Catalytic Hydrogenation Of CO2 Research Articles

In-Situ Characterization Techniques for Mechanism Studies of CO2 Hydrogenation.

The paramount concerns of global warming, fossil fuel depletion, and energy crises have prompted the need of hydrocarbons productions via CO2 conversion. In order to achieve global carbon neutrality, much attention needs to be diverted towards CO2 management. Catalytic hydrogenation of CO2 is an exciting opportunity to curb the increasing CO2 and produce value-added products. However, the comprehensive understanding of CO2 hydrogenation is still a matter of discussion due to its complex reaction mechanism and involvement of various species. This review comprehensively discusses three processes: reverse water gas shift (RWGS) reaction, modified Fischer Tropsch synthesis (MFTS), and methanol-mediated route (MeOH) for CO2 hydrogenation to hydrocarbons. Along with analysing the reaction pathways, it is also very important to understand the real-time evolvement of catalytic process and reaction intermediates by employing in-situ characterization techniques under actual reaction conditions. Subsequently, in second part of this review, we provided a systematic analysis of advancements in in-situ techniques aimed to monitor the evolution of catalysts during CO2 reduction process. The section also highlights the key components of in-situ cells, their working principles, and applications in identifying reaction mechanisms for CO2 hydrogenation. Finally, by reviewing respective achievements in the field, we identify key gaps and present some future directions for CO2 hydrogenation and in-situ studies.

Recent Advances Hydrogenation of Carbon Dioxide to Light Olefins over Iron-Based Catalysts via the Fischer-Tropsch Synthesis.

The massive burning of fossil fuels has been important for economic and social development, but the increase in the CO2 concentration has seriously affected environmental sustainability. In industrial and agricultural production, light olefins are one of the most important feedstocks. Therefore, the preparation of light olefins by CO2 hydrogenation has been intensively studied, especially for the development of efficient catalysts and for the application in industrial production. Fe-based catalysts are widely used in Fischer-Tropsch synthesis due to their high stability and activity, and they also exhibit excellent catalytic CO2 hydrogenation to light olefins. This paper systematically summarizes and analyzes the reaction mechanism of Fe-based catalysts, alkali and transition metal modifications, interactions between active sites and carriers, the synthesis process, and the effect of the byproduct H2O on catalyst performance. Meanwhile, the challenges to the development of CO2 hydrogenation for light olefin synthesis are presented, and future development opportunities are envisioned.

Experimental investigation on the origin of carbonaceous materials in the fault zone of the Wenchuan earthquake

Carbonaceous materials in seismic fault zones may considerably influence seismic fault slip; however, the formation mechanism of carbonaceous materials remains unclear. In this study, we proposed a novel hypothesis for the formation of carbonaceous materials in fault gouge. Thus, we conducted a CO2 hydrogenation experiment in a high-temperature reactor at a co-seismic temperature, with fault gouge formed during the Wenchuan earthquake as the catalyst. Our experimental results demonstrate that carbonaceous materials in fault zones are formed on the fault gouge during the chemical reaction process, suggesting that the carbonaceous materials are possibly generated from the catalytic hydrogenation of CO2, followed by thermal cracking of its products. The results of this study provide a theoretical basis for understanding fault behavior and earthquake physics.

Engineering Frustrated Lewis Pair Active Sites in Porous Organic Scaffolds for Catalytic CO2 Hydrogenation.

Frustrated Lewis pairs (FLPs), featuring reactive combinations of Lewis acids and Lewis bases, have been utilized for myriad metal-free homogeneous catalytic processes. Immobilizing the active Lewis sites to a solid support, especially to porous scaffolds, has shown great potential to ameliorate FLP catalysis by circumventing some of its inherent drawbacks, such as poor product separation and catalyst recyclability. Nevertheless, designing immobilized Lewis pair active sites (LPASs) is challenging due to the requirement of placing the donor and acceptor centers in appropriate geometric arrangements while maintaining the necessary chemical environment to perform catalysis, and clear design rules have not yet been established. In this work, we formulate simple guidelines to build highly active LPASs for direct catalytic hydrogenation of CO2 through a large-scale screening of a diverse library of 25,000 immobilized FLPs. The library is built by introducing boron-containing acidic sites in the vicinity of the existing basic nitrogen sites of the organic linkers of metal-organic frameworks collected in a "top-down" fashion from the CoRE MOF 2019 database. The chemical and geometrical appropriateness of these LPASs for CO2 hydrogenation is determined by evaluating a series of simple descriptors representing the intrinsic strength (acidity and basicity) of the components and their spatial arrangement in the active sites. Analysis of the leading candidates enables the formulation of pragmatic and experimentally relevant design principles which constitute the starting point for further exploration of FLP-based catalysts for the reduction of CO2.

Experimental PSA reactor for methanol-enhanced production VIA CO2 hydrogenation

Methanol synthesis via catalytic CO2 hydrogenation has emerged as one of the main ways to valorize CO2. The main problem is that the methanol synthesis reaction is thermodynamically controlled, and there is a parallel endothermic reaction, reverse water gas shift (RWGS), so low methanol production ratios are achieved.In this scenario, process intensification, particularly multifunctional reactors where reaction and separation occur simultaneously, is of great interest. Sorption-enhanced reaction processes (SERP) technologies are widely used in equilibrium-controlled processes to increase reagent conversion through selective product removal.Various authors have proposed SERP processes for CO2 hydrogenation to methanol, but most of them are simulations studies and it is difficult to find experimental data. The aim of the work is the experimental study of the CO2 conversion and selectivity to methanol of a SERP process based on a four-step PSA reactor. The process has been carried out with a commercial Cu/ZnO/Al2O3 catalyst and commercial 3A zeolite as adsorbent.Conversions beyond the equilibrium have been achieved in the SERP process, even complete conversion of CO2 at 50 bar, 250 °C, and 300 °C. In the cyclic process, high CO2 conversions far from equilibrium are achieved in all the range of temperatures, 200–300 °C. The best results of methanol yield are achieved at 250 °C and 50 bar, followed closely by 200 °C. It is worth mentioning that methane is detected in the transitory state at 300 °C and 50 bar. Also, the purge step has been studied, concluding that it is necessary for adsorbent regeneration, improving CO2 conversion in the cyclic steady state.

An Air and Moisture Stable Boat Shaped Hydroxo‐Bridged Ruthenium(II) Binuclear Complex for the Catalytic Hydrogenation of CO2

AbstractA new hydroxo‐bridged ruthenium (II) complex [{Ru(η6‐p‐cymene)(iPr2P−O)}2(μ‐OH)]Cl (2) has fortuitously been isolated from the reaction between the known ruthenium(II) complex [RuCl2(η6‐p‐cymene)(iPr2P‐OH)] (1) in either CDCl3 or CHCl3 solutions in the presence of excess DBU (1,8‐diazabicyclo(5.4.0)undec‐7‐ene) at room temperature. Complex 2 is only formed under specific conditions as an orange‐colored air and moisture stable binuclear complex. It is formed via the deprotonation of the P−OH unit in [RuCl2(η6‐p‐cymene)(iPr2P‐OH)]. Complex 2 has been fully characterized by spectroscopic and analytical methods. Its structure was determined by single crystal X‐ray diffraction which reveals a boat‐shaped motif containing a bridging hydroxide unit which undergoes hydrogen bonding with a chloride counterion. Complex 2 was utilized as a catalyst for the hydrogenation of CO2 to formic acid salt using molecular hydrogen. The catalytic reactions were performed at 100 °C in THF in the presence of DBU as a base to isolate [DBU+H][OC(O)H] salt as the final product. Using catalyst loadings down to 0.01 mol%, it was possible to hydrogenate gaseous CO2 with TONs up to 9900.

Utilizing in situ construction of N-doped hierarchical porous carbon to achieve electronic control of highly dispersed Pd nanoparticles for efficient catalytic hydrogenation of CO2 to formic acid

Hydrogenation of CO2 to produce formic acid/formate is a significant pathway for future energy storage and utilization. The development of heterogeneous catalysts with high activity and stability for this process is still a challenge. In this work, the in-situ N-doped hierarchical porous carbon derived from distiller's grains was used as a support for Pd-based catalysts (Pd/NC) to convert CO2 into valuable chemicals while making high-value use of waste biomass. The optimum catalyst, Pd/NC-800, shown exceptional catalytic performance, achieving a turnover frequency (TOF) of 2060 h−1 at 100℃, 4 MPa in the catalytic CO2 hydrogenation to formate reaction. Comprehensive experimental results and density functional theory calculations indicate that the electronic effect between the pyridine N in the support and the Pd nanoparticles (NPs) can make the Pd surface reach the state of electron enrichment and enhance the metal-support interaction. Moreover, the synthesized material has hierarchical pore structure, which provides abundant Pd anchor location sites and improves mass transfer efficiency. The results not only provide a feasible strategy for the preparation of efficient CO2 hydrogenation catalysts, but also break a new and effective avenue for the resource utilization of distiller's grains.

Electrochemical and catalytic conversion of CO2 into formic acid on Cu-InO2 nano alloy decorated on reduced graphene oxide (Cu-InO2@rGO)

The catalytic and electrochemical hydrogenation of CO2 offers the option of a carbon-neutral cycle for sustainable energy and synthesis of value-added chemicals. The synthesized noble metal-free Cu-InO2@rGO nanocomposite has been characterized by various techniques such as scanning electron microscopy (SEM) confirming the spherical shape of Cu-InO2 nanoalloy embedded on rGO, the average size calculated by high resolution-transmission electron microscopy (HR-TEM) shows Cu-InO2 (∼ 4 nm) alloy is on rGO surface (∼100 nm). The XRD pattern confirms the Face centered cubic (FCC) crystal structure of Cu-InO2@rGO, and Furrier transform- Infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses of Cu-In-O exist in the nanomaterials. The linear sweep voltammetry (LSV) demonstrates an ultra-low potential of −0.9 V vs. SCE. The bulk electrolysis on Cu-InO2@rGO electrocatalyst demonstrated at a potential of −1.1 V vs. SCE to reach HCOOH with a Faradic yield of 76.10%. Electrochemical CO2 reduction on Cu-InO2@rGO is responsible for the variation of adsorption of CO2 intermediates due to controlled selectivity and inhibiting the formation of H2 and CO. In catalytic hydrogenation used as the same catalyst was found, an excellent yield towards HCOOH is 5.5 mmol. Current studies have highlighted the enhancement in activity along with selectivity for product formation could be due to having a capable active interface from electrocatalysts for low cost and proficient production of fuels.

Catalytic CO2 hydrogenation to hydrocarbon fuels in a potassium ion-conducting reactor

The electrochemically assisted CO2 hydrogenation directly to hydrocarbon fuels was studied, apparently for the first time, over a cheap, widespread and non-precious Fe catalyst in a potassium ion conducting (K-β-Al2O3) reactor, under atmospheric pressure, at relatively low temperatures and using representative concentrated CO2 and H2 gas mixtures and an easily scalable tubular catalyst-electrode configuration. The Fe electrocatalytic film was deposited by dip-coating on a commercial K-β-Al2O3 candle and characterized, both as prepared and after activation and testing, by TPR, TGA, XPS, XRD and SEM-EDX. The optimum operating conditions for both Fe activation (300 ºC, 75% H2, 24 hours) and electropromoted CO2 hydrogenation (300 ºC, 1.5 V, H2/CO2=3) were identified. Long-term tests on electrochemically promoted CO2 hydrogenation to hydrocarbons were performed under selected operating conditions to assess electrocatalyst stability. Both the selectivity to the target product (C5+ hydrocarbons) and the stability of the catalyst can be tuned in situ by modifying the potassium surface coverage via electrochemical pumping of potassium ions through the applied polarization. Finally, as an attempt to improve the catalyst-electrode behaviour, powdered catalysts, based on iron nanoparticles dispersed on KVO3 (a K+ and e- co-conductor) with different Fe loadings (17 and 9 wt%) were prepared and comparatively studied for CO2 hydrogenation to hydrocarbons. The catalyst with higher Fe loading was selected as the most promising, in terms of activity, selectivity and stability, for further catalyst-electrode optimisation by deposition, via dip-coating, of a Fe-KVO3 film on the K-β-Al2O3 candle.

Tuning Catalytic Activity of CO2 Hydrogenation to C1 Product via Metal Support Interaction Over Metal/Metal Oxide Supported Catalysts.

The metal supported catalysts are emerging catalysts that are receiving a lot of attention in CO2 hydrogenation to C1 products. Numerous experiments have demonstrated that the support (usually an oxide) is crucial for the catalytic performance. The support metal oxides are used to aid in the homogeneous dispersion of metal particles, prevent agglomeration, and control morphology owing to the metal support interaction (MSI). MSI can efficiently optimize the structural and electronic properties of catalysts and tune the conversion of key reaction intermediates involved in CO2 hydrogenation, thereby enhancing the catalytic performance. There is an increasing attention is being paid to the promotion effects in the catalytic CO2 hydrogenation process. However, a systematically understanding about the effects of MSI on CO2 hydrogenation to C1 products catalytic performance has not been fully studied yet due to the diversities in catalysts and reaction conditions. Hence, the characteristics and modes of MSI in CO2 hydrogenation to C1 products are elaborated in detail in our work.

Selective CO2 hydrogenation to liquid fuels over Na-decorated FeMgMnOx catalyst with high carbon efficiency

Direct synthesis of liquid fuels (C5+ hydrocarbons) through CO2 hydrogenation has attracted considerable interest. However, it is plagued by high selectivity of C1 by-products (CO and CH4) and low reaction activity. Herein, we report that Na-decorated Fe catalysts promoted by combination of Mg and Mn and investigate their synergistic effect in the catalytic CO2 hydrogenation reaction. The optimized amounts of promoters result in a significant improvement in the catalytic performance of NaFe2O3. The CO2 conversion increases by 1.6-fold, while the total selectivity of CO and CH4 is suppressed to below 21.3 %. The characteristic results reveal the enhanced surface alkalinity and electron transfer favor CO2 adsorption and tuned the local H/C ratio in the vicinity of iron species, thus remarkably promoting the carbon chain growth and limiting the production of C1 products. This study offers a promising approach to modulating the metal electronic environment and improving carbon efficiency for CO2 hydrogenation reactions.

Unlocking the Potential of Cu/Ti3C2Tx MXene Catalyst in Plasma Catalytic CO2 Hydrogenation

Plasma catalytic CO2 hydrogenation has emerged as a promising approach for converting CO2 into valuable chemicals such as CO, offering a potential solution to mitigate greenhouse gas emissions. In this study, we investigate the synergistic effect between plasma and a Cu/Ti3C2Tx MXene catalyst for CO2 hydrogenation via the reverse water gas shift (RWGS) reaction in a dielectric barrier discharge (DBD) reactor. Our findings reveal a significant enhancement in CO2 conversion (33.1%) and CO yield (31.9%) when using the Cu/Ti3C2Tx catalyst compared to plasma alone or with a Ti3C2Tx foam. Plasma treatment creates unsaturated Ti sites on the Ti3C2Tx surface, dramatically improving CO2 adsorption and activation, while Cu nanoparticles significantly enhances the activation and dissociation of H2 molecules on the catalyst surface. These surface adsorbed hydrogen species readily hydrogenate adsorbed CO2 molecules through the Langmuir-Hinshelwood mechanism. Furthermore, these surface hydrogen species can also participate in the conversion of gas-phase CO2 molecules through the Eley-Rideal pathway. This work sheds light on the synergistic plasma catalytic mechanism and provide insights for optimizing CO2 hydrogenation processes using MXene catalysts.

Facile Synthesis of Iron Carbide via Pyrolysis of Ferrous Fumarate for Catalytic CO2 Hydrogenation to Lower Olefins.

Hydrogenation of CO2 to olefin catalyzed by iron-based catalysts is a sustainable and important way to achieve carbon neutrality. In this study, iron-based catalysts were facilely prepared by direct pyrolysis of ferric fumarate (FF), which are applied to CO2 hydrogenation to olefin reaction to explore the effects of pyrolysis temperature and atmosphere on catalytic performance of the catalysts. Among them, NaFe-Air-400 catalyst exhibits the highest catalytic activity with 33.7 %, and light olefin selectivity reaches as high as 47.1 %. The catalytic performance of pyrolytic catalysts is better than that the impregnated NaFe catalyst on activated carbon (NaFe/AC). A series of XRD, Raman and SEM characterization results show a suitable pyrolysis temperature would promote the balance between amorphous carbon and graphene, which can affect the formation of FexCy phase, leading the distinctive activity and olefin selectivity. Hence, the presented one-step pyrolysis methodology would provide a facile and quick synthesis of highly-active iron-based catalyst design for CO2 conversion.

Catalytic hydrogenation of CO2 to DME on surface Cu via highly efficient electron redistribution at the Cu0/Cu+ interface

The activity of copper-based bifunctional catalysts for CO2 hydrogenation to dimethyl ether (DME) is generally constrained by the loss of Cu0 sites during the reaction. Previous studies have focused on introducing additional elements to improve the stability of active sites. In this study, an electron redistribution of the Cu/Cu2O interface was constructed. Surface Cu0 provides active sites for H2 adsorption and dissociation, and the Cu0/Cu+ interface sites are more beneficial for the activation and hydrogenation of CO2. The Ointer–H moieties that form at interface sites reduce the reaction energy barrier of CH3OH synthesis, and the decomposition of H2COOH* to CH2O* species is the rate-limiting step. In addition, the Cu0/Cu+ interface restricts the migration of copper species and protects the weak acid sites of HZSM-5 during the reaction. The present work provides an atomic-level description of H2 dissociation and CO2 activation by Cu0/Cu+ surface and interface sites.

Plasma catalytic CO2 hydrogenation to methanol: The interaction between MnOx and ZrO2

AbstractPlasma catalytic CO2 hydrogenation to methanol over MnOx/ZrO2 catalyst was investigated in this work. A boosted methanol yield of 4.6 mg/h was obtained over MnOx/ZrO2 catalyst, while it was only 0.0 and 0.7 mg/h for ZrO2 and MnOx catalyst, respectively. The interaction between MnOx and ZrO2 was responsible for the enhanced methanol yield. It resulted in sufficient oxygen vacancy. The in situ DRIFT spectra was conducted to reveal the plasma catalytic CO2 hydrogenation to methanol reaction mechanism and the key intermediates of HCOO and CH3O species were determined. The sufficient oxygen vacancy promoted the formation of the key intermediates, especially the CH3O species.

Mechanistic insight into the C1 product selectivity for the catalytic hydrogenation of CO2 over metal-doped graphene

The conversion of CO2 into fuels and valuable chemicals presents a viable path toward carbon neutrality. The aim of this study is to investigate the potential of metal-doped graphene catalysts in the reduction of CO2 to C1 products. 20 typical M-graphene (M = metal) catalysts were established based on DFT calculations. Six candidate catalysts, i.e., V-, Cr-, Mn-, Ni-, Mo-, and Ta-graphene catalysts, were selected by combining the hydrogen dissociation ability and the energy band gap of the catalysts. Subsequently, the adsorption characteristics and hydrogenation reactions of CO2 over the six candidates were explored. CO2 tends to adsorb at the M site through vertical adsorption and carbon–oxygen co-adsorption. V- and Cr-graphene catalysts promote the production of intermediate COOH, whereas Mn-, Ni-, Mo-, and Ta-doped surfaces are more favorable for HCOO formation. Concerning the hydrogenation to CO and HCOOH, V-, Cr-, Ni- and Mo-graphene catalysts preferentially yield CO from COOH, whereas Ta-doped graphene favors the formation of HCOOH. In total, the competitive hydrogenation of CO2 reveals the selectivity of the C1 products. Cr- and Ni-graphene favor the production of HCOOH and CH3OH, whereas V-, Mn-, Mo-, and Ta-graphene primarily yield CH3OH.Graphical

Designing Nickel-based catalysts for the hydrogenation of CO2 under Ambient conditions: A computational study

Recent developments, industrialization, and modernization lead to production of more and more pollutants (such as CO2: ∼ 417.06 ppm) and such rapid growth of CO2 level results in global warming and the greenhouse effect. So, it is essential to conduct research on converting CO2 into fuels using carbon-neutral energy. Recent research on molecular catalysts has improved the rates of converting CO2 to formate. However, these catalysts require extremely high temperatures and pressures and are made of expensive metals like iridium, ruthenium, and rhodium. Herein, DFT-based computational studies have been performed on the catalytic hydrogenation of CO2 by different Ni(II) complexes in ambient conditions. Using state-of-the-art calculations, we demonstrate how the geometry and spin states of Ni(II) complexes containing different types of ligands affect their catalytic role in CO2 hydrogenation. It has been reported that hydride transfer is the most crucial step for such kind of hydrogenation reaction. We start with previously synthesised Ni-bis(diphosphine) complexes of type NiP4 and by extrapolating the concept, we propose a novel kind of Ni-PNP complex with a significantly lower hydride transfer barrier. We also calculate the hydricities of the nickel hydride complexes in order to correlate these thermodynamic parameters with the kinetic barrier of hydride transfer.

Ni-Based Catalysts for CO2 Methanation: Exploring the Support Role in Structure-Activity Relationships.

The catalytic hydrogenation of CO2 to methane is one of the highly researched areas for the production of chemical fuels. The activity of catalyst is largely affected by support type and metal-support interaction deriving from the special method during catalyst preparation. Hence, we employed a simple solvothermal technique to synthesize Ni-based catalysts with different supports and studied the support role (CeO2, Al2O3, ZrO2, and La2O3) on structure-activity relationships in CO2 methanation. It is found that catalyst morphology can be altered by only changing the support precursors during synthesis, and therefore their catalytic behaviours were significantly affected. The Ni/Al2O3 with a core-shell morphology prepared herein exhibited a higher activity than the catalyst prepared with a common wet impregnation method. To have a comprehensive understanding for structure-activity relationships, advanced characterization (e. g., synchrotron radiation-based XAS and photoionization mass spectrometry) and in-situ diffuse reflectance infrared Fourier transform spectroscopy experiments were conducted. This research opens an avenue to further delve into the role of support on morphologies that can greatly enhance catalytic activity during CO2 methanation.

Tailored design of novel Co0-Coδ+ dual phase nanoparticles for selective CO2 hydrogenation to ethanol

Catalytic hydrogenation of CO2 to ethanol is a promising solution to address the greenhouse gas (GHG) emissions, but many current catalysts face efficiency and cost challenges. Cobalt based catalysts are frequently examined due to their abundance, cost-efficiency, and effectiveness in the reaction, where managing the Co0 to Coδ+ ratio is essential. In this study, we adjusted support nature (Al2O3, MgO-MgAl2O4, and MgO) and reduction conditions to optimize this balance of Co0 to Coδ+ sites on the catalyst surface, enhancing ethanol production. The selectivity of ethanol reached 17.9% in a continuous flow fixed bed micro-reactor over 20 mol% Co@MgO-MgAl2O4 (CoMgAl) catalyst at 270 °C and 3.0 MPa, when reduced at 400 °C for 8 h. Characterisation results coupled with activity analysis confirmed that mild reduction condition (400 °C, 10% H2 balance N2, 8 h) with intermediate metal support interaction favoured the generation of partially reduced Co sites (Coδ+ and Co0 sites in single atom) over MgO-MgAl2O4 surface, which promoted ethanol synthesis by coupling of dissociative (CHx*)/non-dissociative (CHxO*) intermediates, as confirmed by density functional theory analysis. Additionally, the CoMgAl, affordably prepared through the coprecipitation method, offers a potential alternative for CO2 hydrogenation to yield valuable chemicals.

Kinetic and DRIFTS studies of the CO2 catalytic hydrogenation on Ru/SiO2: A comprehensive and strategic investigation of CO2 methanation mechanisms by kinetic modeling and data regression

The kinetics of the CO2 hydrogenation/methanation is investigated on a Ru/SiO2 catalyst. Diffuse reflectance infrared Fourier transform spectroscopy experiments attest the presence of linearly adsorbed and bridge-bonded carbonyls on the metallic sites, as well as bicarbonate and formate species. Kinetic assessments at different temperatures and partial pressures show a direct relationship between methane turnover frequency and H2 pressure, suggesting that H* is involved in the rate-determining step. Contrariwise, increases in CO2 pressure inhibited methane formation. Applying Langmuir-Hinshelwood kinetics and non-linear regression, strategic kinetic models for CH4 formation rate were conceived and tested. The best model indicates that methanation starts off with CO2 dissociation into CO*reactive, proceeding along a H*-assisted pathway. The model also points out that competing oxygenated species (O*, HO*), intrinsically generated by CO2 activation, are hydrogenated faster on key sites, hindering the hydrogenation of carbon intermediates, which explained the inhibitory effect observed when CO2 pressure was increased.