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We report herein the preparation and characterization of six readily assembled bis-coordinated homoleptic silver(I) N,N′-bis(arylimino)acenaphthene (BIAN) complexes of general structure [Ag(I)(BIAN)2]BF4 and the influence of the electronic properties of the ligand substitution pattern on their performance in electrochemical CO2 reduction (CO2R). All the explored catalysts displayed substantial current enhancements in carbon-dioxide-saturated solvents dependent on the ligated BIAN and no significant concurrent H2 evolution when utilizing 2% H2O as a proton source. Additionally, preliminary studies, employing a drop-casted ink of 0.4 mg cm−2 [Ag(I)(4-OMe-BIAN)2]BF4 (Ag4) immobilized onto carbon paper gas diffusion electrodes in a flow cell with 1M KHCO3 aqueous electrolyte, resulted in a propitious Faradaic efficiency of 51% for CO at a current density of 50 mA cm−2. [ABSTRACT FROM AUTHOR]

The preparation of CO2-containing polymers with improved degradation properties is still very challenging. An elegant method for preparing these polymers is to use CO2-containing monomers in ring-opening polymerizations (ROP) which are particularly gentle and energy-saving methods. However, cyclic carbonates are required for this which are not readily available. This paper therefore aims to present the optimization and comparison of two synthesis methods to obtain cyclic carbonates for ROP. Within this work, cyclic styrene carbonate was synthesized from readily available raw materials by using a Jacobsen catalyst for the reaction of styrene oxide and carbon dioxide or an organocatalyst for the transesterification of methyl carbonate with 1-phenyl-1,2-ethanediol. The latter performed with 100% selectivity to the desired styrene carbonate, which was succesfully tested in ROP, producing an amorphous thermoplastic polymer with a TG of 185 °C. [ABSTRACT FROM AUTHOR]

This multi-disciplinary paper aims to provide a roadmap for the development of an integrated, process-intensified technology for the production of H2, NH3 and NH3-based symbiotic/smart fertilizers (referred to as target products) from renewable feedstock with CO2 sequestration and utilization while addressing environmental issues relating to the emerging Food, Energy and Water shortages as a result of global warming. The paper also discloses several novel processes, reactors and catalysts. In addition to the process intensification character of the processes used and reactors designed in this study, they also deliver novel or superior products so as to lower both capital and processing costs. The critical elements of the proposed technology in the sustainable production of the target products are examined under three-sections: (1) Materials: They include natural or synthetic porous water absorbents for NH3 sequestration and symbiotic and smart fertilizers (S-fertilizers), synthesis of plasma interactive supported catalysts including supported piezoelectric catalysts, supported high-entropy catalysts, plasma generating-chemical looping and natural catalysts and catalysts based on quantum effects in plasma. Their performance in NH3 synthesis and CO2 conversion to CO as well as the direct conversion of syngas to NH3 and NH3—fertilizers are evaluated, and their mechanisms investigated. The plasma-generating chemical-looping catalysts (Catalysts, 2020, 10, 152; and 2016, 6, 80) were further modified to obtain a highly active piezoelectric catalyst with high levels of chemical and morphological heterogeneity. In particular, the mechanism of structure formation in the catalysts BaTi1−rMrO3−x−y{#}xNz and M3O4−x−y{#}xNz/Si = X was studied. Here, z = 2y/3, {#} represents an oxygen vacancy and M is a transition metal catalyst. (2) Intensified processes: They include, multi-oxidant (air, oxygen, CO2 and water) fueled catalytic biomass/waste gasification for the generation of hydrogen-enriched syngas (H2, CO, CO2, CH4, N2); plasma enhanced syngas cleaning with ca. 99% tar removal; direct syngas-to-NH3 based fertilizer conversion using catalytic plasma with CO2 sequestration and microwave energized packed bed flow reactors with in situ reactive separation; CO2 conversion to CO with BaTiO3−x{#}x or biochar to achieve in situ O2 sequestration leading to higher CO2 conversion, biochar upgrading for agricultural applications; NH3 sequestration with CO2 and urea synthesis. (3) Reactors: Several patented process-intensified novel reactors were described and utilized. They are all based on the Multi-Reaction Zone Reactor (M-RZR) concept and include, a multi-oxidant gasifier, syngas cleaning reactor, NH3 and fertilizer production reactors with in situ NH3 sequestration with mineral acids or CO2. The approach adopted for the design of the critical reactors is to use the critical materials (including natural catalysts and soil additives) in order to enhance intensified H2 and NH3 production. Ultimately, they become an essential part of the S-fertilizer system, providing efficient fertilizer use and enhanced crop yield, especially under water and nutrient stress. These critical processes and reactors are based on a process intensification philosophy where critical materials are utilized in the acceleration of the reactions including NH3 production and carbon dioxide reduction. When compared with the current NH3 production technology (Haber–Bosch process), the proposed technology achieves higher ammonia conversion at much lower temperatures and atmospheric pressure while eliminating the costly NH3 separation process through in situ reactive separation, which results in the production of S-fertilizers or H2 or urea precursor (ammonium carbamate). As such, the cost of NH3-based S-fertilizers can become competitive with small-scale distributed production platforms compared with the Haber–Bosch fertilizers. [ABSTRACT FROM AUTHOR]

This paper presents an experimental study of using a double-layered Cu/TiO2 and P4O10/TiO2 as photocatalysts for CO2 reduction with an extended wavelength of range light from ultraviolet light (UV) to infrared light (IR). The lights studied were UV + visible light (VIS) + IR, VIS + IR and IR only. This study also investigated the impact of the molar ratio of CO2:H2O on the CO2 reduction performance. This study revealed that the optimum molar ratio of CO2:H2O to produce CO was 1:1, irrespective of light illumination condition, which matched the theoretical molar ratio to produce CO according to the reaction scheme of CO2 reduction with H2O. Comparing the results of double-layered Cu/TiO2 and P4O10/TiO2 with those of double-layered TiO2 obtained under the UV + VIS + IR light illumination condition, the highest concentration of formed CO and the molar quantity of formed CO per unit weight of the photocatalyst increased by 281 ppmV and 0.8 μmol/g, in the case of the molar ratio of CO2:H2O = 1:1. With IR-only illumination, the highest concentration of formed CO and the molar quantity of CO formed per unit weight of the photocatalyst was 251 ppmV and 4.7 μmol/g, respectively. [ABSTRACT FROM AUTHOR]

Carbon nitride MXene exhibits good metal conductivity, high photothermal conversion, carrier mobility, and high exposure of active sites, which makes it a promising co-catalyst for photothermal synergistic transformation of CO2. In this paper, Ti3CN/TiO2 heterojunction was constructed in situ using Ti3CN as TiO2 precursor to investigate the performance of Ti3CN MXene in photothermal synergistic transformation of CO2, and then the monolayer structure was utilized to enhance the interfacial charge transfer and improve the photothermal catalytic activity of Ti3CN. The catalysts were characterized by SEM, XRD, XPS, and UV-Vis DRS, and it was found the heterojunction constructed by monolayer MXene had a narrower bandgap and a higher carrier generation mobility, which, combined with the catalytic activity test, proved the single monolayer Ti3CN MXene had better photothermal synergistic conversion efficiency of CO2, and the heterojunction yield was 11.36 μmol·g−1·h−1 after layering, compared with that before layering (9.41%), which was 1.2 times higher than that before layering (9.41 μmol·g−1·h−1). [ABSTRACT FROM AUTHOR]

In this paper, we explore the catalytic CO2 reduction process on 13-atom bimetallic nanoclusters with icosahedron geometry. As copper and nickel atoms may be positioned in different locations and either separated into groups or uniformly distributed, the possible permutations lead to many unnecessary simulations. Thus, we have developed a machine learning model aimed at predicting the energy of a specific group of bimetallic (CuNi) clusters and their interactions with CO2 reduction intermediates. The training data for the algorithm have been provided from DFT simulations and consist only of the coordinates and types of atoms, together with the related potential energy of the system. While the algorithm is not able to predict the exact energy of the given complex, it is able to select the candidates for further optimization with reasonably good certainty. We have also found that the stability of the complex depends on the type of central atom in the nanoparticle, despite it not directly interacting with the intermediates. [ABSTRACT FROM AUTHOR]

Fossil fuels are still the main source of energy in today's society, so emissions of CO2 are inevitable, but when the CO2 level in the atmosphere is too high, many environmental problems will arise, such as the greenhouse effect, among others. Electrocatalytic reduction of CO2 is one of the most important methods that one can use to reduce the amount of CO2 in the atmosphere. This paper reviews bimetallic catalysts prepared on the basis of copper materials, such as Ag, Au, Zn and Ni. The effects of different ratios of metal atoms in the bimetallic catalysts on the selectivity of CO2RR were investigated and the effects of bimetallic catalysts on the CO2RR of different ligands were also analysed. Finally, this paper points out that the real reaction of CO2RR still needs to be studied and analysed, and the effect of the specific reaction environment on selectivity has not been thoroughly studied. This article also describes some of the problems encountered so far. [ABSTRACT FROM AUTHOR]

The kinetics of methanol synthesis remains debatable for various reasons, such as the lack of scientifically conclusive agreement about reaction mechanisms. The focus of this paper is on the evaluation of the intrinsic kinetics of the methanol synthesis reaction based on CO2 hydrogenation and the associated reverse water–gas shift as overall reactions. The industrial methanol synthesis catalyst, Cu/ZnO/Al2O3/MgO, was used for performing the kinetic studies. An optimal kinetic model was assessed for its ability to predict the experimental data from differential to integral conditions, contrary to the typical fitting of only the integral conditions' data (common practice, as reported in the literature). The catalyst testing and kinetic evaluations were performed at various temperatures (210–260 °C) and pressures (40–77 bar), and for different stoichiometric numbers (0.9–1.9), H2/CO2 ratios (3.0–4.4) and carbon oxide ratios (0.9–1.0), in an isothermal fixed bed reactor, operated in a plug-flow mode. Experiments with CO in the feed were also generated and fitted. Different literature kinetic models with different assumptions on active sites, rate-determining steps, and hence, model formulations were fitted and compared. The original Seidel model appeared to fit the kinetic data very well, but it has twelve parameters. The modified model (MOD) we propose is derived from this Seidel model, but it has fewer (nine) parameters—it excludes CO hydrogenation, but it takes into consideration the morphological changes of active sites and CO adsorption. This MOD model, with three active sites, gave the best fit to all the data sets. [ABSTRACT FROM AUTHOR]

The conceptual design and engineering of an integrated catalytic reactor requires a thorough understanding of the prevailing mechanisms and phenomena to ensure a safe operation while achieving desirable efficiency and product yields. The necessity and importance of these requirements are demonstrated in this investigation in the case of novel membrane-assisted reactors tailored for CO2 hydrogenation. Firstly, a carbon molecular sieve membrane was developed for simultaneous separation of CO2 from a hot post-combustion CO2-rich stream, followed by directing it along a packed-bed of hybrid CuO-ZnO/ZSM5 catalysts to react with hydrogen and produce DiMethyl Ether (DME). The generated water is removed from the catalytic bed by permeation through the membrane which enables reaction equilibrium shift towards more CO2-conversion. Extra process intensification was achieved using a membrane-assisted reactive distillation reactor, where similarly several such parallel membranes were erected inside a catalytic bed to form a reactive-distillation column. This provides the opportunity for a synchronized separation of CO2 and water by a membrane, mixing the educts (i.e., hydrogen and CO2) and controlling the reaction along the catalytic bed while distilling the products (i.e., methanol, water and DME) through the catalyst loaded column. The hybrid catalyst and carbon molecular sieve membrane were developed using the synthesis methods and proved experimentally to be among the most efficient compared to the state-of-the-art. In this context, selective permeation of the membrane and selective catalytic conversion of hybrid catalysts under the targeted operating temperature range of 200–260 °C and 10–20 bar pressure were studied. For the membrane, the obtained high flux of selective CO2-permeation was beyond the Robeson upper bound. Moreover, in the hybrid catalytic structure, a combined methanol and DME yield of 15% was secured. Detailed results of catalyst and membrane synthesis and characterization along with catalyst test and membrane permeation tests are reported in this paper. The performance of various configurations of integrated catalytic and separation systems was studied through an experimentally supported simulation along with the systematic analysis of the conceptual design and operation of such reactive distillation. Focusing on the subnano-/micro-meter scale, the performance of sequential reactions while considering the interaction of the involved catalytic materials on the overall performance of the hybrid catalyst structure was studied. On the same scale, the mechanism of separation through membrane pores was analyzed. Moreover, looking at the micro-/milli-meter scale in the vicinity of the catalyst and membrane, the impacts of equilibrium shift and the in-situ separation of CO2 and steam were analyzed, respectively. Finally, at the macro-scale separation of components, the impacts of established temperature, pressure and concentration profiles along the reactive distillation column were analyzed. The desired characteristics of the integrated membrane reactor at different scales could be identified in this manner. [ABSTRACT FROM AUTHOR]

In the face of increasing global carbon dioxide emissions and the urgent need to mitigate climate change, the development of efficient and sustainable strategies for CO2 conversion has gained significant attention. One of the methods of eliminating the harmful effects of CO2 is its photoreduction. In this paper, ZnO was used as an effective photocatalyst for the photoreduction of CO2 in a gas-phase system. The influence of particle size on the process efficiency was investigated. The ZnO materials applied in the studies were characterized using XRD, SEM, and low-temperature nitrogen adsorption (BET) methods. The pore volume distribution was calculated based on the DFT method. The investigation confirmed that it had a significant impact on the formation of the product of photocatalysis carbon dioxide. The main identified product was carbon monoxide. Hydrogen and methane were detected as well. Based on the results, it was found that the process efficiency was enhanced with decreasing ZnO particle size, and the most effective catalyst for the photoreduction of CO2 was the ZnO sample with the smallest particle size (18 nm). [ABSTRACT FROM AUTHOR]

As a typical organic semiconductor photocatalyst, graphitic carbon nitride (g-C3N4) suffers from low photocatalytic activity. In this paper, g-C3N4 was prepared by polymerization of dicyandiamide (C2H4N4) in the presence of ammonium chloride (NH4Cl). It was found that the addition of ammonium chloride can greatly improve the photocatalytic activity of g-C3N4 towards CO2 reduction. The optimal photocatalyst (CN-Cl 20) exhibited a CO2-to-CO conversion activity of 50.6 μmolg−1h−1, which is 3.1 times that of pristine bulk g-C3N4 (BCN) that was prepared in the absence of any ammonium chloride. The enhanced photoactivity of g-C3N4 was attributed to the combined effects of chloride modification and an enlarged specific surface area. Chloride modification of g-C3N4 can not only reduce the bandgap, but also causes a negatively shifted conduction band (CB) potential level, while ammonia (NH3) gas from the decomposition of NH4Cl can act as a gas template to exfoliate layered structure g-C3N4, improving the specific surface from 6.8 to 21.3 m2g−1. This study provides new ideas for the synthesis of highly efficient g-C3N4-based photocatalytic materials for CO2 conversion and utilization. [ABSTRACT FROM AUTHOR]

CO2 resourceful utilization contributes to the goal of carbon neutrality. Chemical Looping Dry Reforming (CLDR) has attracted significant attention as a method for converting CO2 to CO. NiFe2O4 oxygen carrier (OC) is found to be a potential material for CLDR. However, the migration process of lattice oxygen, which are critical for the conversion of CO2 to CO, was not extensively investigated. In this study, the reduction and oxidation degrees of the NiFe2O4 were finely modulated in a thermogravimetric analyzer. The lattice oxygen migration mechanism of the NiFe2O4 in redox cycles was characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and in-situ Raman. The novelty of this paper is clarifying the release-uptake paths of lattice oxygen during CO2 resourceful utilization. The result indicates that the concentration gradient between the surface and the bulk drives the diffusion of lattice oxygen. The stabilization of surface lattice oxygen content is attributed to the rapid migration of O anion, which is closely associated with the movement process of Ni particles inward and outward through the spinel bulk. In addition, a highly reactive chemical reaction interface consisting of lattice oxygen and the corresponding metal atoms is always present on the surface of the oxygen carrier and is confirmed by an in-situ Raman and XPS during the whole process of CLDR. The results of this paper offer reference and basis for further development and design of CLDR using spinel OC. [ABSTRACT FROM AUTHOR]

Electrocatalytic CO2-reduction technology can convert CO2 into methanol and other chemicals using renewable electricity, but the techno-economic prospects of the large-scale electrocatalytic reduction in CO2 into methanol are not clear. This paper conducted sensitivity analysis to confirm the key parameters affecting the cost of methanol production from an alkaline flow cell and a neutral MEA electrolyzer, compared the cost of the two electrolyzers under laboratory data and optimized data scenarios, and analyzed the key parameter requirements of the two electrocatalytic systems to achieve profitable methanol production. The results show that electricity price, Faradaic efficiency, cell voltage, and crossover/carbonate formation ratio are the most sensitive parameters affecting the cost of methanol production. The alkaline flow cell had higher energy efficiency than the MEA cell, but the saving cost of electricity and the eletrolyzer cannot cover the cost of the regeneration of the electrolyte and CO2 lost to carbonate/bicarbonate, resulting in higher methanol production costs than the MEA cell. When the crossover/carbonate formation ratio is zero, the cost of methanol production in an alkaline flow cell and a neutral MEA cell can reach under 400 USD/tonne in the cases of energy efficiency more than 70% and 50%, respectively. Therefore, enhancing energy efficiency and ensuring a low crossover/carbonate formation ratio is important for improving the economy of electrocatalytic methanol production from CO2 reduction. Finally, suggestions on the development of electrocatalytic CO2 reduction into methanol in the future were proposed. [ABSTRACT FROM AUTHOR]

In this study, Pt1Sn1 intermetallic nanoparticles (NPs) on SiO2/CeO2@SiO2 composites were located either on SiO2 or on CeO2@SiO2, thereby varying the average distance (intimacy) between metal sites and CeOx sites from "closest" to "nanoscale". The catalytic performance of these catalysts was compared to dual-bed mixtures of Pt1Sn1@SiO2 and CeO2@SiO2 powders, which provided a "milliscale" distance between sites. Several beneficial effects on the catalytic performance of CO2-assisted oxidative dehydrogenation of C5-paraffins were observed when Pt1Sn1 nanoparticles were located on SiO2 in nanoscale proximity to the CeO2 sites, as opposed to Pt and Sn species located on CeO2@SiO2 with the closest proximity and milliscale intimacy between Pt1Sn1 and CeO2. The former catalysts exhibited the highest C5-paraffin conversion of 32.8%, with a C5 total olefin selectivity of 68.7%, while the closest-proximity sample had a lower conversion of 17.4%, with a C5 total olefin selectivity of 20.9%. The FT-IR (Fourier transform infrared spectroscopy) spectroscopic study of the CO adsorption and X-ray photoelectron spectroscopy results revealed that the closest proximity between Pt and Ce inhibited PtSn alloy formation due to their strong interaction. However, for the nanoscale-proximity sample, neighboring CeO2@SiO2 did not disturb Pt1Sn1 intermetallic formation. This strategy can be applied to other CO2 activation catalysts, instead of CeO2@SiO2. This paper aims to provide insights into the influence of metal–CeOx intimacy in bi-functional catalysts. [ABSTRACT FROM AUTHOR]

Cu2O is a p-type direct bandgap semiconductor with a band gap of 2~2.2 eV, which has excellent visible light absorption and utilization. However, slow charge transfer and poor stability hinder its practical application. In this paper, a facile electrodeposition approach successfully synthesized the heterostructure of p-Cu2O and n-Cu2O. The protective layer of n-Cu2O on the surface of p-Cu2O nanoparticles forms a p/n heterojunction. Due to the p/n heterojunction, the PEC performance of p/n-Cu2O is enhanced significantly. The charge separation efficiency of photogenerated electron/hole pairs in p/n-Cu2O is greatly improved. Therefore, p/n-Cu2O shows superior photoelectrochemical (PEC) CO2 reduction reaction (CO2RR) efficiency when used as a photocathode. [ABSTRACT FROM AUTHOR]

A stable life support system in the spacecraft can greatly promote long-duration, far-distance, and multicrew manned space flight. Therefore, controlling the concentration of CO2 in the spacecraft is the main task in the regeneration system. The electrocatalytic CO2 reduction can effectively treat the CO2 generated by human metabolism. This technology has potential application value and good development prospect in the utilization of CO2 in the space station. In this paper, recent research progress for the electrocatalytic reduction of CO2 was reviewed. Although numerous promising accomplishments have been achieved in this field, substantial advances in electrocatalyst, electrolyte, and reactor design are yet needed for CO2 utilization via an electrochemical conversion route. Here, we summarize the related works in the fields to address the challenge technology that can help to promote the electrocatalytic CO2 reduction. Finally, we present the prospective opinions in the areas of the electrocatalytic CO2 reduction, especially for the space station and spacecraft life support system. [ABSTRACT FROM AUTHOR]

In this paper, a bimetallic Metal-Organic Framework (MOF) CoNiBTC was employed as a precursor for the fabrication of bimetallic nanoalloys CoNi@C evenly disseminated in carbon shells. These functional nanomaterials are characterized by powdered X-ray diffraction (PXRD), Fourier Transform Infra-Red spectroscopy (FTIR), surface area porosity analyzer, X-ray photoelectron spectroscopy (XPS), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Hydrogen Temperature-Programmed Reduction (H2 TPR), CO2 Temperature-Programmed Desorption (CO2-TPD), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). This nanocatalyst was utilized in the synthesis of benzimidazole from o-phenylenediamine in the presence of CO2 and H2 in a good yield of 81%. The catalyst was also efficient in the manufacture of several substituted benzimidazoles with high yield. Due to the existence of a bimetallic nanoalloy of Co and Ni, this catalyst was also employed in the methanation of CO2 with high selectivity (99.7%). [ABSTRACT FROM AUTHOR]

In-situ conversion of carbon dioxide into value-added products is an essential process in terms of heavy oil upgrading and utilization of the main anthropogenic greenhouse gas. In this paper, we discuss a synthesis of sodium-coated magnetite (Fe3O4) particles for in-reservoir hydrogenation of CO2. The performance of the obtained catalyst was tested in upgrading of heavy oil in a High Pressure/High Temperature (HPHT) reactor imitating the reservoir conditions during steam injection techniques. The experiments were conducted for 48 h in a CO2 environment under the steam temperature and pressure of 250 °C and 90 bar, respectively. The results showed irreversible viscosity reduction of oil from 3931 mPa.s to 2432 mPa.s after the degassing of unreacted carbon dioxide. The content of resins in the composition of upgraded oil was significantly altered from 32.1 wt% to 19.01 wt%, while the content of aromatics rose from 32.5 wt% to 48.85 wt%. The GC-MS results show the presence of alkyl benzenes and phenanthrenes, which were initially concentrated in resins and asphaltenes, in the aromatics fraction of upgraded crude oil. Thus, Na-Fe3O4 exhibits promising results for in-situ heavy oil upgrading through the hydrogenation of carbon dioxide, which contributes not only to the reduction of greenhouse gas emissions, but also enhances heavy oil recovery. [ABSTRACT FROM AUTHOR]

This paper investigates the effects of substituents in PNP-type ruthenium complexes in the catalytic hydrogenation of CO2 to formate using the DFT method. Six groups were considered as substituents linked to the P atom of the PNP ligand: hydrogen, methyl, iso-propyl, tert-butyl, cyclopentyl, and cyclohexyl. The substituent effects were analyzed from the perspectives of steric hindrance and promotion of hydrogen bonding. With the joint functions of steric hindrance and hydrogen bonding promotion during the CO2 coordination step, hydride addition step, and HCOO− rotation step, these groups exhibited very different substituent effects. The results showed that the methyl group was the most favorable substituent when the solvent's effects were not included, as it formed hydrogen bonding with relatively weak steric hindrance. The second favorable substituent was the iso-propyl group, while the tert-butyl group was the most unfavorable one, due to remarkable steric hindrance. When the substituent was cyclopentyl or cyclohexyl, the complex provided a wider open space for the reaction compared with the tert-butyl-substituted complex, because cyclopentyl and cyclohexyl are cyclic groups. Therefore, the principle for choosing the substituent in PNP-type complexes allowing the design of highly efficient catalysts for CO2 hydrogenation indicates that more hydrogen atoms but wider open space are ideal. In addition, the substituent's effects can be markedly impacted by the solvent used. [ABSTRACT FROM AUTHOR]

This paper presents the kinetics of methanol synthesis from carbon dioxide and hydrogen over a Cu/Zn/Zr/Ga catalyst. Kinetic studies were carried out in a continuous-flow fixed-bed reactor in a temperature range from 433 to 513 K, pressures from 3 to 8 MPa, and GHSV from 1660 to 10,000 1/h for initial molar fractions of hydrogen from about 0.48 to 0.70, carbon dioxide from 0.05 to about 0.22, and carbon monoxide from 0 to about 0.07. Significant effects of temperature and the composition of the reaction mixture on the conversion degrees α1 and α2 were found. The Cu/Zn/Zr/Ga catalyst showed good stability over 960 h. XRD and CO2TPD characterisation were performed. Thefinally obtained results of kinetic tests were developed in the form of Langmuir–Hinshelwood kinetic equations. The numerical Levenberg–Marquardt method was used to estimate the kinetic equations. The average relative error of fitting the kinetic equations to the experimental data was 18%. [ABSTRACT FROM AUTHOR]

The aim of this work was to study the influence of copper content and particle morphology on the performance of Cu/FeOx catalysts in the gas-phase conversion of CO2 with hydrogen. All four investigated catalysts with a copper content between 0 and 5 wt% were found highly efficient, with CO2 conversion reaching 36.8%, and their selectivity towards C1 versus C2-C4, C2-C4=, and C5+ products was dependent on catalyst composition, morphology, and temperature. The observed range of products is different from those observed for catalysts with similar composition but synthesized using other precursors and chemistries, which yield different morphologies. The findings presented in this paper indicate potential new ways of tuning the morphology and composition of iron-oxide-based particles, ultimately yielding catalyst compositions and morphologies with variable catalytic performances. [ABSTRACT FROM AUTHOR]

A facile and green synthetic strategy is developed in this paper for the construction of an efficient catalyst for the industrially important carbon dioxide reforming of methane, which is also named the dry reforming of methane (DRM). Through controlling the synthetic strategy and Ni content, a high-performance Ni@CeO2 catalyst was successfully fabricated. The catalyst showed superb efficiency for producing the syngas with high and stable conversions at prolonged operating conditions. Incorporating Ni during the ceria (CeO2) crystallization resulted in a more stable structure and smaller nanoparticle (NP) size with a more robust interaction with the support than loading Ni on CeO2 supports by the conventional impregnation method. The H2/CO ratio was almost 1.0, indicating the promising applicability of utilizing the obtained syngas for the Fischer–Tropsch process to produce worthy chemicals. No carbon deposits were observed over the as-synthesized catalyst after operating the DRM reaction for 50.0 h, even at a more coke-favoring temperature (700 °C). Owing to the superb resistance to coke and sintering, control of the size of the Ni-NPs, uniform dispersion of the active phase, and potent metal interaction with the support, the synthesized catalyst achieved a magnificent catalytic activity and durability during serving for the DRM reaction for extended operating periods. [ABSTRACT FROM AUTHOR]

Organic carbonates are considered the chemicals of the future. In particular, propylene carbonate is widely used as a non-reactive solvent, plasticizer, fuel additive, and reagent, especially in the production of environmentally friendly polymers that are not harmful to human health. This paper reviews recent literature findings regarding the development of propylene carbonate synthetic methods starting from propane-1,2-diol and urea. The ammonia formed during the synthesis is recycled to obtain urea from carbon dioxide. [ABSTRACT FROM AUTHOR]

The conversion of carbon dioxide into value-added products is progressively gaining momentum. Several strategies have been used to develop technologies that reduce the net emissions of CO2. The utilisation of CO2 could either contribute to carbon recycling. In this paper, the transformation of CO2 was investigated in a coelectrolysis cell constituted of a solid polymer electrolyte, a carbon-supported CuO-Ag composite cathode and NiFeOx anode. Noncritical raw materials were synthesised according to the oxalate method and investigated in an alkaline environment. Low-carbon alcohols were obtained with a specific selectivity for ethanol and methanol over the CuO-Ag/KB cathode. The reaction rates at 1.6 V and 1.8 V cell voltages have been determined in steady-state experiments using NaHCO3 supporting electrolyte recirculated at the anode. [ABSTRACT FROM AUTHOR]

Carbon capture and utilization (CCU) is a developing field with significant demand for research in the following aspects: The development of new catalysts, catalytic routes, and technologies for CO SB 2 sb conversion; The study of new processes for obtaining fuels and chemicals from CO SB 2 sb ; Optimization of the catalysts and the reaction conditions for these processes; Further steps in advanced processes using CO SB 2 sb -rich feeds (H SB 2 sb + CO SB 2 sb or CO SB 2 sb mixed with syngas), increasing product yields. Potassium is used as a structural promoter in the iron carbon-supported catalyst to boost catalyst activity and structural stability. The main focus of this review is to provide a useful resource for researchers to correlate catalyst deactivation and the recent research effort on catalyst development for enhanced olefin yields and catalyst stability. The combined TiO SB 2 sb -carbon spheres/silica cloth photocatalysts show higher efficiency in the two-electron CO SB 2 sb reduction towards CO than in the eight-electron reaction to methane. [Extracted from the article]

A series of Cu-ZnO-ZrO2 (CCZ) catalysts were prepared by the solvothermal method with different solvothermal times (1 h, 3 h, 6 h, and 12 h). The physicochemical properties of these catalysts and the catalytic performance for CO2 hydrogenation to methanol were studied. The highest methanol yield was achieved when the solvothermal time was 6 h (CCZ-6). Furthermore, we found that the copper surface area (SCu) increases and then decreases with an increase in the solvothermal time and that there is a strong correlation between the methanol yield and the SCu. This research highlights the crucial influence of the solvothermal time on the structure and catalytic behavior of Cu-ZnO-ZrO2 catalysts, providing a valuable reference for the development of efficient catalysts. [ABSTRACT FROM AUTHOR]

Photocatalytic technology, which is regarded as a green route to transform solar energy into chemical fuels, plays an important role in the fields of energy and environmental protection. An emerging S-scheme heterojunction with the tightly coupled interface, whose photocatalytic efficiency exceeds those of conventional type II and Z-scheme photocatalysts, has received much attention due to its rapid charge carrier separation and strong redox capacity. This review provides a systematic description of S-scheme heterojunction in the photocatalysis, including its development, reaction mechanisms, preparation, and characterization methods. In addition, S-scheme photocatalysts for CO2 reduction are described in detail by categorizing them as 0D/1D, 0D/2D, 0D/3D, 2D/2D, and 2D/3D. Finally, some defects of S-scheme heterojunctions are pointed out, and the future development of S-scheme heterojunctions is proposed. [ABSTRACT FROM AUTHOR]

This study proposes a straightforward strategy utilizing metal–organic frameworks (MOFs) to obtain efficient electrocatalysts for synthesizing C2 products (C2H4 and C2H5OH) via a CO2 reduction reaction. Cu-MOF-74 was chosen as the precursor, while copper oxide nanoparticles were obtained through a calcination method. During the calcination process, by controlling the calcination conditions, the porous structure of the MOF framework was successfully retained, leading to CuO-400 with a high catalytic activity and C2 production efficiency. Compared to CuO-n formed by the calcination of Cu(NO3)2, CuO-400 derived from MOFs exhibits a 1.6 times higher C2 activity as an electrocatalytic material at −1.15 V vs. RHE. [ABSTRACT FROM AUTHOR]

The extensive use of single-atom catalysts (SACs) has appeared as a significant area of investigation in contemporary study. The single-atom catalyst, characterized by its maximum atomic proficiency and great discernment of the transition-metal center, has a unique combination of benefits from both heterogeneous and homogeneous catalysts. Consequently, it effectively bridges the gap between these two types of catalysts, leveraging their distinctive features. The utilization of SACs immobilized on graphene substrates has garnered considerable interest, primarily because of their capacity to facilitate selective and efficient photocatalytic processes. This review aims to comprehensively summarize the progress and potential uses of SACs made from graphene in photocatalytic carbon dioxide (CO2) reduction and hydrogen (H2) generation. The focus is on their contribution to converting solar energy into chemical energy. The present study represents the various preparation methods and characterization approaches of graphene-based single-atom photocatalyst This review investigates the detailed mechanisms underlying these photocatalytic processes and discusses recent studies that have demonstrated remarkable H2 production rates through various graphene-based single-atom photocatalysts. Additionally, the pivotal roleof theoretical simulations, likedensity functional theory (DFT), to understand the structural functional relationships of these SACs are discussed. The potential of graphene-based SACs to revolutionize solar-to-chemical energy conversion through photocatalytic CO2 reduction and H2 production is underscored, along with addressing challenges and outlining future directions for this developing area of study. By shedding light on the progress and potential of these catalysts, this review contributes to the collective pursuit of sustainable and efficient energy conversion strategies to mitigate the global climate crisis. [ABSTRACT FROM AUTHOR]

Effective electrochemical reduction of carbon dioxide to formate under mild conditions helps mitigate the energy crisis but requires the use of high-performance catalysts. The addition of a third metal to the binary metal catalyst may further promote the electrochemical reduction of carbon dioxide to formate. Herein, we provided a co-electrodeposition method to grow CuSnBi catalysts on pretreated copper foam and discussed the effects of both pH value and molar ratio of metal ions (Cu2+, Sn2+, and Bi3+) in the electrodeposition solution on the electrocatalytic performance of CO2 to HCOO−. When the pH value of the electrodeposition solution was 8.5 and the molar ratio of Cu2+, Sn2+, and Bi3+ was 1:1:1, the electrode showed the highest FEHCOO− of 91.79% and the formate partial current density of 36.6 mA·cm−2 at −1.12 VRHE. Furthermore, the electrode kept stable for 20 h at −1.12 VRHE, and FEHCOO− was always beyond 85% during the electrolysis process, which is excellent compared to the previously reported ternary metal catalytic electrodes. This work highlights the vital impact of changes (pH value and molar ratio of metal ions) in electrodeposition liquid on catalytic electrodes and their catalytic performance, and refreshing the electrolyte is essential to maintain the activity and selectivity during the electrochemical reduction of CO2 to HCOO−. [ABSTRACT FROM AUTHOR]

The dry reforming of methane (DRM) is a promising method for controlling greenhouse gas emissions by converting CO2 and CH4 into syngas, a mixture of CO and H2. Ni-based catalysts have been intensively investigated for their use in the DRM. However, they are limited by the formation of carbonaceous materials on their surfaces. In this review, we explore carbon-induced catalyst deactivation mechanisms and summarize the recent research progress in controlling and mitigating carbon deposition by developing coke-resistant Ni-based catalysts. This review emphasizes the significance of support, alloy, and catalyst structural strategies, and the importance of comprehending the interactions between catalyst components to achieve improved catalytic performance and stability. [ABSTRACT FROM AUTHOR]

Due to ever-increasing global warming, the scientific community is concerned with finding immediate solutions to reduce or utilize carbon dioxide (CO2) and convert it in useful compounds. In this context, the reductive process of CO2 methanation has been well-investigated and found to be attractive due to its simplicity. However, it requires the development of highly active catalysts. In this mini-review, the focus is on biochar-immobilized nanocatalysts for CO2 methanation. We summarize the recent literature on the topic, reporting strategies for designing biochar with immobilized nanocatalysts and their performance in CO2 methanation. We review the thermochemical transformation of biomass into biochar and its decoration with CO2 methanation catalysts. We also tackle direct methods of obtaining biochar nanocatalysts, in one pot, from nanocatalyst precursor-impregnated biomass. We review the effect of the initial biomass nature, as well as the conditions that permit tuning the performances of the composite catalysts. Finally, we discuss the CO2 methanation performance and how it could be improved, keeping in mind low operation costs and sustainability. [ABSTRACT FROM AUTHOR]

The characteristics of industrial catalysts for conventional water-gas shifts, methanol syntheses, methanation, and Fischer-Tropsch syntheses starting from syngases are reviewed and discussed. The information about catalysts under industrial development for the hydrogenation of captured CO2 is also reported and considered. In particular, the development of catalysts for reverse water-gas shifts, CO2 to methanol, CO2-methanation, and CO2-Fischer-Tropsch is analyzed. The difference between conventional catalysts and those needed for pure CO2 conversion is discussed. The surface chemistry of metals, oxides, and carbides involved in this field, in relation to the adsorption of hydrogen, CO, and CO2, is also briefly reviewed and critically discussed. The mechanistic aspects of the involved reactions and details on catalysts' composition and structure are critically considered and analyzed. [ABSTRACT FROM AUTHOR]

The present paper describes a greener sustainable route toward the synthesis of NIPHUs. We report a highly efficient solvent-free process to produce [4,4′-bi(1,3-dioxolane)]-2,2′-dione (BDC), involving CO2, as renewable feedstock, and bis-epoxide (1,3-butadiendiepoxide) using only metal–organic frameworks (MOFs) as catalysts and cetyltrimethyl-ammonium bromide (CTAB) as a co-catalyst. This synthetic procedure is evaluated in the context of reducing global emissions of waste CO2 and converting CO2 into useful chemical feedstocks. The reaction was carried out in a pressurized reactor at pressures of 30 bars and controlled temperatures of around 120–130 °C. This study examines how reaction parameters such as catalyst used, temperature, or reaction time can influence the molar mass, yield, or reactivity of BDC. High BDC reactivity is essential for producing high molar mass linear non-isocyanate polyhydroxyurethane (NIPHU) via melt-phase polyaddition with aliphatic diamines. The optimized Al-OH-fumarate catalyst system described in this paper exhibited a 78% GC-MS conversion for the desired cyclic carbonates, in the absence of a solvent and a 50 wt % chemically fixed CO2. The cycloaddition reaction could also be carried out in the absence of CTAB, although lower cyclic carbonate yields were observed. [ABSTRACT FROM AUTHOR]

2–(1H–1,2,4–Triazol–3–yl)phenol (CAT–1) was used as an organocatalyst for the coupling reaction of CO2 and epoxides at an ambient temperature and atmospheric CO2 pressure (1 bar). This compound has a structure in which a hydrogen bond donor, a hydrogen bond acceptor, and another hydrogen bond donor are adjacent in sequence in a molecule. The binary catalytic system of CAT–1/nBu4NI showed TON = 19.2 and TOF = 1.60 h−1 under 1 bar CO2 at room temperature within 12 h using 2–butyloxirane. Surprisingly, the activity of CAT–1, in which phenol and 1H–1,2,4–triazole are chemically linked, showed a much greater synergistic effect than when simply mixing the same amount of phenol and 1H–1,2,4–triazole under the same reaction conditions. In addition, our system showed a broad terminal and internal epoxide substrate scope. [ABSTRACT FROM AUTHOR]

Two series of Ni and Co catalysts supported onto La-Al2O3 were prepared and the CO2 hydrogenation reactions investigated. The catalytic performance was evaluated in terms of the evolution with the reaction temperature of the CO2 conversion and product (CH4 and CO) yields, as well as specific activities (TOF) and apparent activation energies. CH4 was the favored product over both metals while the TOF for CH4 formation was about three times higher for Ni than Co at 240–265 °C. Metallic particle size effects were found, with the TOF for CH4 formation decreasing over both Ni and Co as the mean metallic size decreased. In contrast, the TOF for CO formation tended to increase at a decreasing particle size for the catalysts with the smallest Ni particle sizes. The apparent activation energies for Ni and Co were very similar and significantly decreased to values of 73–79 kJ/mol when the metallic dispersion increased. The catalysts were prepared using the all-in-one method, resulting in (poly)vinyl alcohol (PVA) being a key additive that allowed us to enhance the dispersion of Ni and Co to give very effective catalysts. This comparative study joins the few existing ones in the literature in which catalysts based on these metals operated under strictly the same reaction conditions. [ABSTRACT FROM AUTHOR]

Addressing the challenges associated with the highly exothermic nature of CO2 methanation, there is considerable interest in innovative catalyst designs on structural metallic supports. One promising solution in this regard involves thin films containing cobalt oxide within a carbon matrix, fabricated using the cold plasma deposition method (PECVD). The objective of this study was to search for a relationship between the molecular structure, nanostructure, and electronic structure of such films and their catalytic activity. The investigations employed various techniques, including X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), X-ray diffraction (XRD), UV-VIS absorption, and catalytic tests in the CO2 methanation process. Three types of films were tested: untreated as-deposited (ad-CoO), thermally post-treated (TT-CoO), and argon plasma post-treated (PT-CoO) films. Among these, TT-CoO exhibited the most favorable catalytic properties, demonstrating a CO2 conversion rate of 83%, CH4 selectivity of 98% at 400 °C, and stability during the catalytic process. This superior performance was attributed to the formation of nanoscale heterojunctions in the TT-CoO film, where p-type CoO nanocrystallites interacted with the n-type carbon matrix. This work provides compelling evidence highlighting the key role of nanoscale heterojunctions in shaping the properties of nanocatalysts in thermal catalysis. These findings suggest promising prospects for designing new catalytic systems by manipulating interactions at the nanoscale. [ABSTRACT FROM AUTHOR]

In this study, we report on how to design efficient catalysts for glucose oxidation via the transitional metal doping of nanohybrids of polyoxometalates (POMs) and metal-organic frameworks (MOFs). ZIF-67, a cobalt-based MOF, as well as phosphomolybdic acid (PMo), were used as precursors for the fabrication of pyrolyzed PMo@ZIF-67 (T-PMo@ZIF-67). A different amount of Ni2+ was doped into PMo@ZIF-67 to produce NixCoy@T-PMo@ZIF-67. Among them, Ni2Co2@T-PMo@ZIF-67 had the best performance. The power density of the fuel cell that used Ni2Co2@T-PMo@ZIF-67 as an anode catalyst was 3.76 times that of the cell that used active carbon as an anode catalyst. SEM and EDS mapping results indicate that Ni2Co2@T-PMo@ZIF-67 has a spherical structure and rough surface, and elements such as cobalt, nickel, and molybdenum are evenly distributed. XRD characterization indicates that Co3O4, CoMoO4, CoNiO4, and MoNiO4 co-exist in the composites. It is supposed that Co2+, Mo6+, and Ni2+ in the composites may have synergistic effects on the catalytic oxidation of glucose. [ABSTRACT FROM AUTHOR]

CO2 methanation offers a promising route for converting CO2 into valuable chemicals and energy fuels at the same time as hydrogen is stored in methane, so the development of suitable catalysts is crucial. In this review, the performance of catalysts for CO2 methanation is presented and discussed, including noble metal-based catalysts and non-noble metal-based catalysts. Among the noble metal-based catalysts (Ru, Rh, and Pd), Ru-based catalysts show the best catalytic performance. In the non-noble metal catalysts, Ni-based catalysts are the best among Ni-, Co-, and Fe-based catalysts. The factors predominantly affecting catalytic performance are the dispersion of the active metal; the synergy of the active metal with support; and the addition of dopants. Further comprehensive investigations into (i) catalytic performance under industrial conditions, (ii) stability over a much longer period and (iii) activity enhancement at low reaction temperatures are anticipated to meet the industrial applications of CO2 methanation. [ABSTRACT FROM AUTHOR]

A prepared FeZnNa@SiO2-C catalyst with graphitized carbon (C)-modified mesoporous SiO2 supports metal nanoparticles with the sol–gel method. The effect of adding metal Na and Zn promoters as a dispersion on the CO2 hydrogenation to low olefins was systematically studied. The results showed that Zn–Na, as a combination, could promote the absorption of CO2 and improved the conversion rate of CO2. Na as an alkaline substance can improve the absorption of more acidic CO2, which could increase the conversion rate of CO2 to 59.03%. Meanwhile, the addition of secondary metal Zn to Fe-based catalysts to form a surface alloy could alter the adsorption of CO2 and the activation of C-O bonds, inhibit the subsequent hydrogenation of olefins to paraffins, and facilitate the reduction of Fe2O3 and the formation of active Fe5C2 species. The formation of active Fe5C2 species was found in TEM and XRD, and the selectivity of the target product was 41.07%. The deep hydrogenation of olefins was inhibited, and the space–time yield (STY) of low olefins was raised again by inhibiting their deep hydrogenations, up to 0.0436. However, the corresponding STY did not increase infinitely with the increase of Na doping, and higher catalytic performance for CO2 hydrogenation could be exhibited when the Na doping reached 6.4%. Compared with Fe@SiO2-C catalyst, Na- and Zn-promoted Fe-based catalysts, prepared by the modified sol-gel method, can be used directly for highly efficient CO2 hydrogenation to low olefins and thus has a more promising application prospect in the future. [ABSTRACT FROM AUTHOR]

Reducing the amount of CO2 in the atmosphere is a very important task. Therefore, the development and search for new approaches to the synthesis of catalytic systems, allowing for the catalytic conversion of CO2 into valuable products, is an urgent task. In this work, the catalyst was obtained by the thermolysis of a double complex compound. In this regard, kinetic studies of the parameters of the thermolysis process of double complex salts-[Co(NH)3]6][Fe(CN)6] were additionally determined using isoconversion and model approaches of non-isothermal kinetics. The catalyst was studied using various physicochemical methods—X-ray diffraction (XRD), infrared (IR)-spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). It was shown that, at the stage of catalyst preparation, the formation of a CoFe alloy occurred, while the surface mainly consisted of carbon in sp2-hybridization, and the metals existed in the form of spinel CoFe2O4. It was shown that catalysts based on bimetallic salts were active in the process of hydrogenation of carbon dioxide without a pre-activation stage (CO2 conversion reached 28%, with a specific activity of 4.0 µmolCO2/gMe·s). It was established that it was possible to change the selectivity of the carbon dioxide hydrogenation process by pre-treating the catalyst with hydrogen (selectivity for methane formation in the presence of an unreduced catalyst is 46.4–68.0%, whereas in the presence of a reduced catalyst it is 5.1–16.5%). [ABSTRACT FROM AUTHOR]

This document discusses the process of CO2 methanation, which involves converting carbon dioxide and hydrogen gases into methane and water. This reaction is important for carbon capture and utilization strategies, as it allows for the recycling of CO2 emissions into valuable methane. The document explores different catalysts and reactor types used in CO2 methanation, as well as studies on catalyst deactivation and regeneration, reactor performance prediction, plasmonic catalysts, chemical reduction methods, and fluidized-bed reactor design. The Special Issue on "Catalytic CO2 Methanation Reactors and Processes" provides valuable insights into catalyst preparation, reaction kinetics, and reactor modeling, contributing to advancements in renewable energy storage. [Extracted from the article]

Syngas is produced through the carbon dioxide reforming of methane. The traditional nickel-based catalysts are substantially destroyed by carbon deposition. The reforming reaction was conducted in a tubular microreactor at 700 °C using bimetallic Ni catalysts supported over 37% Al2O3 and 63% MgO mixtures. The impregnation process formed the catalysts, which were subsequently examined by N2-physisorption, XRD, H2-TPR, TGA, and Raman spectroscopy. The 2.5Ni+2.5Co/37%Al2O3+63%MgO bimetallic catalyst, which displayed 72% and 76% conversions of CH4 and CO2 over the course of a seven-hour procedure, was discovered to be the most active in DRM. The bimetallic catalyst with the largest weight loss in TGA, 2.5Ni+2.5Fe-MG63, had a loss of 61.3%, a difference of 26% and 21% in the activity performance of CH4 and CO2, respectively, of the tested bimetallic Ni catalysts was recorded. The long-time of 30 h on-stream CH4 and CO2 conversion reactions for 2.5Ni+2.5Co-MG63 and 2.5Ni+2.5Ce-MG63 catalysts showed the catalysts' high stability. The TPO analysis for the 2.5Ni+2.5Cs-MG63 catalyst showed a peak at 650 °C, attributed to the oxidation of the filamentous carbon, whereas the TPO analysis for the 2.5Ni+2.5Co-MG63 catalyst depicted a peak at 540 °C, ascribed to the presence of amorphous/graphite carbon. [ABSTRACT FROM AUTHOR]

The conversion of carbon dioxide to fuels and chemicals is a promising long-term approach for mitigating CO2 emissions. Despite extensive experimental efforts, a fundamental understanding of the bimetallic catalytic structures that selectively produce the desired products is still lacking. Here, we report on a computational surface science approach into the effect of the Fe doping of Co(111) surfaces in relation to CO2 hydrogenation to C1 products. Our results indicate that Fe doping increases the binding strength of surface species but slightly decreases the overall catalytic activity due to an increase in the rate-limiting step of CO dissociation. FeCo(111) surfaces hinder hydrogenation reactions due to lower H coverages and higher activation energies. These effects are linked to the Lewis basic character of the Fe atoms in FeCo(111), leading to an increased charge on the adsorbates. The main effect of Fe doping is identified as the inhibition of oxygen removal from cobalt surfaces, which can be expected to lead to the formation of oxidic phases on bimetallic FeCo catalysts. Overall, our study provides comprehensive mechanistic insights related to the effect of Fe doping on the catalytic behavior and structural evolution of FeCo bimetallic catalysts, which can contribute to the rational design of bimetallic catalysts. [ABSTRACT FROM AUTHOR]

The co-electrolysis of CO2 and H2O at an intermediate temperature is a viable approach for the power-to-gas conversion that deserves further investigation, considering the need for green energy storage. The commercial solid oxide electrolyser is a promising device, but it is still facing issues concerning the high operating temperatures and the improvement of gas value. In this paper we reported the recent findings of a simple approach that we have suggested for solid oxide cells, consisting of the addition of a functional layer coated to the fuel electrode of commercial electrochemical cells. This approach simplifies the transition to the next generation of cells manufactured with the most promising materials currently developed, and improves the gas value in the outlet stream of the cell. Here, the material in use as a coating layer consists of a Ni-modified La0.6Sr0.4Fe0.8Co0.2O3, which was developed and demonstrated as a promising fuel electrode for solid oxide fuel cells. The results discussed in this paper prove the positive role of Ni-modified perovskite as a coating layer for the cathode, since an improvement of about twofold was obtained as regards the quality of gas produced. [ABSTRACT FROM AUTHOR]

The CO2 electrochemical reduction reaction (CO2RR) is one of the most promising methods to reduce carbon dioxide emissions and store energy. At the same time, the pathways of CO2 reduction reaction are diverse and the products are abundant. Converting carbon dioxide to C2+ products, a critical feedstock, requires a C–C coupling step with the transfer of more than 10 electrons per molecule and, hence, is kinetically sluggish. The production of some key adsorptions is conducive to the formation of C2+ products. In this work, we used in situ techniques to figure out the reason why hexagonal-close-packed (hcp) Co nanosheets (NSs) have high activity in CO2RR to ethanal. According to the in situ Raman spectra, the high local pH environment on the catalyst surface is favorable for CO2RR. The high pH at low potentials not only suppresses the competing hydrogen evolution reaction but also stimulates the production of COCO* intermediate. The isotopic labeling experiment in differential electrochemical mass spectrometry (DEMS) provides a possible sequence of the products. The 13CO is generated when we replace 12CO2 with 13CO2, which identifies the origin of the products. Besides, in situ electrochemical impedance spectroscopy (EIS) shows that the hcp Co at −0.4 V vs. RHE boosts the H2O dissociation and proton transfer, feeding sufficient H* for CO2 to *COOH. In the end, by analyzing the transmission electronic microscopy (TEM), we find that the Co (002) plane may be beneficial to the conversion of CO2 and the adsorption of intermediates. [ABSTRACT FROM AUTHOR]

New heterojunction materials (HJs) were synthesized in-situ by molecularly bonding the monomers of a triazine-based covalent organic framework (bulk COF) on the template of exfoliated carbon nitride (g-C3N4). The photocatalysts reduced carbon dioxide to carbon monoxide in aqueous dispersions under UV irradiation. The g-C3N4 showed production of 6.50 μmol CO g−1 h−1 and the bulk COF of 2.77 μmol CO g−1 h−1. The CO yield was evaluated in sustainability photoreduction cycles and their CO2 uptake capacity and isosteric heat of adsorption were estimated. All the heterojunction photocatalysts obtained ameliorated CO production rates compared to the bulk COF. Finally, the influence of the Pt co-catalyst on the photocatalytic activities was determined without the addition of any sacrificial agent, and the COF:g-C3N4 heterojunction with the ratio of 1:10 was proven to be a photocatalytic system with an optimum and selective, CO yield of 7.56 μmol g−1 h−1. [ABSTRACT FROM AUTHOR]

Cu-based catalysts for efficient C2+ production from CO2 electrocatalytic reduction reaction (CO2ERR) exhibit significant promise, but still suffer from ambiguous mechanisms due to the intrinsic structure instability during electroreduction. Herein, we report an oxide-derived copper nanowire bundle (OD-Cu NWB) for efficient CO2ERR to C2+ products. OD-Cu NWBs with a well-preserved nanowire bundle morphology lead to promoted multi-carbon production compared to commercial copper powders. The formation of OD-Cu NWBs shows a great dependence on the precipitation/calcination temperatures and per-reduction potentials, which further influence the ultimate CO2ERR performance correspondingly. The optimized preparation parameters for the formation of a well-ordered nanowire bundle morphology are found, leading to a preferred C2+ production ability. Besides the nanowire bundle morphology, the oxide-derived Cu essence of OD-Cu NWBs with stabilized Cu+ species from per-reduction also promotes the CO2ERR activity and facilitates the C-C coupling of key intermediates for C2+ production. This work provides a facile strategy and inspiration for CO2ERR catalyst developments targeting high-valued multi-carbon products. [ABSTRACT FROM AUTHOR]

Ni-supported SBA-15 catalysts were prepared by physical mixing of Ni(NO3)2·6H2O and SBA-15 (Ni/SBA-15-M) and in the presence of citric acid as the complexing agent (Ni/SBA-15-M-C). Moreover, an Ni-supported SBA-15 catalyst was also prepared by the conventional incipient impregnation method (Ni/SBA-15-I). All the catalysts were systematically evaluated for carbon dioxide reforming of methane (CDR) at CO2/CH4 = 1.0, gas hourly space velocity of 60,000 mL·g−1·h−1, and reaction temperature of 700 °C. The characterization results show that the Ni particle size of Ni/SBA-15-M-C is significantly smaller than that of Ni/SBA-15-M due to the coordination effect of citric acid and Ni2+. Consequently, the Ni/SBA-15-M-C exhibits superior anti-coking and anti-sintering during the CDR-operated period because of the higher Ni dispersion and stronger Ni–support interaction. Compared to the Ni/SBA-15-I, the physical mixing of nickel salt and mesoporous material for preparing of Ni-based catalyst is easy to operate, although the crystal size and catalytic performance of Ni/SBA-15-C are very similar to that of Ni/SBA-15-M-I. Thus, the efficient and easily controlled catalyst structure makes the physical mixing strategy very promising for preparing highly active and stable CDR catalysts. [ABSTRACT FROM AUTHOR]

The adsorption and hydrogenation of carbon dioxide on γ-Al2O3(110) surface-supported copper clusters of different sizes are investigated using density functional theory calculations. Our results show that the activation of CO2 is most obvious at the Cu/γ-Al2O3 interface containing the size-selected Cu4 cluster. It is interesting that the CO2 activation is more pronounced at the partially hydroxyl-covered interface. The catalytic mechanisms of CO2 conversion to methanol at the dry and hydroxylated Cu4/γ-Al2O3 interfaces via the formate route and the pathway initiated through the hydrogenation of carbon monoxide produced by the reverse water–gas shift reaction are further explored. On both interfaces, the formate pathway is identified as the preferred reaction pathway, in which the hydrogenation of HCOO to H2COO is the rate-limiting step (RLS). However, since the surface OH group can act as a hydrogen source in some elementary reactions, unlike the dry surface, the production of H2COOH species along the formate pathway is found at the hydroxylated interface. In addition, the introduction of OH at the interface leads to an increase in the kinetic barrier of the RLS, indicating that surface hydroxylation has a negative effect on the catalytic activity of CO2 conversion to CH3OH at the Cu/γ-Al2O3 interface. [ABSTRACT FROM AUTHOR]