Photothermal CO2 Research Articles

Near‐Unity Photothermal CO2 Hydrogenation to Methanol based on a Molecule/Nanocarbon Hybrid Catalyst

Solar‐driven CO2‐to‐methanol conversion provides an intriguing route for both solar energy storage and CO2 mitigation. For scalable applications, near‐unity methanol selectivity is highly desirable to reduce the energy and cost endowed by low‐value byproducts and complex separation processes, but so far has not been achieved. Here we demonstrate a molecule/nanocarbon hybrid catalyst composed of carbon nanotube‐supported molecularly dispersed cobalt phthalocyanine (CoPc/CNT), which synergistically integrates high photothermal conversion capability for affording an optimal reaction temperature with homogeneous and intrinsically‐efficient active sites, to achieve a catalytic activity of 2.4 mmol gcat‐1 h‐1 and selectivity of ~99% in direct photothermal CO2 hydrogenation to methanol reaction. Both theoretical calculations and operando characterizations consistently confirm that the unique electronic structure of CoPc and appropriate reaction temperature cooperatively enable a thermodynamic favorable reaction pathway for highly selective methanol production. This work represents an important milestone towards the development of advanced photothermal catalysts for scalable and cost‐effective CO2 hydrogenation.

Near-Unity Photothermal CO2 Hydrogenation to Methanol based on a Molecule/Nanocarbon Hybrid Catalyst.

Solar-driven CO2-to-methanol conversion provides an intriguing route for both solar energy storage and CO2 mitigation. For scalable applications, near-unity methanol selectivity is highly desirable to reduce the energy and cost endowed by low-value byproducts and complex separation processes, but so far has not been achieved. Here we demonstrate a molecule/nanocarbon hybrid catalyst composed of carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc/CNT), which synergistically integrates high photothermal conversion capability for affording an optimal reaction temperature with homogeneous and intrinsically-efficient active sites, to achieve a catalytic activity of 2.4 mmol gcat-1 h-1 and selectivity of ~99% in direct photothermal CO2 hydrogenation to methanol reaction. Both theoretical calculations and operando characterizations consistently confirm that the unique electronic structure of CoPc and appropriate reaction temperature cooperatively enable a thermodynamic favorable reaction pathway for highly selective methanol production. This work represents an important milestone towards the development of advanced photothermal catalysts for scalable and cost-effective CO2 hydrogenation.

Pt-supported on N-doped carbon/TiO2 nanomaterials derived from NH2-MIL-125 for efficient photo-thermal RWGS reaction

To mitigate carbon dioxide (CO2) emissions and advance carbon neutrality, the conversion of CO2 into value-added fuels and chemicals via the reverse water–gas shift (RWGS) reaction is recognized as a promising approach. In this study, we designed platinum (Pt)-loaded nitrogen-doped carbon composite dual-phase titanium dioxide (TiO2) nanomaterials to achieve efficient photo-thermal performance in the RWGS reaction. The incorporation of Pt, nitrogen doping, and the selection of an appropriate calcination temperature enhance light responsiveness and reduce the recombination of photo-generated carriers, thereby improving the efficiency of the photo-thermal RWGS reaction. The optimized catalysts exhibited a high CO2 conversion (42.79 %), a carbon monoxide (CO) production rate (81.46 mmol gcat−1 h−1) and over 99.9 % selectivity under conditions of 400 °C and 1.2 W cm−2 light illumination. In addition, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analyses revealed that Pt/TiO2@CN-525 was enriched with more oxygen defects, which was facilitate the adsorption and activation of CO2. CO temperature-programmed desorption (CO-TPD) showed that Pt/TiO2@CN-525 possesses a strong desorption capacity for CO. In addition, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) pointed to COOH* as a key intermediate in the reaction process. The photo-thermal co-catalyzed CO2 reduction by CO-TPD as well as in-situ DRIFTS indicated that Pt/TiO2@CN-525 follows the RWGS reaction. This work provides a potential strategy for the synthesis of catalysts for enhancing photo-thermal co-catalyzed RWGS reactions.

Z-scheme ZnIn2S4/CuxO heterostructure on flexible substrate for efficient photothermal catalytic CO2 reduction

The ZnIn2S4 nanosheets were successfully synthesized on the surface of compacted stainless steel mesh using a simple solvothermal method, and further modified with CuxO nanoparticles to form ZnIn2S4/CuxO heterojunction photocatalyst via a wet chemistry approach. These photocatalysts were then utilized for photothermal catalytic CO2 reduction under full spectrum solar light. The experimental results demonstrated that the deposition of the photocatalyst on the flexible substrate effectively prevented the aggregation of ZnIn2S4 nanosheets. The incorporation of CuxO nanoparticles enhanced the specific surface area of the photocatalyst, and created a Z-scheme heterojunction with ZnIn2S4 to improve the utilization efficiency of photogenerated electrons. It was noteworthy that the dark red CuxO exhibited a full spectrum response and excellent photothermal effect, thereby facilitating carrier migration and reducing CO2 catalytic reaction barriers. Consequently, the optimized ZnIn2S4/CuxO exhibited significantly enhanced CO2 to CO yield of 1515.8 μmol m-2h−1 and CH4 yield of 1579.4 μmol m-2h−1, which was about 7.5 and 7.6 times higher than those achieved by pure ZnIn2S4, respectively. Furthermore, this study provided detailed insights into the mechanism of photocatalytic CO2 reduction over composite material as well as valuable guidance for designing immobilized photocatalysts with high activity for CO2 reduction.

A C-modified engineering strategy of porous In2O3 catalysts for point-concentrated solar-driven photothermal CO2 hydrogenation

The solar-driven photothermal CO2 conversion serves as an effective approach for addressing the substantial challenges of energy crises and global environmental issues. In this work, various forms of In2O3 catalysts, including In2O3-c, In2O3-r, In2O3-s, and porous spherical In2O3, along with a C-modified porous spherical In2O3 catalyst (C-In2O3), were successfully synthesized through a hydrothermal method. An in-depth analysis was conducted to evaluate the performance of these catalysts in the point-concentrated solar-driven photothermal CO2 hydrogenation. As a result, the porous C-In2O3 catalyst exhibited a superior CO2 conversion rate of approximately 13.2 % under simulated sunlight irradiation, with a light intensity of 44.6 mW/cm2. Notably, all catalysts demonstrated nearly 100 % selectivity towards CO (CO production rate of around 8.51 mmol gcat−1h−1) during the photothermal catalytic reaction, without any formation of CH4. The outstanding performance of the C-In2O3 catalyst was attributed to the modification of In2O3 band structure by the incorporation of C, which significantly enhanced the intensive solar light absorption of the catalyst. Furthermore, incorporating C into In2O3 substantially augments its basic strength and significantly elevates the quantity of basic sites, thereby endowing it with outstanding CO2 adsorption and conversion capabilities. This work provides a C-modified engineering strategy to design efficient photothermal catalysts for boosting point-concentrated photothermal CO2 hydrogenation.

Revealing the Mechanism of Converting CO2 into Methanol by the Cu2O and Oxygen Vacancy on MgO: Experiments and Density Functional Theory.

Given the great significance of defect and Cu compounds for the reduction of CO2 as well as the few reaction mechanisms of converting CO2 into different hydrocarbons, the effects of oxygen vacancies and Cu2O on the reduction of CO2 were thoroughly investigated, and possible mechanisms were also proposed. A series of Cu2O/Ov-MgO catalysts were synthesized for photothermal catalytic reduction of CO2 to methanol under visible-light irradiation, among which the 7%Cu2O/Ov-MgO composite exhibited the best reduction activity and the yield of methanol was 19.78 μmol·g-1·h-1. The successful composite of Cu2O and Ov-MgO can yield a loose and porous nanosheet, uniform distribution, favorable absorbance and photoelectric performance, and increased specific surface area and adsorption ability of CO2, which are all vital to the adsorption and conversion of CO2. The introduction of oxygen vacancy and Cu2O not only promotes the adsorption of CO2 but also provides more electron-triggered CO2 activation. Density functional theory (DFT) calculation was also performed to reveal the reaction mechanism for effective enhanced CO2 reduction to ethanol or methanol by the comparison of CuO/MgO and Cu2O/Ov-MgO composites, illustrating the reaction pathways of different products. By comparing the key steps in determining the selectivity of C1 or C2, the kinetic barriers of obtaining CH3OH for the Cu2O/Ov-MgO composite with CH3OH as the main product were found to be lower than those of generating CH2*, while the opposite is true for CuO/MgO composites, whereby it may be easier to obtain more C2 products. These insights into the reaction mechanism of converting CO2 into different hydrocarbons are expected to provide guidance for the further design of high-performance photothermal catalytic CO2 reduction catalysts.

Hot Electrons Induced by Localized Surface Plasmon Resonance in Ag/g-C3N4 Schottky Junction for Photothermal Catalytic CO2 Reduction.

Converting carbon dioxide (CO2) into high-value-added chemicals using solar energy is a promising approach to reducing carbon dioxide emissions; however, single photocatalysts suffer from quick the recombination of photogenerated electron-hole pairs and poor photoredox ability. Herein, silver (Ag) nanoparticles featuring with localized surface plasmon resonance (LSPR) are combined with g-C3N4 to form a Schottky junction for photothermal catalytic CO2 reduction. The Ag/g-C3N4 exhibits higher photocatalytic CO2 reduction activity under UV-vis light; the CH4 and CO evolution rates are 10.44 and 88.79 µmol·h-1·g-1, respectively. Enhanced photocatalytic CO2 reduction performances are attributed to efficient hot electron transfer in the Ag/g-C3N4 Schottky junction. LSPR-induced hot electrons from Ag nanoparticles improve the local reaction temperature and promote the separation and transfer of photogenerated electron-hole pairs. The charge carrier transfer route was investigated by in situ irradiated X-ray photoelectron spectroscopy (XPS). The three-dimensional finite-difference time-domain (3D-FDTD) method verified the strong electromagnetic field at the interface between Ag and g-C3N4. The photothermal catalytic CO2 reduction pathway of Ag/g-C3N4 was investigated using in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS). This study examines hot electron transfer in the Ag/g-C3N4 Schottky junction and provides a feasible way to design a plasmonic metal/polymer semiconductor Schottky junction for photothermal catalytic CO2 reduction.

Applications of Ni-Based Catalysts in Photothermal CO2 Hydrogenation Reaction.

Heterogeneous CO2 hydrogenation catalytic reactions, as the strategies for CO2 emission reduction and green carbon resource recycling, play important roles in alleviating global warming and energy shortages. Among these strategies, photothermal CO2 hydrogenation technology has become one of the hot catalytic technologies by virtue of the synergistic advantages of thermal catalysis and photocatalysis. And it has attracted more and more researchers' attentions. Various kinds of effective photothermal catalysts have been gradually discovered, and nickel-based catalysts have been widely studied for their advantages of low cost, high catalytic activity, abundant reserves and thermal stability. In this review, the applications of nickel-based catalysts in photothermal CO2 hydrogenation are summarized. Finally, through a good understanding of the above applications, future modification strategies and design directions of nickel-based catalysts for improving their photothermal CO2 hydrogenation activities are proposed.

Activation of Bi2MoO6/Zn0.5Cd0.5S charge transfer through interface chemical bonds and surface defects for photothermal catalytic CO2 reduction

The photocatalytic reduction of CO2 to high-value fuels has been proposed as a solution to the energy crisis caused by the depletion of energy resources. Despite significant advancements in photocatalytic CO2 reduction catalyst development, there are still limitations such as poor CO2 adsorption/activation and low charge transfer efficiency. In this study, we employed a defect-induced heterojunction strategy to construct atomic-level interface Cd-O bonds and form Bi2MoO6/Zn0.5Cd0.5S heterojunctions. The sulfur vacancies (VS) formed in Bi2MoO6/Zn0.5Cd0.5S acted as activation sites for CO2 adsorption. While the interfacial stability provided by the Cd-O bonds served as an electron transfer channel that facilitated the movement of electrons from the interface to the catalytic site. The VS and Cd-O bonds simultaneously influence the distribution of charge, inducing the creation of an interface electric field that facilitates the upward displacement of the center of the d-band. This enhances the adsorption of reaction intermediates. The optimized Bi2MoO6/Zn0.5Cd0.5S heterostructure exhibited high selectivity and stability of photoelectrochemical properties for CO, generating 42.97 μmol⋅g−1⋅h−1 of CO, which was 16.65-fold higher than Zn0.5Cd0.5S under visible light drive. This research provides valuable insights for designing photocatalyst interfaces with improved CO2 adsorption conversion efficiency.

Ferrocene Derivatives for Photothermal Applications.

Ferrocene (Fc) and Fc derivatives have gained popularity in recent years due to their unique structure and characteristics. Among Fc's diverse performances, photothermal conversion, as a primary source of energy conversion, has sparked substantial study attention. This Review summaries Fc and Fc derivatives with photothermal characteristics, as well as their applications developed recently. First, methods for the synthesis of Fc-based materials are systematically discussed. Then, the photothermal conversion mechanism based on nonradiative relaxation is summarized. Furthermore, the most recent advances in Fc-based materials in photothermal applications are described, including photothermal degradation, photothermal antibacterial, photothermal therapies, photothermal catalysis, solar-driven water production, and photothermal CO2 separation. Finally, a summary and insights on the photothermal application of Fc-based materials are provided. This paper seeks to provide researchers with a better knowledge of photothermal behavior while also highlighting the potential of Fc and its derivatives in photothermal fields.

Modulation of Selectivity and Activity of Ni/TiO2 Catalysts by Metal Dispersion in Photothermal CO2 Hydrogenation

Ni/TiO2 catalysts are efficient and cost‐effective for photothermal CO2 hydrogenation. However, the achieved CO/CH4 ratio strongly depends on the specific characteristics of these catalysts. To further ascertain the role of metal dispersion and photoactivation on selectivity, in this work we investigate the impact of Ni loading over high surface area anatase on the photothermal performance. Catalysts with 3 and 10 wt. % of Ni prepared by incipient wetness impregnation show initial good dispersion of the metal, although after activation in H2 metallic Ni nanoparticles are observed for 10%Ni/TiO2. This last catalyst demonstrates superior CO2 hydrogenation activity at high temperature, but below 200 ºC it is overpassed by the catalyst with 3 wt % Ni/TiO2. The selectivity varies remarkably with Ni loadings. Thus, at 350 °C about 93 % of methane is obtained over 10 wt.% Ni/TiO2, while 3%Ni/TiO2 yields about 97 % of CO. Low‐intensity UV irradiation enhances performance, particularly at temperatures below 200 ºC, where an increment in the production of methane of up to 75 % is observed for 3 wt.% Ni/TiO2 at 200 ºC. These results highlight the influence of metal dispersion, along with irradiation on modulating the selectivity of the photothermal CO2 hydrogenation

In Situ Pyrolysis of ZIF-67 to Construct Co2N0.67@ZIF-67 for Photocatalytic CO2 Cycloaddition Reaction.

The development of heterogeneous catalysts with abundant active sites is pivotal for enhancing the efficiency of photothermal CO2 conversion. Herein, we report the construction of Co2N0.67@ZIF-67 through the in situ pyrolysis of ZIF-67 under low-temperature pyrolysis conditions. During the pyrolysis process, the crystal structure of ZIF-67 is predominantly preserved concurrently with the formation of Co2N0.67 nanoparticles (NPs) within the ZIF-67 pores. The optimal catalyst Co2N0.67@ZIF-67(450,2) not only possesses high photothermal efficiency but also can efficiently activate CO2. Benefiting from these characteristics, Co2N0.67@ZIF-67(450,2) exhibited significant catalytic activity in the photocatalytic cycloaddition of CO2 and epichlorohydrin. The yield of (chloromethyl)ethylene carbonate reached 95%, which is more than 4 times higher than that of ZIF-67 under visible light irradiation (300 W·m2 Xe lamp, 3 h). This study could offer an alternative approach to enhance the photocatalytic activity of MOFs through low-temperature pyrolysis.

Dual nanoparticles with rich Ni–CeO2 interfaces for efficient photothermal catalytic CO2 reduction by CH4

Reducing CO2 by CH4 (CRM) is of great significance for alleviating greenhouse effects and fuel shortages. However, the high energy consumption and low yield of fuel, as well as the deactivation of Ni based catalysts constrained its development. Herein, a novel Ni–CeO2/Al2O3 catalyst for photothermal catalytic CRM merely upon focused light irradiation was reported. Very high yield of H2 and CO (80.2 and 96.3 mmol min−1 g−1) and excellent catalytic durability were achieved. The results of UV-VIS-IR diffuse reflectance spectra and experimental test indicate that high yield of H2 and CO originates from efficient photothermal conversion and the molecular activation effect of light. More importantly, Ni–CeO2/Al2O3 exhibits better carbon deposition resistance than Ni/Al2O3. The structural characterization and experimental evidences reveal that the active lattice oxygen in CeO2 nanoparticles can be transferred to Ni nanoparticles via Ni–CeO2 interface to accelerate carbon oxidation and form oxygen vacancies. The formed oxygen vacancies can re-adsorb and activate CO2 to form new active lattice oxygen.

Hierarchical Carbon Nanocages as Superior Supports for Photothermal CO2 Catalysis.

The exploitation of hierarchical carbon nanocages with superior light-to-heat conversion efficiency, together with their distinct structural, morphological, and electronic properties, in photothermal applications could provide effective solutions to long-standing challenges in diverse areas. Here, we demonstrate the discovery of pristine and nitrogen-doped hierarchical carbon nanocages as superior supports for highly loaded, small-sized Ru particles toward enhanced photothermal CO2 catalysis. A record CO production rate of 3.1 mol·gRu-1·h-1 with above 90% selectivity in flow reactors was reached for hierarchical nitrogen-doped carbon-nanocage-supported Ru clusters under 2.4 W·cm-2 illumination without external heating. Detailed studies reveal that the enhanced performance originates from the strong broadband sunlight absorption and efficient light-to-heat conversion of nanocage supports as well as the excellent intrinsic catalytic reactivity of sub-2 nm Ru particles. Our study reveals the great potential of hierarchical carbon nanocages in photothermal catalysis to reduce the fossil fuel consumption of various industrial chemical processes and stimulates interest in their exploitation for other demanding photothermal applications.

Photothermal-boosted S-scheme heterojunction of α-Fe2O3@NiOx for high-selective reduction of CO2 to CO

Self-heating photothermal catalysis, combining light promotion and thermal activation, offers unique advantages for CO2 conversion. The meticulous design of active sites and light-absorbing materials is crucial for high-performance photothermal catalysts. Herein, a S-Scheme heterostructure composed of NiOx subunits with abundant oxygen vacancies (Vo) bonded with α-Fe2O3 nanoplatelets has been fabricated for solar-driven photothermal catalytic CO2 reduction. Under continuous full-spectrum light irradiation (0.3 W·cm−2), the α-Fe2O3@NiOx hybrids exhibited a CO yield rate of 199.3 μmol∙g−1·h−1 in a gas–solid reaction models with near-unity selectivity. Additionally, the apparent quantum yield for CO production at 420 nm reaches 1.56 %. The prominent activity is attributed to three key factors: (1) The Vo-rich NiOx facilitates the accumulation of photogenerated electrons and activation of chemisorbed CO2. (2) The implemented S-Scheme heterostructures boost interfacial charge-transfer and provide spatially separated catalytic sites for efficient overall CO2 reduction. (3) The substantial photothermal effect of NiOx, which arises from nonradiative exciton recombination, induces local heating of the catalyst, thereby enhancing reaction kinetics. This work provides valuable insights into the utilization of a photothermal-photocatalytic S-Scheme heterojunction system for the photothermal catalytic CO2 reduction.

RuCo/ZrO2 Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO2 Methanation.

Photothermal CO2 methanation reaction represents a promising strategy for addressing CO2-related environmental issues. The presence of efficient tandem catalytic sites with a localized high-temperature is an effective pathway to enhance the performance of CO2 methanation. Here the bimetallic RuCo nanoparticles anchored on ZrO2 fiber cotton (RuCo/ZrO2) as a photothermal catalyst for CO2 methanation are prepared. A significant photothermal CO2 methanation performance with optimal CH4 selectivity (99%) and rate (169.93mmol gcat -1 h-1) is achieved. The photothermal energy of the RuCo bimetallic nanoparticles, confined by the infrared insulation and low thermal conductivity of the ZrO2 fiber cotton (ZrO2 FC), provides a localized high-temperature. In situ spectroscopic experiments on RuCo/ZrO2, Ru/ZrO2, and Co/ZrO2 indicate that the construction of tandem catalytic sites, where the Co site favors CO2 conversion to CO while incorporating Ru enhances CO* adsorption for subsequent hydrogenation, results in a higher selectivity toward CH4. This work opens a new insight into designing tandem catalysts with a photothermal confinement effect in CO2 methanation reaction.

Photothermal CO2 conversion to ethanol through photothermal heterojunction-nanosheet arrays

Photothermal CO2 conversion to ethanol offers a sustainable solution for achieving net-zero carbon management. However, serious carrier recombination and high C-C coupling energy barrier cause poor performance in ethanol generation. Here, we report a Cu/Cu2Se-Cu2O heterojunction-nanosheet array, showcasing a good ethanol yield under visible–near-infrared light without external heating. The Z-scheme Cu2Se-Cu2O heterostructure provides spatially separated sites for CO2 reduction and water oxidation with boosted carrier transport efficiency. The microreactors induced by Cu2Se nanosheets improve the local concentration of intermediates (CH3* and CO*), thereby promoting C-C coupling process. Photothermal effect of Cu2Se nanosheets elevates system’s temperature to around 200 °C. Through synergizing electron and heat flows, we achieve an ethanol generation rate of 149.45 µmol g−1 h−1, with an electron selectivity of 48.75% and an apparent quantum yield of 0.286%. Our work can serve as inspiration for developing photothermal catalysts for CO2 conversion into multi-carbon chemicals using solar energy.

Z-scheme heterojunctions of NF@ZnO/0.5CeO2 monolithic catalyst for photothermal catalytic CO2 reduction under concentrated solar irradiation

Z-scheme heterojunctions of NF@ZnO/0.5CeO2 monolithic catalyst for photothermal catalytic CO2 reduction under concentrated solar irradiation

Unraveling active sites regulation and temperature-dependent thermodynamic mechanism in photothermocatalytic CO2 conversion with H2O

In the photothermal synergistic catalytic conversion of CO2 and H2O, the catalyst harnesses solar energy to accumulate heat, thereby elevating the reaction system’s temperature. The influence of this temperature effect on surface chemical reactions remains an underexplored area. Here the impact of temperature on the surface-level thermodynamic reactions and conversion of CO2 with H2O on oxide semiconductors at the atomic scale was investigated using first-principle calculations. 13 different metal oxides and 5 transition metal clusters were used to introduce surface functional sites on the TiO2 supporting catalyst. The potential metal oxide cocatalysts that could be most beneficial to the following conversion of CO2 by H2O were initially screened by calculating the degrees of promotion of CO2 adsorption and activation of surface H to provide protons. The proton donation and hydrogen evolution difficulty from H2O were further analyzed, identifying transition metal cocatalysts that promote direct CO2 hydrogenation. Upon introducing bifunctional sites to facilitate adsorption and reduction, the production of CH3OH and CH4 could be further enhanced through the facilitation of the proton donation process of H2O. The results of Gibbs free-energy calculations revealed that increasing temperature enhances the reaction thermodynamics for each C1 product formation at different surface sites to varying degrees. These findings offer valuable theoretical insights for designing and regulating active sites on oxide semiconductor surfaces for efficient photothermal catalytic CO2 reduction by H2O.

Enhancing the Lewis acidity of single atom Tb via introduction of boron to achieve efficient photothermal synergistic CO2 cycloaddition

Nowadays, it is becoming increasingly urgent to lower the escalating carbon dioxide (CO2) to reduce greenhouse effect. Fortunately, it is an ideal strategy by using the inexhaustible solar energy as the driving force to manipulate the cycloaddition reaction, the atomic efficiency of which is 100 %. This work represents the first attempt on utilization of rare-earth metal Tb with atomic dispersion, and the structure of Tb coordinated with 4 N-atoms and 2B-atoms was constructed on interconnected carbon hollow spheres. The introduction of electron-deficient B reduces the electron density of Tb, thereby boosting Lewis acidity and promoting the occurrence of ring-opening reaction. The mechanism exploration enunciates that TbN4B2/C is a photothermal synergistic catalyst, the combined action of photogenerated electrons and strong Lewis acidic site of Tb reduces the free energy of the rate-determining step, and then improving the yield of cyclic carbonate up to 739 mmol g-1h−1.