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Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Environmental Catalysis".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 45635

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Special Issue Editor

Prof. Dr. Francis Verpoort

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Guest Editor

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430000, China
Interests: organometallics; metal–organic frameworks; porous organic polymers, and their applications in electro-, photo-, and thermo-catalysis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

With modern industry development, carbon dioxide (CO₂) has attracted increasing attention for its unignorable influence on the greenhouse effect. In synthetic chemistry, CO₂is considered an ideal C1 source for its merits, such as nontoxicity, economy, renewability, and abundance. Because CO₂is a stable molecule, transforming it into a different molecule is usually energy-intensive, costly, and requires excellent catalysts. Based on this, the transformation of CO₂into organics using homogeneous catalysts has become an up-and-coming area in modern green and sustainable chemistry. Numerous strategies have been developed to utilize CO₂for the synthesis of valuable chemicals effectively.

Moreover, heterogeneous catalysts are also intensively investigated for utilization of carbon dioxide, especially metal–organic frameworks and their derivatives. The catalytic use of MOF-based materials is cutting-edge in the field of scientific and technological developments. Recently, MOFs have been investigated as promising catalysts for synthesizing industrially important cyclic carbonates under solvent-free ambient conditions. A wide variety of terminal and internal substrates are converted efficiently with high selectivity.

Furthermore, novel electrocatalysts that convert CO₂into formic acid, methanol, ethanol, etc., with very high energy efficiency and high selectivity are highly sought after. The electrocatalytic reduction of CO₂is among the most attractive opportunities to address this issue by mitigating CO₂emission while converting it into valuable chemicals and fuels. A central challenge for using such a technique is developing effective electrocatalysts with excellent activity, selectivity, durability, and economic consideration towards the desired products. In addition, various electrocatalysts created to date have shown their unique opportunities in CO₂reduction and could potentially meet the abovementioned demands.

The goal of this Special Issue is to provide the frontiers of academic research in catalysis for carbon dioxide conversion. This Special Issue deals with all aspects of catalysis, from homogeneous to heterogeneous catalysis, catalyst synthesis, and characterization to their various applications in carbon dioxide utilization. Both original research and comprehensive review papers and perspectives contributing to the field are welcome.

The primary area of study can, however, span a broad research area, which focusses on catalysis in combination with carbon dioxide:

Homogeneous catalysis for chemicals;
Electrocatalysis for chemicals;
Photocatalysis;
Heterogeneous catalysis;
MOFs, COFs, and nanomaterials;
Further areas for development (perspectives).

Prof. Dr. Francis Verpoort
Guest Editor

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Keywords

carbon dioxide utilization
homogeneous catalysis
heterogeneous catalysis
electrocatalysis
green chemistry
sustainable chemistry
energy
environment

Published Papers (11 papers)

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Research

Jump to: Review

10 pages, 1410 KiB

Open AccessArticle

Trans Influence of Boryl Ligands in CO₂ Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO₂ Reduction

by Tian Liu, Zhangyong Liu, Lipeng Tang, Jun Li and Zhuhong Yang

Catalysts 2021, 11(11), 1356; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111356 - 12 Nov 2021

Cited by 4 | Viewed by 1799

Abstract

In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H₂ for the hydrogenation of CO₂. The theoretical calculation results show that only the B ligands exhibit a stronger trans influence than the hydride ligand and are along increasing order of trans influence as follows: –H < –BBr₂ < –BCl₂ ≈ –B(OCH)₂ < –Bcat < –B(OCH₂)₂ ≈ –B(OH)₂ < –Bpin < –B(NHCH₂)₂ < –B(OCH₃)₂ < –B(CH₃)₂ < –BH₂. The computed activation free energy for the direct hydride addition to CO₂ and the NBO analysis of the property of the Ru–H bond indicate that the activity of the hydride can be enhanced by the strong trans influence of the B ligands through the change in the Ru–H bond property. The function of the strong trans influence of B ligands is to decrease the d orbital component of Ru in the Ru–H bond. The design of a more active catalyst than the Ru(PNP)(CO)H₂ complex is possible. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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14 pages, 3203 KiB

Open AccessArticle

Hierarchical Mesoporous SSZ-13 Chabazite Zeolites for Carbon Dioxide Capture

by Lucy Hillen and Volkan Degirmenci

Catalysts 2021, 11(11), 1355; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111355 - 12 Nov 2021

Cited by 4 | Viewed by 2085

Abstract

Artificial carbon dioxide capture is an alternative method to remove the carbon dioxide already accumulated in the atmosphere as well as to stop its release at its large-scale emission points at the source, such as at power plants. However, new adsorbents are needed to make the approach feasible. For this purpose, in this study, hierarchical mesoporous-microporous chabazite-type zeolites were synthesised by applying a dual-templating method. The microporous zeolite structure-directing agent N,N,N-trimethyl-1-adamantanammonium hydroxide was combined with an organosilane mesopore-generating template, 3-(trimethoxysilyl)propyl octadecyl dimethyl ammonium chloride. Materials were characterised for their structural and textural properties and tested for their carbon dioxide capture capacity both in their original sodium form and in their proton-exchanged form by means of breakthrough curve analysis and sorption isotherms. The influence of template ratios on their structure, carbon dioxide capture, and capacity have been identified. All mesoporous materials showed fast adsorption-desorption kinetics due to a reduction in the steric limitations via the introduction of a meso range network of pores. The hierarchical zeolites are recyclable with a negligible loss in crystallinity and carbon dioxide capture capacity, which makes them potential materials for larger-scale application. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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13 pages, 2490 KiB

Open AccessArticle

Electrochemical Incorporation of Carbon Dioxide into Fluorotoluene Derivatives under Mild Conditions

by Silvia Mena, Jesus Bernad and Gonzalo Guirado

Catalysts 2021, 11(8), 880; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11080880 - 22 Jul 2021

Cited by 3 | Viewed by 2707

Abstract

One of the main challenges to combat climate change is to eliminate or reuse Carbon dioxide (CO₂), the largest contributor to the greenhouse gases that cause global warming. It is also important to synthesize compounds through greener technologies in order to obtain more environmentally friendly solutions. This study describes the electrocarboxylation process of α,α,α-trifluorotoluene using different working electrodes (glassy carbon, silver and copper) and electrolytes (polar aprotic solvent and ionic liquid). Carboxylated compounds were obtained in the same way in both electrolytic medias with more than 80% conversion rates, high yields, good selectivity, and moderate efficiencies using silver and copper as cathodes in organic electrolytes and ionic liquids. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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14 pages, 5636 KiB

Open AccessFeature PaperArticle

Changes in CO₂ Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study

by Aleksandar Živković, Michiel Somers, Eloi Camprubi, Helen E. King, Mariette Wolthers and Nora H. de Leeuw

Catalysts 2021, 11(4), 486; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11040486 - 10 Apr 2021

Cited by 10 | Viewed by 2802

Abstract

Metal sulphides constitute cheap, naturally abundant, and environmentally friendly materials for energy storage applications and chemistry. In particular, iron (II) monosulphide (FeS, mackinawite) is a material of relevance in theories of the origin of life and for heterogenous catalytic applications in the conversion of carbon dioxide (CO₂) towards small organic molecules. In natural mackinawite, Fe is often substituted by other metals, however, little is known about how such substitutions alter the chemical activity of the material. Herein, the effect of Ni doping on the structural, electronic, and catalytic properties of FeS surfaces is explored via dispersion-corrected density functional theory simulations. Substitutional Ni dopants, introduced on the Fe site, are readily incorporated into the pristine matrix of FeS, in good agreement with experimental measurements. The CO₂ molecule was found to undergo deactivation and partial desorption from the doped surfaces, mainly at the Ni site when compared to undoped FeS surfaces. This behaviour is attributed to the energetically lowered d-band centre position of the doped surface, as a consequence of the increased number of paired electrons originating from the Ni dopant. The reaction and activation energies of CO₂ dissociation atop the doped surfaces were found to be increased when compared to pristine surfaces, thus helping to further elucidate the role Ni could have played in the reactivity of FeS. It is expected that Ni doping in other Fe-sulphides may have a similar effect, limiting the catalytic activity of these phases when this dopant is present at their surfaces. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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10 pages, 1661 KiB

Open AccessArticle

The Ionic Organic Cage: An Effective and Recyclable Testbed for Catalytic CO₂ Transformation

by Wenlong Wang, Yuanyou Mao, Jutao Jin, Yanping Huo and Lifeng Cui

Catalysts 2021, 11(3), 358; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11030358 - 10 Mar 2021

Cited by 4 | Viewed by 3307

Abstract

Porous organic cages (POC) are a class of relatively new molecular porous materials, whose concept was raised in 2009 by Cooper’s group and has rarely been directly used in the area of organic catalysis. In this contribution, a novel ionic quasi-porous organic cage (denoted as Iq-POC), a quaternary phosphonium salt, was easily synthesized through dynamic covalent chemistry and a subsequent nucleophilic addition reaction. Iq-POC was applied as an effective nucleophilic catalyst for the cycloaddition reaction of CO₂ and epoxides. Owing to the combined effect of the relatively large molecular weight (compared with PPh₃⁺I⁻) and the strong polarity of Iq-POC, the molecular catalyst Iq-POC displayed favorable heterogeneous nature (i.e., insolubility) in this catalytic system. Therefore, the Iq-POC catalyst could be easily separated and recycled by simple centrifugation method, and the catalyst could be reused five times without obvious loss of activity. The molecular weight augmentation route in this study (from PPh₃⁺I⁻ to Iq-POC) provided us a “cage strategy” of designing separable and recyclable molecular catalysts. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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15 pages, 11183 KiB

Open AccessFeature PaperArticle

Green Synthesis of 2-Oxazolidinones by an Efficient and Recyclable CuBr/Ionic Liquid System via CO₂, Propargylic Alcohols, and 2-Aminoethanols

by Chao Bu, Yanyan Gong, Minchen Du, Cheng Chen, Somboon Chaemchuen, Jia Hu, Yongxing Zhang, Heriberto Díaz Velázquez, Ye Yuan and Francis Verpoort

Catalysts 2021, 11(2), 233; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11020233 - 09 Feb 2021

Cited by 14 | Viewed by 2990

Abstract

With the aim of profitable conversion of carbon dioxide (CO₂) in an efficient, economical, and sustainable manner, we developed a CuBr/ionic liquid (1-butyl-3-methylimidazolium acetate) catalytic system that could efficiently catalyze the three-component reactions of propargylic alcohols, 2-aminoethanols, and CO₂ to produce 2-oxazolidinones and α-hydroxy ketones. Remarkably, this catalytic system employed lower metal loading (0.0125–0.5 mol%) but exhibited the highest turnover number (2960) ever reported, demonstrating its excellent activity and sustainability. Moreover, our catalytic system could efficiently work under 1 atm of CO₂ pressure and recycle among the metal-catalyzed systems. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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Review

Jump to: Research

21 pages, 2198 KiB

Open AccessReview

Ni-Based Catalyst for Carbon Dioxide Methanation: A Review on Performance and Progress

by Nur Diyan Mohd Ridzuan, Maizatul Shima Shaharun, Mohd Azrizan Anawar and Israf Ud-Din

Catalysts 2022, 12(5), 469; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12050469 - 22 Apr 2022

Cited by 26 | Viewed by 6564

Abstract

Catalytic conversion of CO₂ into methane is an attractive method because it can alleviate global warming and provide a solution for the energy depletion crisis. Nickel-based catalysts were commonly employed in such conversions due to their high performance over cost ratio. However, the major challenges are that Ni tends to agglomerate and cause carbon deposition during the high-temperature reaction. In the past decades, extensive works have been carried out to design and synthesize more active nickel-based catalysts to achieve high CO₂ conversion and CH₄ selectivity. This review critically discusses the recent application of Ni-based catalyst for CO₂ methanation, including the progress on the effect of supporting material, promoters, and catalyst composition. The thermodynamics, kinetics, and mechanism of CO₂ methanation are also briefly addressed. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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16 pages, 3401 KiB

Open AccessReview

Research Progress in Semiconductor Materials with Application in the Photocatalytic Reduction of CO₂

by Yan Cui, Pengxiang Ge, Mindong Chen and Leilei Xu

Catalysts 2022, 12(4), 372; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12040372 - 24 Mar 2022

Cited by 12 | Viewed by 3737

Abstract

The large-scale burning of non-renewable fossil fuels leads to the gradual increase of the CO₂ concentration in the atmosphere, which is associated with negative impacts on the environment. The consequent need to reduce the emission of CO₂ resulting from fossil fuel combustion has led to a serious energy crisis. Research reports indicate that the photocatalytic reduction of CO₂ is one of the most effective methods to control CO₂ pollution. Therefore, the development of novel high-efficiency semiconductor materials has become an important research field. Semiconductor materials need to have a structure with abundant catalytic sites, among other conditions, which is of great significance for the practical application of highly active catalysts for CO₂ reduction. This review systematically describes various types of semiconductor materials, as well as adjustments to the physical, chemical and electronic characteristics of semiconductor catalysts to improve the performance of photocatalytic reduction of CO₂. The principle of photocatalytic CO₂ reduction is also provided in this review. The reaction types and conditions of photocatalytic CO₂ reduction are further discussed. We believe that this review will provide a good basis and reference point for future design and development in this field. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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24 pages, 1749 KiB

Open AccessReview

Research Progress and Reaction Mechanism of CO₂ Methanation over Ni-Based Catalysts at Low Temperature: A Review

by Li Li, Wenqing Zeng, Mouxiao Song, Xueshuang Wu, Guiying Li and Changwei Hu

Catalysts 2022, 12(2), 244; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12020244 - 21 Feb 2022

Cited by 42 | Viewed by 7734

Abstract

The combustion of fossil fuels has led to a large amount of carbon dioxide emissions and increased greenhouse effect. Methanation of carbon dioxide can not only mitigate the greenhouse effect, but also utilize the hydrogen generated by renewable electricity such as wind, solar, tidal energy, and others, which could ameliorate the energy crisis to some extent. Highly efficient catalysts and processes are important to make CO₂ methanation practical. Although noble metal catalysts exhibit higher catalytic activity and CH₄ selectivity at low temperature, their large-scale industrial applications are limited by the high costs. Ni-based catalysts have attracted extensive attention due to their high activity, low cost, and abundance. At the same time, it is of great importance to study the mechanism of CO₂ methanation on Ni-based catalysts in designing high-activity and stability catalysts. Herein, the present review focused on the recent progress of CO₂ methanation and the key parameters of catalysts including the essential nature of nickel active sites, supports, promoters, and preparation methods, and elucidated the reaction mechanism on Ni-based catalysts. The design and preparation of catalysts with high activity and stability at low temperature as well as the investigation of the reaction mechanism are important areas that deserve further study. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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40 pages, 6243 KiB

Open AccessReview

En Route to CO₂-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

by Antoine Brege, Bruno Grignard, Raphaël Méreau, Christophe Detrembleur, Christine Jerome and Thierry Tassaing

Catalysts 2022, 12(2), 124; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12020124 - 20 Jan 2022

Cited by 12 | Viewed by 7106

Abstract

This review is dedicated to the state-of-the art routes used for the synthesis of CO₂-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages and limitations. The first section reviews the synthesis of organic carbonates such as dialkyl carbonates or cyclic carbonates from the carbonation of alcohols. Many different synthetic strategies have been reported (dehydrative condensation, the alkylation route, the “leaving group” strategy, the carbodiimide route, the protected alcohols route, etc.) with various substrates (mono-alcohols, diols, allyl alcohols, halohydrins, propargylic alcohols, etc.). The second section reviews the formation of polycarbonates via the direct copolymerization of CO₂ with diols, as well as the ring-opening polymerization route. Finally, polycondensation processes involving CO₂-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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35 pages, 10755 KiB

Open AccessReview

Tandem Reactions Based on the Cyclization of Carbon Dioxide and Propargylic Alcohols: Derivative Applications of α-Alkylidene Carbonates

by Bowen Jiang, Xiangyu Yan, Yong Xu, Natalya Likhanova, Heriberto Díaz Velázquez, Yanyan Gong, Ye Yuan and Francis Verpoort

Catalysts 2022, 12(1), 73; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010073 - 10 Jan 2022

Cited by 7 | Viewed by 2604

Abstract

As a well-known greenhouse gas, carbon dioxide (CO₂) has attracted increasing levels of attention in areas of energy, environment, climate, etc. Notably, CO₂ is an abundant, nonflammable, and renewable C1 feedstock in view of chemistry. Therefore, the transformation of CO₂ into organic compounds is an extremely attractive research topic in modern green and sustainable chemistry. Among the numerous CO₂ utilization methods, carboxylative cycloaddition of CO₂ into propargylic alcohols is an ideal route due to the corresponding products, α-alkylidene cyclic carbonates, which are a series of highly functionalized compounds that supply numerous potential methods for the construction of various synthetically and biologically valuable agents. This cyclization reaction has been intensively studied and systematically summarized, in the past years. Therefore, attention has been gradually transferred to produce more derivative compounds. Herein, the tandem reactions of this cyclization with hydration, amination, alcoholysis, and isomerization to synthesize α-hydroxyl ketones, oxazolidinones, carbamates, unsymmetrical carbonates, tetronic acids, ethylene carbonates, etc. were systematically reviewed. Full article

(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)

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