Catalytic Hydrogenation Of Carbon Dioxide Research Articles

A new perspective on hydrogenation of CO2 into methanol over heterogeneous catalysts

The utilization of carbon dioxide is critical to realize the objective of "carbon peak and neutrality". Among various carbon dioxide exploitation approaches, catalytic hydrogenation of carbon dioxide is a significant method to selectively convert the CO2 into methanol and other valuable chemicals. Among these products, methanol is a crucial chemical feedstock that can be utilized as a platform molecule for the synthesis of chemicals and fuels as well as a fuel for internal combustion engines and fuel cells, causing particular interest. Nowadays, Catalytic hydrogenation of carbon dioxide into methanol has shifted its focus on the creation of low-cost, environmentally friendly, and efficient catalysts. Inspired of this, we have concluded the mechanism of catalytic hydrogenation of carbon dioxide, and reviewed the research progress of multiple heterogeneous catalysts with high catalytic application prospect, especially the supported catalysts.

Catalysis for CO2 Hydrogenation—What We Have Learned/Should Learn from the Hydrogenation of Syngas to Methanol

This short review provides an in-depth analysis of the achievements and further developments of the catalytic hydrogenation of carbon dioxide (CO2) to methanol from those that are worth learning about based on the transformation of syngas into methanol. We begin by exploring the environmental and energy-related implications of utilizing CO2 as a feedstock for methanol production by emphasizing its potential to mitigate greenhouse gas emissions and facilitate renewable energy integration. Then, different catalytic formulations focusing on precious metals, copper-based catalysts, and metal oxides are summarized, and insights into their advantages and limitations in the aspects of catalytic activity, selectivity, and stability are discussed. Precious metal catalysts, such as platinum and iridium, exhibit high activity but are cost-prohibitive, while copper-based catalysts present a promising and cost-effective alternative. Metal oxides are considered for their unique properties in CO2 activation. Mechanistic insights into reaction pathways are explored, with a particular emphasis on copper-based catalysts. Moreover, the complex steps involved in CO2 hydrogenation to methanol are discussed to shed light on the key intermediates and active sites responsible for catalysis, which is crucial for catalyst design and optimization. Finally, we stress the importance of ongoing research and development efforts to enhance catalyst efficiency, mechanistic comprehension, and process optimization. This review serves as a valuable resource for researchers, engineers, and policymakers working toward a more sustainable and carbon-neutral energy future. By harnessing CO2 as a carbon feedstock for methanol synthesis, we have the potential to address environmental concerns and advance the utilization of renewable energy sources, further contributing to the transition to a cleaner and more sustainable energy landscape.

Palladium complexes bearing aromatic Bis-aldimine N^N^N pincer ligands; activity as catalysts in the hydrogenation of carbon dioxide

CO2 hydrogenation can serve as an avenue for the use of CO2 as a C1 carbon source whiles simultaneously serving as a means of hydrogen ‘storage’. Herein we report on the synthesis of new pyridine-2,6-bis(methanylylidene)bis(CH = NR)- palladium chloridecomplexes were(R = Ph, p-Br-C6H4, 2,6-dimethyl-C6H3). All the complexes were fully characterized by 1H NMR, 13C NMR, FT-IR, elemental analysis, mass spectrometry and single-crystal X-ray diffraction studies where appropriate. This work sought to investigate and discuss the role of substituents in respect of electronic effects, choice of pincer ligand system backbone, and steric effects of the substituents and the role it has on the hydrogenation of CO2. These pincer complexes were investigated as catalysts in the hydrogenation of CO2 and were found to be efficient in the direct catalytic carbon dioxide hydrogenation to formate with the highest TON at 520.

Oxygenated Hydrocarbons from Catalytic Hydrogenation of Carbon Dioxide

Once fundamental difficulties such as active sites and selectivity are fully resolved, metal-free catalysts such as 3D graphene or carbon nanotubes (CNT) are very cost-effective substitutes for the expensive noble metals used for catalyzing CO2. A viable method for converting environmental wastes into useful energy storage or industrial wealth, and one which also addresses the environmental and energy problems brought on by emissions of CO2, is CO2 hydrogenation into hydrocarbon compounds. The creation of catalytic compounds and knowledge about the reaction mechanisms have received considerable attention. Numerous variables affect the catalytic process, including metal–support interaction, metal particle sizes, and promoters. CO2 hydrogenation into different hydrocarbon compounds like lower olefins, alcoholic composites, long-chain hydrocarbon composites, and fuels, in addition to other categories, have been explained in previous studies. With respect to catalyst design, photocatalytic activity, and the reaction mechanism, recent advances in obtaining oxygenated hydrocarbons from CO2 processing have been made both through experiments and through density functional theory (DFT) simulations. This review highlights the progress made in the use of three-dimensional (3D) nanomaterials and their compounds and methods for their synthesis in the process of hydrogenation of CO2. Recent advances in catalytic performance and the conversion mechanism for CO2 hydrogenation into hydrocarbons that have been made using both experiments and DFT simulations are also discussed. The development of 3D nanomaterials and metal catalysts supported on 3D nanomaterials is important for CO2 conversion because of their stability and the ability to continuously support the catalytic processes, in addition to the ability to reduce CO2 directly and hydrogenate it into oxygenated hydrocarbons.

A review of catalytic hydrogenation of carbon dioxide: From waste to hydrocarbons.

With the rapid development of industrial society and humankind’s prosperity, the growing demands of global energy, mainly based on the combustion of hydrocarbon fossil fuels, has become one of the most severe challenges all over the world. It is estimated that fossil fuel consumption continues to grow with an annual increase rate of 1.3%, which has seriously affected the natural environment through the emission of greenhouse gases, most notably carbon dioxide (CO2). Given these recognized environmental concerns, it is imperative to develop clean technologies for converting captured CO2 to high-valued chemicals, one of which is value-added hydrocarbons. In this article, environmental effects due to CO2 emission are discussed and various routes for CO2 hydrogenation to hydrocarbons including light olefins, fuel oils (gasoline and jet fuel), and aromatics are comprehensively elaborated. Our emphasis is on catalyst development. In addition, we present an outlook that summarizes the research challenges and opportunities associated with the hydrogenation of CO2 to hydrocarbon products.

Synthesis of hydrophobic Pd-poly(ionic liquid)s with excellent CO2 affinity to efficiently catalyze CO2 hydrogenation to formic acid

The catalytic hydrogenation of carbon dioxide (CO2) into formic acid is among the most important reactions to alleviate global warming and realize the carbon cycle. How to achieve rapid activation of CO2 remains a challenge. In this work, we designed two novel hydrophobic poly(ionic liquid)s (PILs) with a good affinity for CO2. Since the abundant N atoms in the PILs can anchor palladium (Pd) nanoparticles, the designed catalyst can rapidly activate CO2 and H2 simultaneously, thus efficiently catalyzing the hydrogenation of CO2 to formic acid under mild conditions. Due to the synergy from the bis(trifluoromethanesulfonyl)amide anion ([Tf2N−]) with strong hydrophobicity and CO2 affinity and trimethylamine (NEt3) as a low dissociation energy alkaline additive, the resultant Pd/PIL-bip-Tf2N exhibited the best catalytic performance on the hydrogenation of CO2 to formic acid. The TOF value reached 1,190 h−1 in the aqueous solution of NEt3 at 100 °C, 1 h, and a total pressure of 4 MPa. The activation energy and dissociation energy during the catalytic process were calculated by DFT, indicating that the synergistic effect of NEt3 is better than that of other alkaline additives. In addition, the catalytic activity of the catalyst remained stable after several cycling experiments. Based on the obtained results, we proposed a possible reaction pathway. Therefore, PILs have great potential as catalyst carrier material for CO2 hydrogenation.

Formic Acid Dehydrogenation Using Noble-Metal Nanoheterogeneous Catalysts: Towards Sustainable Hydrogen-Based Energy

The need for sustainable energy sources is now more urgent than ever, and hydrogen is significant in the future of energy. However, several obstacles remain in the way of widespread hydrogen use, most of which are related to transport and storage. Dilute formic acid (FA) is recognized asa a safe fuel for low-temperature fuel cells. This review examines FA as a potential hydrogen storage molecule that can be dehydrogenated to yield highly pure hydrogen (H2) and carbon dioxide (CO2) with very little carbon monoxide (CO) gas produced via nanoheterogeneous catalysts. It also present the use of Au and Pd as nanoheterogeneous catalysts for formic acid liquid phase decomposition, focusing on the influence of noble metals in monometallic, bimetallic, and trimetallic compositions on the catalytic dehydrogenation of FA under mild temperatures (20–50 °C). The review shows that FA production from CO2 without a base by direct catalytic carbon dioxide hydrogenation is far more sustainable than existing techniques. Finally, using FA as an energy carrier to selectively release hydrogen for fuel cell power generation appears to be a potential technique.

Metal-organic frameworks as catalyst precursors in Catalytic Hydrogenation of Carbon Dioxide: Review

Catalytic hydrogenation of carbon dioxide to value-added chemicals is an attractive process to address both energy and environmental issues. Several approaches have been used to convert the greenhouse gas to useful products. This conversion has been done mainly through homogeneous catalytic systems of platinum group metal complexes. In recent years there has been a growing concern to design heterogeneous catalysts that are able to convert carbon dioxide to C1 products. The large surface area that metal-organic frameworks coupled with porosity make them better candidates for catalytic conversion of carbon dioxide to the desired products. Results from these studies indicate that metal-organic frameworks (MOFs) may answer both environmental and energy issues associated with the production of the greenhouse gas. This contribution will focus on the recent development in the design and application of MOFs in catalytic hydrogenation of carbon dioxide. Special emphases on tandem capture of carbon dioxide and hydrogen followed by subsequent hydrogenation of carbon dioxide in the presence of frustrated Lewis pairs functionalised MOF will be discussed.

Copper–zinc oxide interface as a methanol-selective structure in Cu–ZnO catalyst during catalytic hydrogenation of carbon dioxide to methanol

The proper contact of zinc oxide and copper phases is essential achieving high activity/selectivity toward methanol in the Cu–ZnO system.

Каталитическое гидрирование диоксида углерода в пласте при освоении месторождений высоковязкой нефти

Каталитическое гидрирование диоксида углерода в пласте при освоении месторождений высоковязкой нефти

Single Ni supported on Ti3C2O2 for uninterrupted CO2 catalytic hydrogenation to formic acid: A DFT study

Catalytic hydrogenation of carbon dioxide to formic acid (CO2 + H2 → HCOOH) is considered as promising strategy for CO2 fixation and recycling utilization. Supported single metal atom exhibits exceptional activity resulted from its unique local chemical environment. In this work, single Ni atom immobilized on O-vacancy defected Ti3C2O2 ([email protected]3C2O2) is investigated for CO2 hydrogenation to HCOOH by first principles calculations. Results show that Ni atom can be steadily immobilized on Ti3C2O2, while CO2 catalytic hydrogenation to HCOOH is favorable with a small energy barrier of 0.54 eV via ER mechanism through HCOO intermediate. Importantly, the hydrogenation process could be occurred uninterruptedly. The as-generated HCOOH will be rapidly released during the subsequent CO2 hydrogenation process owning to the lowest desorption barrier of 0.12 eV, which will not restrict the overall catalytic hydrogenation efficiency. Moreover, the large barrier of side reactions, such as C-C coupling, dehydroxylation and further hydrogenation suggests the high selectivity of CO2 hydrogenation to HCOOH. These findings improve our understanding of CO2 hydrogenation mechanism over supported single atom catalysts, and provide a potential platform for CO2 fixation.

Unraveling the Effect of Aromatic Groups in Mn(I)NNN Pincer Complexes on Carbon Dioxide Activation Using Density Functional Study.

Carbon dioxide utilization is necessary to reduce carbon footprint and also to synthesize value-added chemicals. The transition metal pincer complexes are attractive catalysts for the hydrogenation of carbon dioxide to formic acid. There is a need to understand the factors affecting the catalytic performance of these pincer complexes through a structure–activity relationship study using computational methods. It is a well-established fact that aromatic functionalities offer stability and selectivity to transition metal catalysts. However, their impact on the performance of the catalysts is lesser known in the case of metal pincer complexes. Hence, it is necessary to investigate the catalytic performance of Mn(I)NNN pincer complexes with variably activated aromatic functionalities. In this context, 15 catalysts are designed by placing different types of aromatic rings at the pincer carbons and two terminal nitrogen of Mn(I)NNN pincer complexes. A benzene moiety, placed at C2–C3 carbons of Mn(I)NNN pincer complex with identical aromatic groups at the terminal nitrogen, is found to be most efficient toward CO2 hydrogenation than the rest of the catalysts. On the other hand, when N,N-dimethyl aniline is placed at C2–C3 carbons of Mn(I)NNN pincer complexes, then the catalytic performance is significantly decreased. Thus, the present study unravels the impact of aromatic groups in Mn(I)NNN pincer complexes toward the catalytic hydrogenation of carbon dioxide.

CO2 Methanation Over Ni-Sepiolite Catalysts

In this study, it was aimed to develop new catalysts to increase the conversion of environmentally harmful carbon dioxide gas to methane which is a valuable fuel. By using a natural clay mineral sepiolite (SEP) as support material; 6-8% (weight-weight) Ni-containing catalysts were prepared by impregnation. Catalysts were characterized by XRD and FT-IR analysis. Reaction conditions of catalytic hydrogenation of carbon dioxide for methane production were determined as: H2/CO2 = 4 molar ratio, the temperature range of 300-600°C at atmospheric pressure. The output gas mixture was analyzed using the µGC. The activities of the catalysts were determined in terms of carbon dioxide conversion and methane selectivity. 6%Ni/SEP and 8%Ni/SEP provided 65.76% and 68.42% carbon dioxide conversion at 400°C, respectively. In addition, both catalysts exhibited high methane selectivity at 300 and 400°C (>98%).

Mechanistic insight into catalytic carbon dioxide hydrogenation to formic acid over Pt-doped boron nitride nanosheets

In this work, we investigated the mechanism of CO2 hydrogenation over the Pt-doped boron nitride nanosheets (Pt-BNNSs) by using the density functional theory (DFT). It is found that a Pt adatom can be effectively stabilized in boron vacancy site (Pt-BV). Our investigation shows that the reaction mechanisms of CO2 hydrogenation over Pt-BV can be found in three possible reaction pathways: (i) co-adsorption, (ii) H2 dissociation, and (iii) co-adsorption together with H2 dissociation pathways. The co-adsorption together with H2 dissociation provides the most favorable pathway among of these three proposed mechanisms. The important finding of our study is that the presence of CO2 in step of hydrogen dissociation plays an important role in producing the FA on the Pt-BV catalyst. Moreover, we found that the hydrogenation of CO2 via carboxylate (COOH) has the rate-determining step of 0.63 eV in the step of hydrogen dissociation. In addition, the microkinetic modelling suggests that the COOH route is found to be more energetically and kinetically feasible rather than that it is formate route (HCOO) with the reaction temperature at 350 K and pressure of 5 bar. Our calculation results provide an important information for developing Pt-BV catalysts and might shed light on experimental design the novel Pt-BV catalyst for the CO2 hydrogenation and the conversion of greenhouse gases into value-added products.

Catalytic Hydrogenation of Carbon Dioxide over Magnetic Nanoparticles: Modification in Fixed-Bed Reactor

A specific finger-projected fixed-bed reactor (FPFBR) was designed to efficiently utilize magnetic nanoparticles (MnFe2O4/Bi-MnFe2O4) for a model reaction (hydrogenation of a greenhouse gas, CO2, to valuable products: VPs). Coprecipitation method, with desired modification was used for the preparation of magnetic nanoparticles (MNPs) with controlled shape and size. Eighteen fingers in a single chamber were designed in the fixed-bed reactor’s skeleton; each finger worked as an independent reaction core. Controlled flow of hydrogen and CO2 was continuously provided to preheated reaction cores (catalyst beds) from saturator. One of the major products methanol {(%: Conv, 22/Sel 61)} among VPs was identified and quantified by GC. The efficiency of self-designed reactor was 74% for the direct catalytic hydrogenation of CO2 to valuable organic products.

Theoretical studies on the catalytic hydrogenation of carbon dioxide by 3d transition metals single-atom catalyst supported on covalent triazine frameworks

• The co-adsorption configuration of hydrogen and CO 2 on the unsaturated coordination single-atom catalysts (SACs) gives it a unique selectivity for CO 2 hydrogenation to formic acid. • A ‘volcano’ plot was established between the 3d-orbital electron number and barrier energy, in which Ni appeared at the summit. • Part of the overlap population density of states (OPDOS) of Ni and H atom is located in unoccupied orbitals, resulting in a weak Ni H bond. • Inert intermediates lead to low activity of Sc, Ti, V. The catalytic conversion of carbon dioxide (CO 2 ) into value-added products is a significant emission reduction method. Among numerous catalysts, single-atom catalysts (SACs) show great potential in CO 2 hydrogenation. However, it is difficult to predict the CO 2 hydrogenation products because the SACs consisting of the same metal and different supports commonly show various catalytic selectivity. Here we study the catalytic mechanism of the CO 2 hydrogenation process catalyzed by the SAC with 3d transition metals. The metal atoms are anchored on the covalent triazine frameworks (CTFs). We find the correlation between adsorption configuration and the selectivity of the CO 2 hydrogenation. The coadsorption configuration of the H atom and CO 2 molecule is favorable to forming the C H bond in formate. A volcano relation based on activation barrier and 3d-orbital electron numbers was obtained. We found that the catalyst with Ni metal has the lowest activation barrier. We also explained the low catalytic activity of Sc, Ti, and V metals due to the inert intermediates occupying the active sites. This work may be helpful to design highly selective and highly active catalysts in CO 2 hydrogenation.

Multi-criteria sustainability assessment of potential methanol production processes

Due to rapidly increasing world population and growing energy demands, the development of cleaner technologies to exploit renewable energy systems has become of primary importance in the collective efforts to reduce greenhouse gases emissions. The chemical conversion of renewable power into synthetic liquid fuels, such as methanol, allows an easier storage and transportation and avoids any fluctuating issues. Alternative process routes for methanol production other than from raw materials derived from fossil fuels have, during the past decade, grown in interest, where valorising the carbon capture and utilization concept and promoting synergies with the oil & gas industry are potentially achieved. The aim of this study is, in this regard, to investigate the sustainability aspects of alternative processes for synthetic methanol synthesis by applying a systematic methodology based on multi-criteria performance indicators (such as technological, economic, environmental and inherent safety). A total of eleven alternative methanol production schemes, based on synthetic methane or carbon dioxide transformation, are considered, analyzed and comparatively evaluated. The present results demonstrate that the process schemes using catalytic hydrogenation of carbon dioxide offers the best performance when considering a methanol capacity of 500 kg/h. A sensitivity analysis based on the Monte Carlo approach is also performed to verify the robustness of the results.

Light-Assisted Catalytic Hydrogenation of Carbon Dioxide at a Low Pressure by a Dinuclear Iridium Polyhydride Complex

A dinuclear iridium pentahydride complex bearing a diphosphine ligand with a fluorene backbone was synthesized and characterized for use as a photocatalyst for CO2 hydrogenation. The complex can be...

Temperature and Solvent Effects on H2 Splitting and Hydricity: Ramifications on CO2 Hydrogenation by a Rhenium Pincer Catalyst.

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex (tBuPOCOP)Re(CO)2 (tBuPOCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO2 hydrogenation to formate with faster rates at lower temperatures. Because the catalyst follows the prototypical "outer sphere" hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H2 splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [(tBuPOCOP)Re(CO)2H]- present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K are developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO2 hydrogenation to formate with high activity (up to 364 h-1 at 1 atm or 3330 h-1 at 20 atm of 1:1 H2:CO2). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H2 splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Ramifications on catalyst structure-function relationships are discussed, including comparisons between "outer sphere" mechanisms and "metal-ligand cooperation" mechanisms.

二氧化碳催化加氢制备甲醇的研究进展

二氧化碳催化加氢制备甲醇的研究进展