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Review

Catalysis: Key Technology for the Conversion of CO2 into Fuels and Chemicals

by
Raquel Pinto Rocha
1,2 and
José Luís Figueiredo
1,2,*
1
LSRE-LCM—Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
2
ALiCE—Associate Laboratory in Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
*
Author to whom correspondence should be addressed.
Catalysts 2025, 15(7), 614; https://doi.org/10.3390/catal15070614 (registering DOI)
Submission received: 7 May 2025 / Revised: 4 June 2025 / Accepted: 16 June 2025 / Published: 21 June 2025
(This article belongs to the Special Issue Catalytic Processes for a Green and Sustainable Future)
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Abstract

:
The sustainability of the chemical industry requires replacing oil and natural gas with alternative raw materials and reducing CO2 emissions from processes and utilities. In the particular case of petrochemicals, decarbonization is not easy, since carbon is an integral part of the products. Fossil carbon can be replaced with recycled carbon and renewable carbon, but it is the use of CO2 as a raw material that will finally make it possible to close the carbon cycle in the chemical industry. The options available are discussed herein, highlighting recent breakthroughs in catalysis and identifying areas where further research is needed.

1. Introduction

The concentration of carbon dioxide in the atmosphere has been rising steadily since the Industrial Revolution (from 280 ppm in 1780 to 425 ppm in 2024), contributing to global warming and causing significant climate change. The burning of fossil fuels is responsible for the majority of anthropogenic CO2 emissions, amounting to around 36 Gt/year. A large part is retained by the soil, plants and oceans, but more than 40% accumulates in the atmosphere, increasing the CO2 concentration by 2 ppm/year [1]. In order to meet the 2015 Paris Agreement targets, the energy transition must be based on four pillars: renewable electricity; biofuels; hydrogen; and carbon dioxide capture, utilization and storage (CCUS) [2].
The chemical industry is one of the sectors of the economy where decarbonization is considered most difficult, especially in the case of petrochemicals, since carbon is part of the products. In this case, fossil carbon can be replaced with renewable carbon (from biomass) and recycled carbon (namely by recycling plastics), but carbon dioxide can also be used as a raw material. The use of CO2 as a carbon source for the synthesis of chemical products has a long history dating back to the 1970s [3,4], but the topic has now gained momentum by becoming one of the most relevant technologies for achieving carbon neutrality. In particular, it will be shown herein that transportation fuels, as well as the “base chemicals” (or primary products) on which the whole petrochemical industry is based (light alkenes, aromatics and methanol), can all be obtained from carbon dioxide. In this context, catalysis plays a key role, enabling the transition of the chemical industry to a circular carbon economy.

2. Carbon Dioxide Capture, Utilization and Storage (CCUS)

Carbon dioxide can be captured from localized emission sources, such as thermal power plants and large industrial plants (cement plants, refineries, chemical industrial plants, steelworks), taking advantage of processing streams with high concentrations (typically 12–15% in the flue gases of a thermal power station), or directly from the atmosphere (direct air capture, DAC). In the latter case, there is a much greater expenditure of energy, since it is necessary to move large amounts of air through the capture modules by means of fans (remember that the concentration of CO2 in the atmosphere is only 0.04%).
The main techniques available for removing CO2 from gaseous streams are absorption in aqueous solutions of an alkaline compound (ethanolamine, potassium carbonate, ammonia) and adsorption on porous materials (Table 1). In either case, when saturation is reached, it is necessary to regenerate the absorbent solution or the solid adsorbent, which implies additional energy consumption. The regenerative calcium cycle (or calcium looping) is already a relatively mature technology that allows CO2 removal from combustion flue gases by reaction with lime (CaO), the resulting calcium carbonate being subsequently calcined to regenerate and reuse the lime. Among the other technologies under development for application in combustion processes are chemical looping combustion (CLC) and Oxyfuel. In both cases, the objective is to obtain a gas stream of pure CO2 to avoid subsequent separation costs. In CLC, the oxygen needed for the combustion is supplied by means of a metal oxide, which is then reoxidized in a separate reactor and reused in a closed loop; in the Oxyfuel process, oxygen is used for the combustion, instead of air. In addition, a number of promising technologies have emerged, as shown in Table 1 [5].
DAC technology could become an important option for achieving carbon neutrality, especially if its energy costs can be reduced [6]. Climeworks (in Switzerland) was the pioneering company in this sector, having started its first commercial unit (with an annual capacity of 900 tons of CO2) in 2017. A larger plant (“Orca”, 4000 t/year) began operating in Iceland in 2021, injecting the carbon dioxide underground where it is converted into carbonates and stored permanently. This installation uses renewable energy (geothermal). There are other companies developing DAC technology, namely Carbon Engineering, in Canada, and Global Thermostat, in the United States.
On the other hand, the oceans are the largest natural reservoir of anthropogenic CO2; its average concentration at the surface is around 90 mg/L, two orders of magnitude higher than the concentration in the atmosphere (420 ppm ≈ 0.7 mg/L). At the pH values of seawater (8.1–8.3), carbon dioxide is mainly found in the form of bicarbonate ions (more than 85%), the remaining being in the form of carbonate and dissolved gas, according to the following equilibria:
CO32− + 2H+ ⇆ HCO3− + H+ ⇆ CO2 + H2O
These equilibria shift to the right as the pH decreases; thus, at pH < 6, most of the carbon is in the form of dissolved CO2 and can be extracted from seawater.
The first study to assess the feasibility of producing fuels from carbon dioxide dissolved in the ocean dates back to 2010, although at that time there was no technology available for this [7]. The first proposal appeared two years later and was based on a process of electrodialysis of seawater using bipolar membranes, which allow the H+ and OH− ions to be separated, originating an acid current (from which CO2 can be extracted) and an alkaline current [8]. A more interesting proposal is based on the continuous electrodeionization of seawater using a cation exchange module, with simultaneous production of CO2 and H2 [9]. Very recently, it was reported that Captura Corporation, a Caltech spin-off, has been set up with the aim of implementing off-shore CO2 capture using electrodialysis technology. The extraction of CO2 dissolved in the ocean has an additional advantage, since for every molecule of CO2 removed, an OH− ion is released, which promotes the capture of CO2 from the atmosphere (a process that takes place slowly over months) in order to rebalance the natural carbon cycle [10].
CCUS technologies aim to remove CO2 from the atmosphere and store it permanently underground in geological formations or use it as a valuable resource, namely as a fluid with technological applications (fire extinguishers, solvents for supercritical extraction, refrigerants, carbonated drinks, tertiary oil recovery) or as a raw material for the chemical industry. The latter application will be developed in the following section.

3. Conversion of Carbon Dioxide into Chemicals and Fuels

Carbon dioxide has been used as a raw material in the chemical industry since the 20th century, mainly in the synthesis of urea (by reaction with ammonia) but also as an additive in the synthesis of methanol and, to a lesser extent, to produce carbonates and inorganic pigments. These applications consume around 220 Mt/year. However, there is a wide range of new processes that make it possible to recycle carbon while mitigating or eliminating the environmentally harmful effects of CO2, such as the production of synthetic fuels and high-value-added chemical products [11].
CO2 conversion reactions can be classified into three groups according to the degree of reduction required and the replacement of C–O bonds by C–H, C–C, C–N or other bonds, as shown in Table 2 [12].
At one extreme, there are processes in which the entire CO2 molecule is incorporated without any change in the oxidation state of the carbon atom, which remains equal to +4. At the other extreme, we have the complete reduction of CO2, obtaining saturated hydrocarbons after removing the two oxygen atoms. Examples include the Sabatier reaction (methanation) and the Fischer–Tropsch process. The intermediate group includes processes for the synthesis of functionalized molecules, in which there is both a partial reduction of carbon and the formation of new bonds.

3.1. Synthesis of Carbonates from CO2

The production of organic carbonates from CO2 is expected to be a promising technique for the utilization of CO2, due to the possible synthesis of several chemicals used as electrolytes in Li-Na batteries, as additives for cosmetics, and in coatings, paints and other applications [13]. The most common and effective route to prepare cyclic carbonates, including at the industrial level, is the cycloaddition of CO2 to epoxides, typically to produce propylene carbonate and ethylene carbonate from propylene and ethylene oxides, respectively, which are two epoxides produced from petroleum-based propylene and ethylene [14]. This is a 100% atom-efficient reaction; however, the nonrenewable origin of the epoxides, along with the high toxicity and volatility of propylene oxide and, in particular, ethylene oxide (which is a gas at room temperature), has motivated the search for other feedstocks to improve the sustainability of the overall process. Alternative routes are being investigated using bio-based wastes, like glycerol, which is a renewable resource available on a large scale as the main side product of the manufacture of biodiesel. Glycerol and CO2 can be used to produce glycerol carbonate, a valuable chemical that has received much attention over the last several years [15,16,17] due to its application as a building block in polymer synthesis, beauty/personal care/pharmaceutical products and lithium batteries [18]. Indirect synthetic routes for glycerol carbonate production include the transcarbonation of glycerol with phosgene, carbonation with urea and transesterification with dimethyl carbonate [19]. The most desirable route for glycerol carbonate synthesis is the direct reaction of glycerol with CO2; however, the conversion is limited by thermodynamics, and finding a suitable dehydrating agent to remove H2O as the reaction proceeds is essential to reach high yields [20].
In recent years, there have been an increasing number of reports on heterogeneous catalysts used in the synthesis of glycerol carbonate from glycerol and CO2 (Scheme 1). Some examples of the catalysts that have been reported for this process are compiled in Table 3. Sn catalysts were the first reported catalysts in the carbonation of glycerol with CO2, followed by several homogenous and heterogeneous catalysts (2-Cyanopyridine; CH2Br2; several oxides of Ca, Zn, Sn, Fe, Ce and La; mixtures of La2O2CO3/ZnO; Ti-SBA-15; and Ag-, Zn-impregnated zeolites) [18,21,22,23,24,25,26,27,28]. The approaches developed to greatly improve the glycerol carbonate yield (between 7 and 90%) include the use of organic solvents such as N,N-dimethyl formamide, methanol or 2-cyanopyridine and uneasily recoverable or homogeneous catalysts, high pressures (50–150 bar) and long heating times at high temperatures (80–180 °C). More recently, the addition of Cu nanoparticles (NPs) to a La2O3 system allowed up to 33% glycerol conversion, with 45.4% selectivity towards glycerol carbonate (150 °C; 70 bar); the activity was strictly ascribed to the small size of the Cu-NPs and to the presence of basic sites on the support, which could both be involved in the activation of glycerol and CO2 [29]. Also, CeO2 nanorods with abundant basic sites and oxygen vacancies showed good glycerol carbonate yields (up to 78.9%) under conditions of 150 °C and 40 bar in 5 h [25]. Investigations have been carried out using a few carbon-based catalysts for the coupling of CO2 with epoxides but mainly in direct glycerol carbonate synthesis [30,31,32]. CO2 electro-cycloaddition to epoxides has also been investigated under mild electrochemical conditions for the synthesis of cyclic carbonates [33,34,35].

3.2. Conversion of CO2 into C1 and C2+ Chemicals and Fuels

The processes for converting carbon dioxide with “green hydrogen” (obtained by electrolysis of water with electricity from renewable sources) are generically known as “power-to-X”; examples include “power-to-gas” (methane production), “power-to-liquids” (liquid hydrocarbon production) and “power-to-chemicals” (chemical synthesis), as shown in Table 4.
Table 4. Production of fuels and chemicals from carbon dioxide and green hydrogen: “power-to-X” processes. Sources: references [11,12,44].
Table 4. Production of fuels and chemicals from carbon dioxide and green hydrogen: “power-to-X” processes. Sources: references [11,12,44].
Power-to-XProducts Obtained and Processes Involved
Power-to-gasMethane: Sabatier reaction (CO2 methanation)
Power-to-liquidsLiquid hydrocarbons: “reverse water–gas shift” (RWGS), followed by Fischer–Tropsch synthesis
Power-to-chemicalsSynthesis of chemicals by catalytic hydrogenation or by electrocatalytic reduction
The catalytic hydrogenation of CO2 to produce methane is the “Sabatier reaction”:
CO2 + 4H2 → CH4 + 2H2O
Sabatier and Senderens studied this reaction at the beginning of the 20th century, using Ni catalysts [45]. It is now known that all metals in groups 8–10 of the Periodic Table can catalyze the reaction, Ru being the most active and Ni the most selective [46]. On the basis of cost-effectiveness, nickel is also the catalyst of choice.
The “power-to-gas” process involves converting solar energy into electricity (efficiency = 20%), producing hydrogen by water electrolysis (efficiency = 90%) and methanating carbon dioxide (efficiency = 70%). This results in an overall process efficiency of 12.6%, which is already better than what plants can achieve (1.8–2.2%), or even microalgae (6–10%) [11].
Traditionally, the production of synthetic fuels is based on synthesis gas (CO + H2), which can be obtained from fossil raw materials (coal, oil or natural gas) by reacting them with water vapor and/or oxygen: steam-reforming, partial oxidation and gasification processes. Synthesis gas can be used to produce methanol (methanol synthesis) or liquid hydrocarbons (Fischer–Tropsch synthesis). The “power-to-liquids” process is already being implemented at an industrial level using the existing technology, which involves the initial conversion of CO2 to CO (via the RWGS reaction), followed by the conventional Fischer–Tropsch process (FTS). This is the first of the indirect routes shown in Scheme 2. Catalysts for the RWGS reaction are usually based on iron oxides or on copper, but there is intense research on the development of new catalysts [47,48,49,50]. cobalt and iron are the most widely used FTS catalysts to produce diesel fuels [51].
Liquid hydrocarbons can also be produced by the methanol-to-gasoline (MTG) process developed by Mobil in the 1970s. In this alternative indirect route, CO2 is first converted to CO by the RWGS reaction, followed by methanol synthesis (MS); then, the MTG process converts methanol into high-octane gasoline on a shape-selective zeolite catalyst (ZSM-5, MFI structure). The mechanism of the reaction proceeds through a sequence of steps involving the initial dehydration of methanol into dimethyl ether (DME) and the formation of light alkenes (C2–C5) and C5+ alkenes, then alkanes, cycloalkanes and aromatics. The final product is a mixture of hydrocarbons in the gasoline boiling range (C5–C10) [52,53,54,55]. Methanol-to-olefins (MTO) and methanol-to-aromatics (MTO) are related processes [56].
Obviously, these indirect routes are not an ideal solution, since the RWGS reaction consumes valuable “green” hydrogen to produce water:
CO2 + H2 ⇆ CO + H2O
The same applies to the methanation reaction, where 50% of the hydrogen ends up in water.
The direct use of carbon dioxide in “power-to-liquids” processes is possible but requires some modifications, as discussed in Section 3.2.1 and Section 3.2.2.
Concerning the synthesis of chemicals ("power-to-chemicals"), in addition to C1 compounds (methanol, formic acid, formaldehyde) and their derivatives, the greatest research efforts are focused on the synthesis of oxygenated C2+ compounds (acids, alcohols, aldehydes, ethers) [12,44,57], as well as light olefins (C2–C4), straight-chain α-olefins (C4–C17) and aromatic hydrocarbons (C6–C8) [58]. The formation of C2+ products requires not only efficient CO2 activation and reduction but also selective carbon–carbon (C–C) coupling, which is a significantly more challenging process [59,60,61,62]. The “one-pot” hydrogenation of CO2 via the FTS has attracted significant attention due to its operational simplicity—stemming from a reduced number of process steps—and consequently lower associated costs and energy consumption [63]. This integrated process is particularly challenging, as it requires bifunctional catalysts with active sites capable of catalyzing both the RWGS (CO generation) and FTS (CO hydrogenation) steps under identical operating conditions [64], although the RWGS reaction is mildly endothermic and competes with the strongly exothermic CO2 methanation reaction at lower temperatures [49]. Supported catalysts based on Fe, Co and Ru are among the most widely used, with Fe being particularly effective for olefin production [65,66,67,68] and noble metals like Ru/Pd showing higher activity toward alcohol formation [69,70].
Because the pathway involved in the growth of the carbon chain for any given C2+ product contains many successive reaction steps [71], tandem catalysis, which involves separate but coupled steps (e.g., CO2 to CO followed by CO coupling), is gaining attention for modular and efficient C2+ production [72]. Recent research has focused intensively on the development of efficient and selective bifunctional catalysts.

3.2.1. Hydrogenation of Carbon Dioxide to Methanol

In the synthesis of methanol, a copper metal and zinc oxide catalyst supported on alumina is currently used (a “low-pressure” process at 50–100 bar and 220–300 °C, introduced by ICI in 1966, replacing the original “high-pressure” process developed by BASF in the 1920s). The Cu-ZnO/Al2O3 catalyst also works with a CO2 + H2 mixture; in fact, in the conventional synthesis process, it is already usual practice to add some CO2 (2–8%) to the synthesis gas, to adjust the stoichiometry and to improve the kinetics of the reaction [73]. The methanol is actually produced from CO2 (through the formation of an intermediate formate species adsorbed on the catalyst) according to the following mechanism, where Oa is an adsorbed oxygen atom [74]:
CO2 + 2H2 → CH3OH + Oa
CO + Oa → CO2
CO + 2H2 → CH3OH (methanol synthesis)
However, the hydrogenation of carbon dioxide produces not only methanol but also water:
CO2 + 3H2 → CH3OH + H2O
Water can also be formed by the reverse water–gas shift (RWGS) reaction.
Although the conventional catalyst works well for CO2 hydrogenation, the formation of water can affect its stability, so it is necessary to develop new catalysts that are more tolerant to the presence of water [73,75]. A Cu-ZnO/ZrO2 catalyst was proposed as a promising alternative [76]. More recently, In2O3/ZrO2 was reported as a very active and stable catalyst for the synthesis of methanol from CO2, with 100% selectivity [77]. A further improvement was achieved by promotion with Pd, which is a good catalyst for hydrogen dissociation [78]. A subsequent investigation of this catalyst system by operando spectroscopy showed that the two sites perform separate functions: Pd activates H2, while In2O3 activates carbon dioxide [79]. Another option would be the direct synthesis of dimethyl ether (DME) from carbon dioxide, using bifunctional catalysts, by coupling a MS catalyst with a dehydration component [80]. Core–shell catalysts, where the MS component is in the core and the dehydration component is in the shell, have shown enhanced performance for DME synthesis from syngas [81]. The application of this type of nanostructured catalyst for CO2 hydrogenation has recently been reviewed [82].
Methanol is a very versatile compound as it can be used as an energy carrier and as a fuel (directly or in fuel cells) or as a base chemical for the production of a wide variety of organic compounds: formaldehyde, acetic acid, ethers (MTBE, TAME, DME), methylamines, methyl chloride, methylmethacrylate, dimethylterephthalate, olefins (MTO process) and aromatics (MTA process). It can also be converted into gasoline (MTG process) [12]. The MTG, MTO and MTA processes are based on the use of the ZSM-5 zeolite developed in the 1970s by Mobil [83]. This versatility of methanol led George Olah to propose the "methanol economy" as an alternative to the "hydrogen economy" [84], since methanol has obvious advantages as an energy carrier: it is a liquid at room temperature, which makes it easier to transport and store; and its energy density (15.6 MJ/L), although only about half that of traditional fuels (38.6 MJ/L for diesel, 34.2 MJ/L for gasoline), is much higher than that of hydrogen (8.6 MJ/L in the liquid state, under cryogenic conditions) [73].

3.2.2. Multifunctional Catalysts for Tandem Conversion of CO2 to Hydrocarbons

The direct hydrogenation of carbon dioxide to liquid fuels (gasoline and diesel) can be achieved via methanol or the FTS, with multifunctional catalysts [63]. Gao et al. [71] reported the direct conversion of CO2 to gasoline-range hydrocarbons using a bifunctional catalyst consisting of In2O3 and HZSM-5 (mass ratio 2:1). The selectivity to C5–C11 hydrocarbons was 78.6%, mostly iso-alkanes (59.2%) and aromatics (14.6%), which are high-octane-number hydrocarbons. On the other hand, the CH4 selectivity was only 1% and the CO2 conversion rate was 13.1%. The unwanted RWGS reaction was suppressed as a result of the proximity of the two catalyst components, In2O3 for methanol synthesis and HZSM-5 for C–C coupling. Moreover, different products were obtained by replacing ZSM-5 with other zeolites: 76.9% selectivity to lower alkenes (C2–C4) with SAPO-34 and 38.7% selectivity to LPG (C3–C4 alkanes) with zeolite beta. The direct hydrogenation of CO2 to gasoline-range hydrocarbons was also reported by Wei et al. using a Na-promoted Fe3O4/HZSM-5 catalyst [61]. Iron oxide provides the active sites for the RWGS and FTS reactions. When the catalyst is reduced with H2 before the reaction, metallic iron is formed, which is converted into Fe3O4 and Fe5C2 by the reaction mixture. The Na promoter increases the surface basicity, facilitating the carburization of the iron catalyst. Iron carbides (in this case, Fe5C2) are the active phases involved in the FTS [85,86]. Thus, CO2 is initially reduced to CO on Fe3O4, which is the active phase for the RWGS; then, CO is hydrogenated to α-alkenes on Fe5C2, which are subsequently converted to C5–C11 hydrocarbons on the acid sites of the zeolite HZSM-5. This multifunctional catalyst promotes the tandem conversion of CO2 into gasoline with a selectivity of 78% and only 4% methane selectivity at a CO2 conversion rate of 22%. By replacing HZSM-5 with the zeolite HMCM-22, higher yields of iso-alkanes and lower yields of aromatics are obtained, which is a more favorable composition for gasoline. However, coke formation increases, leading to catalyst deactivation [87].
The hydrogenation of CO2 to α-olefins and aromatics has recently been reviewed [88]. The α-olefins with a carbon chain of length ≥4 are used for the synthesis of polymers, surfactants, lubricants and plasticizers; they are currently produced from oil-derived chemicals. Light olefins (ethene, propene, butenes) and aromatics (benzene, toluene, xylenes), together with methanol, are the so-called “base chemicals” (or primary products) of the petrochemical industry, from which all other products are obtained. The main routes to obtain olefins are the CO2-FTS route, combining the RWGS reaction with subsequent hydrogenation of CO to olefins, and the CO2-MS route, including CO2 hydrogenation to methanol and the MTO process. Iron-based catalysts with promoters are used in the first case, while the methanol route involves oxide catalysts coupled with zeolites. Aromatics can also be obtained by a CO2-FTS route, or by a CO2-MS route. In the CO2-FTS route, iron-based catalysts with different promoters and supports are coupled with an acidic zeolite, usually HZSM-5. For the CO2-MS route, a bifunctional catalyst coupling the MS and MTA reactions is required. Since the zeolites used for MTA usually operate at temperatures above 400 °C, MS catalysts based on Cu cannot be used, as they are not stable above 300 °C. So, high-temperature MS catalysts (based on Zn, Zr, In or Cr oxides) are coupled with the HZSM-5 zeolite to perform this tandem reaction. For instance, a bifunctional ZnZrO/HZSM-5 catalyst was reported to convert CO2 to aromatics with high selectivity (73% at a conversion rate of 14%). The presence of water (formed on the MS catalyst) and CO2 was found to inhibit the formation of polycyclic aromatics (which are precursors for coke formation), leading to excellent stability [89].
A comparison of these two routes for aromatics shows that the CO2 conversion rate in the FTS route is usually higher, and the CO selectivity is lower; thus, it is more efficient than the MS route, although it suffers from a wider product distribution and higher methane production. The main challenge in the MS route is to increase CO2 conversion while preventing the formation of CO from the RWGS reaction. The product distribution can be adjusted by tuning the acid strength and pore size of the zeolites [88,90].

3.2.3. Electrocatalysis

The electrochemical CO2 reduction reaction (CO2RR) is also an appealing idea for CO2 abatement, allowing the direct conversion of carbon dioxide into species that are more reduced (CO, formic acid, methanol, alcohols and C2+ hydrocarbons) [91,92,93]. The industrial sector is very interested, with some companies being created to (electro)recycle CO2 into chemicals and fuels (OPUS12, Berkeley, CA, USA) or leading big projects on the theme (Siemens and Evonik, Solvay) [94]. However, most of the electrochemical conversion technologies remain at low technology readiness levels (TRLs) and need further development before full-scale deployment [95]. To push this electrochemical technology forward, the development of advanced CO2 reduction electrocatalysts is crucial. Considerable progress has already been achieved in CO2RR to one-carbon (C1) products (such as CO and formic acid), with high Faradaic efficiency (>95% selectivity) for, e.g., CO being reported [96]. In contrast, CO2RR into more-added-value C2+ chemicals (such as ethanol, ethylene and propanol) is still a challenging task; monometallic electrocatalysts cannot efficiently reduce CO2 to these products [97], with low selectivity, competitive hydrogen evolution reactions (HERs) and poor stability being reported [98]. Transition metal (Mo, Fe, Co and Ni) [99] catalysts associated with conductive or semiconductive materials (cheap metal oxides or carbon derivatives, like carbon nanotubes [100,101]), are a promising way to obtain higher efficiencies [102], more so when heteroatom dopants (N, B, P, S) are used to adjust the carbon material’s surface chemistry [103,104,105,106]. For example, N-doped graphene quantum dots revealed 90% Faradaic efficiency (FE) in CO2 reduction to C2H4 and 45% in C2H5OH formation. N-doped nanodiamond/Si rod arrays have been reported to reach FEs from 91.2 to 91.8% at −0.8 to −1.0 V vs. RHE in 0.5 M NaHCO3 for CO2 to acetate. N-doped ordered mesoporous carbon containing pyridinic and pyrrolic N species was also reported to have superior performance towards C2H5OH (77% FE at −0.56 V vs. RHE was achieved) [107]. Besides N doping, the introduction of boron, sulfur, and fluorine atoms has been attempted, but most reports deal with C1 product formation [103].
Another possibility is “artificial photosynthesis”, based on the conversion of solar energy into chemicals, in which water is the source of protons and electrons and the reactions of carbon dioxide reduction and water oxidation are combined in the presence of suitable catalysts. These processes are still at the research stage, but their potential contribution to decarbonizing the chemical industry is enormous [108]. Approaches may include photothermal [109,110,111,112] and photoelectro [112,113,114,115,116] CO2 catalytic conversion.

4. Summary and Perspectives

The chemical industry has already begun to adapt to the new challenges of sustainability, which involve replacing oil, coal and natural gas with renewable raw materials. But the concept of the “circular economy” applied to the carbon used by the chemical industry necessarily implies the use of carbon dioxide as a raw material. Nature teaches us that CO2 is renewable carbon, and, as such, it must be captured from localized sources, taken directly from the atmosphere, or extracted from the oceans and converted into fuels and chemicals. The production of methane (by the Sabatier reaction) is already carried out with reasonable energy efficiency using solar energy, while methanol and liquid hydrocarbons can be obtained from CO2 by means of existing technologies (originally developed for the conversion of synthesis gas) using “green hydrogen”; however, these processes can still be optimized, which requires the development of new catalysts. On the other hand, the synthesis of chemicals, particularly C2+ compounds, by catalytic hydrogenation or electrocatalytic reduction of carbon dioxide, is an area that has been the subject of intense research activity. We have particularly focused on the synthesis of hydrocarbons, namely light alkenes and aromatics, by direct hydrogenation of carbon dioxide in tandem reactions with multifunctional catalysts. Together with methanol, these hydrocarbons are the “base chemicals” on which the petrochemical industry is based. Promising results have already been achieved by improving the catalysts for methanol and Fischer–Tropsch syntheses, coupled with shape-selective zeolites. These processes still require optimization in order to enhance the activation of CO2 and improve the selectivity to the desired products and the stability of the catalysts.
Meanwhile, photocatalytic and photoelectrocatalytic CO2 conversion processes, which are still at a less advanced stage of development, offer the possibility of eventually achieving the ultimate goal of “artificial photosynthesis”, mimicking nature. In all these processes, catalysis emerges as a key technology for the efficient conversion of CO2, promoting the chemical industry’s transition to a circular carbon economy, reducing resource consumption and waste production, and minimizing the environmental impacts of its activity.

Author Contributions

Conceptualization, R.P.R. and J.L.F.; Writing—original draft, review and editing, R.P.R. and J.L.F.; Funding acquisition, R.P.R. and J.L.F. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by national funds through FCT/MCTES, under project CATALYSE-CO2, Reference 2023.13478.PEX (DOI: 10.54499/2023.13478.PEX). This research was also supported by UID/50020 of LSRE-LCM—Laboratory of Separation and Reaction Processes—Laboratory of Catalysis and Materials—funded by Fundação para a Ciência e a Tecnologia, I.P./MCTES through national funds, and ALiCE—LA/P/0045/2020 (DOI: 10.54499/LA/P/0045/2020).

Data Availability Statement

No new data was used for the research described in the article. Data sharing is not applicable to this article.

Conflicts of Interest

The authors declare no conflicts of interest.

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Catalysts 15 00614 sch001
Scheme 1. Glycerol carbonylation with CO2 to form glycerol carbonate. Reprinted from reference [36].
Scheme 1. Glycerol carbonylation with CO2 to form glycerol carbonate. Reprinted from reference [36].
Catalysts 15 00614 sch001
Catalysts 15 00614 sch002
Scheme 2. Indirect routes to produce liquid fuels from carbon dioxide (“power-to-liquids”), with green hydrogen.
Scheme 2. Indirect routes to produce liquid fuels from carbon dioxide (“power-to-liquids”), with green hydrogen.
Catalysts 15 00614 sch002
Table 1. Technologies available for carbon dioxide capture [5].
Table 1. Technologies available for carbon dioxide capture [5].
CO2 Capture TechnologyConditions
AbsorptionAqueous solutions of alkanolamines, NH3 or K2CO3
AdsorptionSolid porous adsorbents
Calcium loopingCaO + CO2 ⇆ CaCO3 in two fluidized bed reactors
Chemical looping combustionMetal oxide used to supply oxygen for the combustion
OxyfuelOxygen used for the combustion (instead of air)
Emerging technologiesMembrane separation, ionic liquids, clathrate hydrates
Table 2. Classification of carbon dioxide conversion reactions into chemical products, according to the oxidation state of the carbon atom [12].
Table 2. Classification of carbon dioxide conversion reactions into chemical products, according to the oxidation state of the carbon atom [12].
Type of TransformationCarbon Oxidation StateChemicals and Fuels
Incorporation+4Cyclic carbonates, polycarbonates
Synthesis of functionalized compoundsintermediateC1 (formic acid, formaldehyde, methanol)
C2+ (alcohols, acids, aldehydes)
Complete reduction−4Methane, >C1 hydrocarbons
Table 3. Examples of homogenous and heterogenous catalysts tested in the direct synthesis of glycerol carbonate from CO2.
Table 3. Examples of homogenous and heterogenous catalysts tested in the direct synthesis of glycerol carbonate from CO2.
CatalystTemperature (°C)/
Pressure (Bar)		Solvent/Dehydrating AgentGC Yield (%)Ref.
n-Bu2Sn(OMe)2180/50-/Molecular sieves5.72[37]
nBu2SnO120/138MeOH/13X (soda) zeolite35[38]
Zn(OTf)2/phen180/80N-methyl-2-pyrrolidone/CaC292[39]
ZnY180/100-/-5.8[28]
ZnO180/150-/-8[23]
La2O2CO3/ZnO 170/40CH3CN14.4[26]
Cu/La2O3150/70CH3CN45.4[40]
Cu/MgO
Cu/La2O3		150/40CH3CN26.1
29.3		[41]
CeO2 nanorods150/40DMF/2-cyanopyridine78.9[25]
CeO2 nanopolyhedra180/1502-cyanopyridine14.2[21]
MgO150/80DMF/2-cyanopyridine10.6[42]
LaCoO3150/30DMF/2-cyanopyridine72.4[43]
GC—glycerol carbonate; MeOH—methanol; TEGDME—tetra(ethylene glycol)dimethyl ether; DMF—dimethyl formamide.
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Rocha, R.P.; Figueiredo, J.L. Catalysis: Key Technology for the Conversion of CO2 into Fuels and Chemicals. Catalysts 2025, 15, 614. https://doi.org/10.3390/catal15070614

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Rocha RP, Figueiredo JL. Catalysis: Key Technology for the Conversion of CO2 into Fuels and Chemicals. Catalysts. 2025; 15(7):614. https://doi.org/10.3390/catal15070614

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Rocha, Raquel Pinto, and José Luís Figueiredo. 2025. "Catalysis: Key Technology for the Conversion of CO2 into Fuels and Chemicals" Catalysts 15, no. 7: 614. https://doi.org/10.3390/catal15070614

APA Style

Rocha, R. P., & Figueiredo, J. L. (2025). Catalysis: Key Technology for the Conversion of CO2 into Fuels and Chemicals. Catalysts, 15(7), 614. https://doi.org/10.3390/catal15070614

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