Catalytic Conversion Of Carbon Dioxide Research Articles

ZIF-8 Porous Liquids with Different Sterically Hindered Solvents and Porous Guests for Catalytic Conversion of Carbon Dioxide.

Utilizing carbon dioxide (CO2) as a raw material is an effective way to reduce carbon emissions, and developing catalytic systems with high catalytic activity and stability is crucial for the efficient utilization of CO2. Porous liquids (PLs) with both permanent pores and fluidity have great potential in the fields of catalysis, gas sorption, and storage. Nevertheless, the catalytic performance of PLs is affected by many factors; therefore, further study is needed. Herein, we proposed a general strategy to construct a series of type III PLs with different chemical structures of sterically hindered solvents and different microstructures of porous guests. Benefiting from the unique microstructures, the as-prepared PLs exhibit great potential in catalyzing the reaction of CO2 with propylene oxide under suitable conditions. Moreover, their catalytic activity exceeds that of pure sterically hindered solvents without a porous guest loading. The influences of the nucleophilicity of the anion of the sterically hindered solvent and the microstructure of the porous guests on the catalytic activity and the catalytic stability of the PLs were analyzed. Meanwhile, the mechanism of the catalytic conversion of CO2 was proposed, which is of great significance for the design and development of the subsequent PL catalysts.

Every reaction Detail Matters: An in silico driven Step-by-Step Guide to understand the B2O3-Catalyzed CO2 to cyclic carbonates conversion

The catalytic conversion of carbon dioxide (CO2) to cyclic organic carbonates (COCs) via cycloaddition with epoxides offers a dual benefit of reducing CO2 emissions while producing valuable chemical products. In this detailed in silico study, we employ density functional theory (DFT) to meticulously investigate the mechanisms underlying the B2O3/n-NBu4Br-catalyzed cycloaddition of CO2 and epoxides, following a step-by-step approach according to the reaction details. We provide a comprehensive comparison of the non-catalyzed, n-NBu4Br alone, and B2O3/n-NBu4Br-catalyzed pathways, emphasizing two distinct active sites within the B2O3 framework: Site 1 (six-membered boroxol ring) and Site 2 (open chain configuration). Our computational analysis highlights that the Site 1-catalyzed reaction pathway is more favorable, featuring a lower overall energy barrier of 26.8 kcal/mol, compared to 32.5 kcal/mol for the Site 2-catalyzed pathway. Detailed intrinsic bond orbital (IBO), natural adaptive orbital (NAdO) and distortion-interaction analysis (DIA) reveal significant differences in bonding properties and energy interactions, elucidating why Site 1 exhibits superior catalytic activity over Site 2. These findings are corroborated by experimental observations, which indicate that ball milling B2O3 increases defect sites, thereby enhancing exposure of active sites Site 1 and improving catalytic performance. This study provides an in-depth understanding of how the intrinsic properties of boron active sites influence the catalytic efficiency of B2O3, offering valuable insights for the design and optimization of metal-free catalysts for CO2 conversion.

Direct Catalytic Conversion of Carbon Dioxide to Liquid Hydrocarbons over Cobalt Catalyst Supported on Lanthanum(III) Ion‐Doped Cerium(IV) Oxide

AbstractDirect CO2 conversion to liquid hydrocarbons (HCs) in a single process was achieved using cobalt (Co) catalysts supported on lanthanum ion (La3+)‐doped cerium oxide (CeO2) under a gas stream of H2/CO2/N2=3/1/1. The yield of liquid HCs was the highest for 30 mol% of La3+‐doped CeO2, which was because extrinsic oxygen vacancy formed by doping La3+ could act as an effective reaction site for reverse water gas shift reaction. However, the excess La3+ addition afforded surface covering lanthanum carbonates, resulting in depression of the catalytic performance. On the other hand, bare CeO2 lead to an increase in the selectivity of undesirable methane, which arose from reduction of CO2 to CO proceeding by intrinsic oxygen vacancy generated by only Ce3+, and weaker CO2 capture ability of intrinsic oxygen vacancy than extrinsic one, resulting in the proceeding of Sabatier reaction on Co catalyst. The rational design of reaction sites presented in this study will contribute to sustainability.

Adjacent Reaction Sites of Atomic Mn2O3 and Oxygen Vacancies Facilitate CO2 Activation for Enhanced CH4 Production on TiO2-Supported Nickel-Hydroxide Nanoparticles

The catalytic conversion of carbon dioxide (CO2) to methane (CH4) through the “Sabatier reaction”, also known as CO2 methanation, presents a promising avenue for establishing a closed carbon loop. However, the competitive reverse water gas shift (RWGS) reaction severely limits CH4 production at lower temperatures; therefore, developing highly efficient and selective catalysts for CO2 methanation is imperative. In this regard, we have developed a novel nanocatalyst comprising atomic scale Mn2O3 species decorated in the defect sites of TiO2-supported Ni-hydroxide nanoparticles with abundant oxygen vacancies (hereafter denoted as NiMn-1). The as-prepared NiMn-1 catalyst initiates the CO2 methanation at a temperature of 523 K and delivers an optimal CH4 production yield of 21,312 mmol g−1 h−1 with a CH4 selectivity as high as ~92% at 573 K, which is 45% higher as compared to its monometallic counterpart Ni-TiO2 (14,741 mmol g−1 h−1). Physical investigations combined with gas chromatography analysis corroborate that the exceptional activity and selectivity of the NiMn-1 catalyst stem from the synergistic cooperation between adjacent active sites on its surface. Specifically, the high density of oxygen vacancies in Ni-hydroxide and adjacent Mn2O3 domains facilitate CO2 activation, while the metallic Ni domains trigger H2 splitting. We envision that the obtained results pave the way for the design of highly active and selective catalysts for CO2 methanation.

Converting CO2 Into Natural Gas Within the Autoclave: A Kinetic Study on Hydrogenation of Carbonates in Aqueous Solution.

Catalytic conversion of carbon dioxide (CO2) into value-added chemicals is of pivotal importance, well the cost of capturing CO2 from dilute atmosphere is super challenge. One promising strategy is combining the adsorption and transformation at one step, such as applying alkali solution that could selectively reduce carbonate (CO3 2-) as consequences of CO2 adsorption. Due to complexity of this system, the mechanistic details on controlling the hydrogenation have not been investigated in depth. Herein, Ru/TiO2 catalyst was applied as a probe to elucidate the mechanism of CO3 2- activation, in which with thermodynamic and kinetic investigations, a compact Langmuir-Hinshelwood reaction model was established which suggests that the overall rate of CO3 2- hydrogenation was controlled by a specific C-O bond rupture elementary step within HCOO- and the Ru surface was mainly covered by CO3 2- or HCOO- at independent conditions. This assumption was further supported by negligible kinetic isotope effects (kH/kD≈1), similarity on reaction barriers of CO3 2- and HCOO- hydrogenation (ΔH≠ hydr,Na2CO3 and ΔH≠ hydr,HCOONa) and a non-variation of entropy (ΔS≠ hydr≈0). More interestingly, the alkalinity of the solution is certainly like a two sides in a sword and could facilitate the adsorption of CO2 while hold back catalysis during CO3 2- 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.

Fast and sustainable CO2 conversion to propylene carbonate using fluoroalcohol-based bifunctional ionic liquids: Insights from experiments and theoretical simulations

We report on the metal-free and rapid catalytic conversion of carbon dioxide into cyclic carbonates under solventless conditions utilizing novel bifunctional fluoroalcohol-based ionic liquids (FBILs) as catalsyts. In the presence of 2.5 mol% 4-(1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) phenyl trimethylammonium iodide (FBIL-1), under 0.1 MPa and 90 °C, excellent yield of propylene carbonate(>95%) was achieved in 1 h, which significantly shortens the reaction time, compared with the conventional catalysts. DFT calculations reveal that FBILs with fluorine-substituted hydroxyl groups exhibit stronger hydrogen bonding with epoxides compared to ILs lacking fluorine substitutions. The hydrogen bond length for ILF/PO is 1.658 Å, shorter than that for IL/PO (1.813 Å). This characteristic contributes to reducing the activation energy for the ring-opening reaction of epoxides. In the ILF/PO system, the reaction barrier is 88.72 kJ·mol−1, lower than the 101.46 kJ·mol−1 barrier for IL/PO, allowing the former to more rapidly facilitate the fixation of carbon dioxide into cyclic carbonates. Besides high catalytic efficiency, these FBILs have the characteristics of a facile synthesis route and easy post-reaction recovery.

CO2 utilization for methanol production: a review on the safety concerns and countermeasures.

The catalytic conversion of carbon dioxide is one of the important ways to achieve the goal of carbon neutralization, which can be further divided into electrocatalysis, thermal catalysis, and photocatalysis. Although photocatalysis and electrocatalysis have the advantages of mild reaction conditions and low energy consumption, the thermal catalytic conversion of CO2 has larger processing capacity, better reduction effect, and more complete industrial foundation, which is a promising technology in the future. During the development of new technology from laboratory to industrial application, ensuring the safety of production process is essential. In this work, safety optimization design of equipment, safety performance of catalysts, accident types, and their countermeasures in the industrial applications of CO2 to methanol are reviewed and discussed in depth. Based on that, future research demands for industrial process safety of CO2 to methanol were proposed, which provide guidance for the large-scale application of CO2 thermal catalytic conversion technology.

A single site catalyst supported in mesoporous UiO-66 for catalytic conversion of carbon dioxide to formate

The half-sandwich (tetrazolylpyridyl)iridium(iii) complex shows improved catalytic activity towards hydrogenation of carbon dioxide to formate when supported in a mesoporous m-UiO-66 MOF.

Boron–pyridine nitrogen cooperative catalytic conversion of carbon dioxide and epoxides to cyclic carbonates

A type of N-heterocyclic carbene (NHC)-diboron adduct in combination with tetrabutylammonium iodide (TBAI) was used as a catalyst for the synthesis of cyclic carbonates from CO2 with epoxides.

Catalytic conversion of carbon dioxide (CO2) using coal-based nano-carbon materials.

Carbon dioxide (CO2) is a prominent greenhouse gas and a widely available carbon resource. The chemical conversion of CO2 into high-value chemicals and fuels is a significant approach for mitigating carbon emissions and attaining carbon neutrality. However, enhancing CO2 adsorption and conversion rates remains a primary challenge in CO2 recycling. The development of high-performance catalysts is pivotal for the catalytic conversion of CO2. In this context, coal-based carbon materials, characterized by their extensive specific surface area and adaptable chemical composition, can offer more reactive active sites and have robust CO2 adsorption capabilities. They can function as either standalone catalysts or as components of composite catalysts, making them promising materials for CO2 reduction. The use of affordable and abundant coal as a precursor for carbon materials represents a crucial avenue for achieving clean and efficient coal utilization. This paper reviews the progress of research on coal-based carbon materials and examines their advantages and challenges as catalysts for CO2 reduction.

Review on the recent advances in catalytic conversion of carbon dioxide for synthesis of cyclic propylene carbonate

Generation of carbondioxide in the atmosphere has increased considerably over the past decades due to the increase of industrialization. This led to the increase in the global temperature which affects the eco-system. It is essential to reduce the emission of carbondioxide in the atmosphere for which different researchers are working on re-utilization of the generated carbondioxide either by converting to different products or by trapping them as carbonates. Propylene carbonate is one of the chemicals that are synthesized by using CO2 as a reactant. Propylene carbonate has many applications as an end product and acts as intermediate for synthesis of other useful chemicals. Fixation of CO2 into propylene oxide for the synthesis of propylene carbonate is still a challenging task due to the high thermodynamic stability of CO2. Propylene carbonate can be synthesized by reacting CO2 with different high energy materials using different catalyst. This review is focused on providing an idea about different types of catalyst reported for synthesis of cyclic propylene carbonate using propylene oxide and propylene glycol as the starting materials. This review also provides the mechanism for conversion of CO2 to propylene carbonate by different catalyst and at various working conditions.

Design of bifunctional 1D nanostructures for the catalytic conversion of carbon dioxide into cyclic carbonates

One dimensional silica-based nanotubes represent an innovative and promising morphology in the context of heterogeneous catalysis. Here these nanostructures were prepared for the first time as bifunctional materials, with hafnium or tin atoms inserted as single sites in the silica structure and imidazolium moieties anchored at the surface. The low dimensional solids thus present both acid sites owing to the presence of metal cations in tetrahedral coordination (co-catalyst) and nucleophilic species coming from the counterion of the imidazolium moieties (catalyst). The design of the catalysts consisted of two main steps. The Hf- or Sn-doped silica solids were initially prepared using a straightforward sol-gel method including a pH adjustment step allowing a quantitative insertion of the metal cations in the silica framework. These materials were post-functionalized with imidazolium moieties. The solids were extensively characterized thus confirming the presence of well-defined and open tubular structure, high specific surface area, successful insertion of Hf and Sn in the silica framework, and a correct functionalization with imidazolium salts. The different catalysts were tested in the valorization of CO2 with styrene oxide to give the corresponding cyclic carbonate. The bifunctional solids were stable and recyclable. The versatility of the best catalyst, represented by the Hf-based material, was confirmed using different epoxides. Finally, by tuning the reaction conditions or changing the imidazolium salt, a further boost of the catalytic performances was achieved.

Uncovering the role of yttrium in a cerium-based binary oxide in the catalytic conversion of carbon dioxide and methanol to dimethyl carbonate

Cerium(IV) oxide (CeO2)-based materials are effective catalysts for the synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO2) and methanol (CH3OH). Herein, 5% Y–CeO2 was synthesized by the co-precipitation method. It forms a solid solution structure, which leads to the highest concentration of oxygen vacancies. The Y–VO–Ce active site created by Y3+ doping enhances the adsorption and activation of CO2 based on moderately passivating CH3OH adsorption. Consequently, 5% Y–CeO2 exhibited the highest CH3OH conversion rate of 0.8% and a DMC yield of 15 mmol⋅(g cat)−1, which is 1.4 times of pure CeO2 (reacting in a stainless-steel autoclave at 140 °C with a stirring speed of 1000 r⋅min−1 and an initial pressure of 3.0 MPa for 2 h). An adsorption test and in situ diffuse reflectance infrared Fourier transform spectroscopy showed that 5% Y–CeO2 could effectively inhibit the formation of triple-bonded methoxy species, and promote the formation of bidentate carbonate and bridged methoxy intermediates, which is conducive to the improvement of reaction activity.

Conversion of CO2 Hydrogenation to Methanol over K/Ni Promoted MoS2/MgO Catalyst

The chemical transformation of carbon dioxide (CO2) not only reduces the amount of carbon dioxide emitted into the Earth’s atmosphere by humans, but also produces carbon compounds that can be used as precursors for chemical and fuel production. Herein, a selective catalytic conversion of carbon dioxide to methanol is achieved by a bifunctional molybdenum disulfide catalyst (MoS2) with magnesium oxide and nickel and potassium promoters. Molybdenum disulfide prepared by the supercritical ethanol method has a large specific surface area and presents good catalytic performance with high methanol selectivity when loaded with potassium (K) and nickel (Ni) promoters. In addition, the catalysts were evaluated and it was founded that the addition of the K-promoter improved methanol selectivity. This research provides a new strategy for improved product selectivity and space–time yield (STY) of methanol in CO2 hydrogenation.

Integration of lanthanide-imidazole containing polymer with metal-organic frameworks for efficient cycloaddition of CO2 with epoxides

The heterogeneous catalytic conversion of carbon dioxide (CO2) conversion is an appealing yet highly challenging task. Introducing target-specific active sites into solid catalysts provides an alternative but promising way for boosting the chemical fixation of CO2. Here, we designed a lanthanide (III) complex with 1-vinyl imidazole (Vim) and immobilized it with DUT-5 by a combination of coordination and in situ polymerization. The resultant La-Vim/DUT-5 with high porosity and multiple active sites achieves a catalytic yield of 94% for CO2 cycloaddition of epichlorohydrin, much superior to that of each component. More importantly, such catalytic activities can be well maintained using simulated flue gas as C1 source under both dry and humid conditions. This work opens up a novel and general avenue to tailor the chemical functionality of MOFs for capturing and converting CO2 under actual conditions.

Mechanistic study on the formation of the alkyl acrylates from CO2, ethylene and alkyl iodides over nickel-based catalyst.

The catalytic conversion of carbon dioxide (CO2) and olefins into acrylates has been a long standing target, because society attempts to synthesize commodity chemicals in a more economical and sustainable fashion. In this work, two alkylation reaction pathways were investigated to explore the role of methylene linkage (-CH2-) on the formation of alkyl acrylate from coupling of CO2 and ethylene, catalyzed by a nickel catalyst in the presence of different alkyl iodides. The energy barrier of Ni-O bond cleavage decreases with increasing methylene linkage of alkyl iodides, which may be due to NPA charge transfer of alkyl iodides. Meanwhile, the O1 (ester sp3 O atom) attack route leading to the formation of alkyl acrylate competes with the O2 (carboxylic sp2 O atom) attack route in terms of energy barriers. Further studies on the fluoro-substituted alkyl acrylates show that neither CF3I nor CF3CH2I is effective in releasing trifluoroalkyl acrylates from the nickellacycle, which explains why only negligible amounts of the desired product were detected in the experiment. In addition, we investigated the non-productive pathways leading to byproducts, such as propionic acid, propionates and ion pair complexes, etc. By comparing the results obtained with CH3I, the use of C2H5I as an electrophilic reagent may stabilize the non-productive intermediates. The methylene linkage has little effect on the main productive pathway. However, it has a significant influence on the side reactions, which is detrimental to the formation of alkyl acrylate in competing with the main productive pathway.

Two novel metal-organic frameworks functionalised with pentamethylcyclopentadienyl iridium(III) chloride for catalytic conversion of carbon dioxide to formate.

Hydrogenation of CO2 to formate is a vital reaction, because formate is an excellent hydrogen carrier, which yields blue hydrogen. Blue hydrogen is comparatively cheaper and attractive as the world envisions the hydrogen economy. In this work, two isostructural lanthanide-based MOFs (JMS-6 and JMS-7 [Ln(bpdc)3/2(dmf)2(H2O)2]n) were prepared and used as support materials for molecular catalysts. The bipyridyl MOF backbone were functionalised using pentamethylcyclopentadienyl iridium(III) chloride to give Ir(III)@JMS-6a and Ir(III)@JMS-7a. XPS of the functionalised MOFs show downfield shifts in the N 1s binding energy indicating successful grafting of the complex to the MOF. Hydrogenation experiments in the presence of an organic base showed that the functionalised MOFs were active towards converting CO2 to formate. Ir(III)@JMS-6a and Ir(III)@JMS-7a exhibited the highest turnover numbers of 813 and 621 respectively. ICP-OES indicated insignificant leaching during catalysis. TEM images and XPS data of the recovered catalyst ruled out the presence of Ir(0), confirming that the activity observed was attributed to the molecular Iridium(III) centres.

Effective tri-metallic TiO2 supported catalyst for hydrocarbon production from carbon dioxide

The current socio-economic issues with concerns on environmental quality and global warming are attributed to high concentrations of atmospheric carbon dioxide due to extensive usage of fossil fuels. Thus, over the last two decades, comprehensive work has been reported on carbon capture and storage and catalytic conversion of carbon dioxide to hydrocarbons. Among these, the reactions with hydrocarbons to form value-added products have been in focus. In this work, an attempt was made to identify the feasibility of the reaction: carbon dioxide and steam to form hydrocarbons of fuel value. After reviewing the literature on the development of various catalysts and their mechanism, a multi-metallic catalyst supported by TiO2 Nano-needles was explored. The reaction mechanism is expected to proceed with activated CO2 complex and hydroxyl groups over the metal oxide catalyst. Current reported work on CO2 and Hydrogen proceeds with activated CO2 and protons over the catalyst. The characterization techniques mainly XPS, XRD, TGA, FESEM-EDAX, FTIR, and NMR were used to analyze the catalyst activity and to confirm the products formed. The reaction is found to yield methanol and oxygen only. However, the conversion is found to be 0.4% - 3.8% in the temperature range 350°C to 550°C. The reaction of CO2 with hydroxyl groups from water vapor can be effective as an alternative to the reaction with protons from hydrogen.

Research status, challenges and future prospects of renewable synthetic fuel catalysts for CO2 photocatalytic reduction conversion.

In recent years, with global climate change, the utilization of carbon dioxide as a resource has become an important goal of human society to achieve carbon peaking and carbon neutrality. Among them, the catalytic conversion of carbon dioxide to generate renewable fuels has received great attention. As one of these methods, photocatalysis has its unique properties and mechanism, which can only rely on sunlight without inputting other energy. It is an emerging discipline with great development prospects. The core of photocatalysis lies in the development of photocatalysts with high activity, high selectivity, low cost, and high durability. This review first introduces the background and mechanism of photocatalysis, then introduces various types of photocatalysts based on different substrates, and analyzes the methods and mechanisms to improve the activity and selectivity of photocatalysts. Finally, combining the plasmon effect with photocatalysis, the review analyzes the promoting effect of the plasmon effect on the photocatalytic carbon dioxide synthesis of renewable fuels, which provides a new idea for it.