidable challenge. Herein, we present the synthesis of RuxCo1-x solid-solution alloy nanoparticles (ca. 2 nm) across the entire composition range, for highly efficient, durable, and selective CO2 hydrogenation to CH4 under mild conditions. Notably, Ru0.88Co0.12/TiO2 and Ru0.74Co0.26/TiO2 catalysts, with 12 and 26 atom % of Ru being substituted by Co, exhibit enhanced catalytic activity compared with the monometallic Ru/TiO2 counterparts both in dark and under light irradiation. The comprehensive experimental investigations and density functional theory calculations unveil that the electronic state of Ru is subtly modulated owing to the intimate interaction between Ru and Co in the alloy nanoparticles, and this effect results in the decline in the CO2 conversion energy barrier, thus ultimately culminating in an elevated catalytic performance relative to monometallic Ru and Co catalysts. In the photopromoted thermocatalytic process, the photoinduced charge carriers and localized photothermal effect play a pivotal role in facilitating the chemical reaction process, which accounts for the further boosted CO2 methanation performance.

Molybdenum-doping promoted surface oxygen vacancy of CeO2 for enhanced low-temperature CO2 methanation over Ni-CeO2 catalysts

It is challenging to improve the low-temperature activity of Ni-based catalyst for the CO2 methanation reaction. In this study, a molybdenum-doped cerium oxide supported Ni catalyst (Ni/MoCe) was constructed, and it showed remarkable CO2 methanation performance at low temperatures (<300 °C). Structural analysis revealed that the incorporation of Mo into the CeO2 lattice could enrich the surface oxygen vacancies, reduce the particle size of Ni species and enhance the metal-support interaction. The Ni/MoCe demonstrated a faster HCOO* pathway for the conversion of CO2 to CH4 compared with Ni/CeO2. Besides, the rich surface oxygen vacancies in Ni/MoCe facilitated the adsorption form of bidentate carbonates and the enhanced Ni-CeO2 interaction reduced the approach resistance of active H species from Ni for subsequent hydrogenation process. This work proves that Mo doping is an effective vacancy engineering strategy to design high-performance heterogeneous catalysts for CO2 hydrogenation.

Probing CO2 methanation enhancement on dendritic mesoporous silica nanoparticle supported alkaline-earth ion doped LaNiO3-derived catalysts: The dominant role of Ni0 active sites over oxygen vacancies

To thoroughly explore the role of alkaline-earth ions in enhancing the CO2 methanation performance of LaNiO3/dendritic mesoporous silica nanoparticle (DMSN) catalysts, a series of La1-xAxNiO3/DMSN (x = 0, 0.1; A = Ca, Sr, Ba) catalysts was synthesized. XRD analysis revealed the predominant integration of Sr2+ species into the LaNiO3 crystal lattice, while the Ca2+ and Ba2+-doped samples formed additional crystalline phases of CaO and BaO2, respectively. H2-TPD results demonstrated that Sr2+ and Ba2+ cations significantly enhanced the dispersion of Ni0 active sites within the catalyst compared to LaNiO3/DMSN, contrasting with the effects of Ca2+. Further investigation through H2-TPR revealed a more complex reduction process in the Sr2+ and Ba2+-doped samples compared to the bare catalyst. Analysis of O2-TPD and CO2-TPD data showed a direct relationship between surface oxygen vacancies and moderate alkaline sites, with a more pronounced presence in the Ba2+ and Sr2+-doped samples. The overall activity below 450 °C followed the sequence of La0.9Sr0.1NiO3/DMSN > La0.9Ba0.1NiO3/DMSN > LaNiO3/DMSN > La0.9Ca0.1NiO3/DMSN. From the stability perspective, the La0.9Ba0.1NiO3/DMSN catalyst exhibited lower carbon/coke deposition than its Sr2+-promoted counterpart in TGA and Raman analyses. These findings highlighted that the dispersion of Ni0 species and oxygen vacancies emerged as the primary determinants of catalytic activity and stability, respectively. This indicated that while La0.9Sr0.1NiO3/DMSN achieved higher CO2 conversion and CH4 selectivity compared to La0.9Ba0.1NiO3/DMSN, it also experienced more carbon/coke deposits, leading to a shorter catalytic lifespan.

Enhanced CO2 methanation activity over Ni/CeO2 catalyst by adjusting metal-support interactions

CO2 methanation is an essential means of utilizing CO2, which is crucial to solving environmental problems and alleviating energy crisis. The design and development of high- performance low temperature CO2 methanation catalysts is the key to its further application. In this work, the metal-support interaction of Ni/CeO2 catalyst was regulated by changing the calcination temperature and Ni loadings to optimize the CO2 methanation performance. The results showed that 5NiCe-800 exhibited the best CO2 conversion of 83.1 % and 98.0 % CH4 selectivity at 350 °C, since it has a suitable Ni-CeO2 interaction, higher oxygen vacancy concentration, great reducibility and better basic site distribution. The reaction mechanism and the synergistic effect of CeO2 and Ni in CO2 methanation was revealed by in-situ FTIR, which is of great significance for the development of efficient CeO2 supported Ni-based for CO2 methanation.

Carbon Dioxide Methanation Enabled by Biochar-Nanocatalyst Composite Materials: A Mini-Review

Due to ever-increasing global warming, the scientific community is concerned with finding immediate solutions to reduce or utilize carbon dioxide (CO2) and convert it in useful compounds. In this context, the reductive process of CO2 methanation has been well-investigated and found to be attractive due to its simplicity. However, it requires the development of highly active catalysts. In this mini-review, the focus is on biochar-immobilized nanocatalysts for CO2 methanation. We summarize the recent literature on the topic, reporting strategies for designing biochar with immobilized nanocatalysts and their performance in CO2 methanation. We review the thermochemical transformation of biomass into biochar and its decoration with CO2 methanation catalysts. We also tackle direct methods of obtaining biochar nanocatalysts, in one pot, from nanocatalyst precursor-impregnated biomass. We review the effect of the initial biomass nature, as well as the conditions that permit tuning the performances of the composite catalysts. Finally, we discuss the CO2 methanation performance and how it could be improved, keeping in mind low operation costs and sustainability.

Optimizing low-temperature CO2 methanation through frustrated Lewis pairs on Ni/CeO2 catalysts

The promising realm of carbon dioxide (CO2) conversion offers a compelling avenue to advance environmental sustainability. This study introduces a novel approach by utilizing frustrated Lewis pairs (FLPs) for efficient low-temperature CO2 methanation. Through a tailored ammonium bicarbonate (AB) precipitation method, we engineered Ni/CeO2 catalysts abundant in FLPs. Various morphologies, including aggregated flakes, broom-like structures, and irregular granules, were achieved by modulating the AB-to-cerium molar ratio. The distinctive broom-like Ni/(0.06AB)CeO2 catalyst, comprised of nanorods with abundant FLPs, exhibited outstanding low-temperature CO2 methanation performance: 67.5 % CO2 conversion, 99.6 % CH4 selectivity, and 0.27 s−1 CO2 turnover frequency (TOFCO2) at 240 °C, with excellent stability in a 100-h test at 300 °C. Furthermore, leveraging in-situ DRIFTS and in-situ Raman techniques, and DFT study, we unraveled CO2 hydrogenation pathways and found a dual interplay of CO and formate pathways in the low-temperature methanation over Ni/(0.06AB)CeO2 catalyst.