High CO2 Selectivity Research Articles

Porous nickel-based catalyst doped with fluorine can efficiently electrocatalyze the reduction of CO2 to CO

The electrocatalytic carbon dioxide reduction reaction (CO2RR) to produce high-value-added products is considered an effective method for achieving carbon neutrality and mitigating greenhouse effects. However, due to the coexistence of competing hydrogen evolution reaction (HER) alongside CO2RR, the selectivity of catalysts still requires improvement. Moreover, the complex preparation methods and high cost of noble metal catalysts pose challenges. Therefore, it is crucial to find a catalyst that is easy to prepare, cost-effective in terms of raw materials, and exhibits high selectivity. In this study, chitosan was utilized as a carbon source for the catalyst, with nickel as the primary metal. Through gasification at 650°C and morphology control via formation of hollow structures using Cd metal particles, along with F doping modification, an electrocatalyst (NiCd650F0.2) was prepared. This catalyst exhibited the highest CO selectivity of 90.3 % at −1 V vs. RHE, with a CO partial current density of −10.68 mA·cm−2 at −1.2 V vs. RHE. Stability tests demonstrated that its selectivity and activity remained excellent over 8 hours. Density functional theory (DFT) calculations further indicated that F doping significantly lowers the adsorption energy barrier of reactions, promoting reaction kinetics and enhancing catalyst selectivity.

Hydroxylated TiO2-induced high-density Ni clusters for breaking the activity-selectivity trade-off of CO2 hydrogenation

The reverse water gas shift reaction can be considered as a promising route to mitigate global warming by converting CO2 into syngas in a large scale, while it is still challenging for non-Cu-based catalysts to break the trade-off between activity and selectivity. Here, the relatively high loading of Ni species is highly dispersed on hydroxylated TiO2 through the strong Ni and −OH interactions, thereby inducing the formation of rich and stable Ni clusters (~1 nm) on anatase TiO2 during the reverse water gas shift reaction. This Ni cluster/TiO2 catalyst shows a simultaneous high CO2 conversion and high CO selectivity. Comprehensive characterizations and theoretical calculations demonstrate Ni cluster/TiO2 interfacial sites with strong CO2 activation capacity and weak CO adsorption are responsible for its unique catalytic performances. This work disentangles the activity-selectivity trade-off of the reverse water gas shift reaction, and emphasizes the importance of metal−OH interactions on surface.

Synergistic integration of zeolite engineering and fixed-bed column design for enhanced biogas upgrading: Adsorbent synthesis, CO2/CH4 separation kinetics, and regeneration assessment

Biogas, a renewable energy vector derived from anaerobic digestion of organic waste, requires CO2 separation to enhance its calorific value for engine fuel. This study integrates CO2/CH4 separation in biogas using a novel approach integrating dual chemically-activated zeolites and fixed-bed column purification. Biogas produced via CSTR/ultrafiltration (69 % CH4, 30 % CO2, 14 ppm H2S) was further upgraded using HCl + NaOH and H2SO4 + NaOH activated zeolites. Optimal absorption capacity of 97.77 ± 0.01 % was achieved at 140 mesh, 60-minute H2SO4 + NaOH activation, 2-hour calcination (400 °C), and 200 mL/min flow rate. Breakthrough was observed at 18.12 min. Langmuir isotherm (R2 = 0.9992) and Elovich kinetics (R2 = 0.9846) best described the adsorption process. XRD analysis showed significant crystal size reduction post-activation (53.31 nm to 16.90 nm). Notably, BET analysis revealed enhanced surface properties surface area of 286.71 m2/g, pore volume of 0.213 cc/g, and pore diameter of 3.532 Å. An innovative dual-column system with non-isothermal TSA protocol optimized CO2 adsorption (30 mins) and desorption (17 mins, 40 °C, 100 mL/min), yielding superior near-pure methane biogas (99.29 % CH4, 0.66 % CO2, trace H2S). A methane loss of 2.75 % during upgrading demonstrated high CO2 selectivity. This synergistic approach presents a promising solution for sustainable biogas purification and engine fuel applications.

Disentangling the efficient photocatalytic reduction of CO2 by a stable UiO-66-NH2/Cs2AgBiBr6 catalyst

The compelling global warming crisis as well as extraterrestrial artificial light synthesis craves photocatalytic reduction of CO2 into fuels and value-added chemicals, for which efficient and robust catalysts with high selectivity and conversion rate is a prerequisite but hitherto a rarity. Herein we create a lead-free double metal perovskite of Cs2AgBiBr6, coupling with mesoporous/microporous UiO-66-NH2 MOF to form type-II heterojunctions for efficient photocatalytic reduction of CO2 with a high CO selectivity of 95 % at an electron consumption rate of 33 μmol g−1 h−1 (13.4 μmol g−1 h−1 for CO and 0.72 μmol g−1 h−1 for CH4). Multilayered mesoporous MOF particles manifest higher catalytic activity than their microporous counterparts due to the highly open mesoporous channels and larger pore volume of the former. Femtosecond transient absorption in combination with in situ infrared spectroscopic measurements disentangle the underlying mechanism accounting for the high product selectivity: the ultrafast electron transfer of 12.3 ps from Cs2AgBiBr6 to UiO-66-NH2-2 enables efficient charge separation; primary *COOH intermediates and rapid CO desorption from Bi-based photocatalyst lead to dominant CO product. Moreover, the MOF crystals maintain stability after γ-rays irradiation equivalent of over 45-year accumulation in a typical earth orbit, hinting their promising potential in extraterrestrial artificial light synthesis.

Impact of metal precursor and molar ratios on adsorption and separation of CO2 and CH4 by SOD-ZIF-67 prepared using green solvent-free synthesis

The subclass of metal-organic frameworks (MOFs) known as SOD-ZIF-67 (Sodalite Co (mIm)2, with mIm = 2-methylimidazole) has demonstrated exceptional performance in carbon dioxide (CO2) adsorption and separation. Traditional synthesis methods for SOD-ZIF-67 are often time-consuming and require significant quantities of organic solvents. This study introduces an enhanced, eco-friendly, solvent-free method for synthesizing SOD-ZIF-67. In this approach, SOD-ZIF-67 is produced within 1 h by mechanically grinding a cobalt (Co) metal precursor with an organic linker (mIm), eliminating the need for solvents. The properties of the synthesized SOD-ZIF-67 samples were confirmed through various characterization techniques. Thermal stability tests indicated that the synthesized SOD-ZIF-67 could endure temperatures up to 673 K. Among the samples prepared with different molar ratios, the SOD-ZIF-67 sample with a Co to HmIm molar ratio of 2:1 (denoted as Z-2) demonstrated the highest BET surface area and pore volume, measuring 1923 m2/g and 0.72 cm3/g, respectively. Z-2 exhibited uniform and narrow ultramicropores measuring 0.54 nm, and demonstrated a CO2 adsorption capacity of 91.52 mg (CO2)/g (2.08 mmol/g) at 298 K and 100 kPa. The material showed high selectivity for CO2 over N2 and CH4, with selectivities of 20.44 for CO2/N2 (0.15:0.85) and 4.28 for CO2/CH4 (0.5:0.5). Additionally, breakthrough experiments with CO2/N2 and CO2/CH4 mixtures validated its dynamic separation efficiency, underscoring Z-2′s suitability for selective CO2 capture from flue gases and natural gas purification.

Regulation of surface oxygen vacancy of Cu-CeO2/TiO2 heterostructures via fast Joule heating method for enhanced CO2 electrochemical reduction

Strict control of carbon emissions is crucial for expediting the achievement of carbon neutrality. However, the current CO2RR electrocatalytic exhibits numerous shortcomings that impede the enhancement of catalytic activity. Issues such as lengthy catalyst preparation times, and high levels of precious metal content. Additionally, the aggregation of ultrafine nanoparticles contributes to a rapid deterioration in catalytic performance. Herein, a Joule-heating method is efficiently utilized to synthesize heterostructures nano-catalysts for CO2 electroreduction on carbon cloth substrates. This method takes advantage of the thermoelectric coupling of the carbon cloth to achieve carbothermal reduction, while also regulating phase composition and introduction of oxygen vacancies. The Cu-CeO2/TiO2/CC catalyst synthesized in this method showed a current density in CO2 of −32 mA·cm−2 at −1.0 V (vs. RHE). Notably, this catalyst demonstrated high CO selectivity and Faraday efficiency (FECO) of up to 82.5 % at a low potential of −0.3 V (vs. RHE). Optimal electrochemical performance is achieved at a power of 40 W. The ultra-fast temperature change process prevented the agglomeration of catalyst particles and facilitated the construction of a stable heterogeneous interface with a high oxygen vacancy concentration. In conclusion, this study presents a promising approach, particularly for the rapid preparation of low-cost, highly selective non-precious metal electrocatalysts.

Amphiphilic heterojunctions with atomically dispersed copper–alkynyl active units for highly efficient CO2 photoreduction

The efficiency of CO2 photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO2 and H2O over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (IV-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/IV-BX) for visible-light-driven CO2 photoreduction. CA-CP/IV-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g−1 h−1 coupled with O2 releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO2, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO2 reduction and H2O oxidation, but also promotes charge separation and proton feeding, boosting CO2 photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO2 reduction and H2O oxidation.

CoCorrole-Functionalized PCN-222 for Carbon Monoxide Selective Adsorption.

The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm-ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O2, CO2, N2, opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO2 physisorption, allowing the co-detection of CO and CO2. In this work, PCN-222, a stable Zr-based MOF made from Ni(TCPP) with natural vacancies, has been used as a porous matrix for the grafting of electron-poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN-222 was observed. At 1 atm, the adsorbed CO(g) volumes measured for the best materials were 12.15 cm3 g-1 and 14.01 cm3 g-1 for CoCorr2@PCN-222 and CoCorr3@PCN-222 respectively, and both materials exhibited high CO chemisorption and selectivity against O2, N2, and CO2 at low pressure due to the highest energy of the chemisorption process vs physisorption.

Fabrication of a high-performance MOF-COP-based porous hollow fiber membrane for carbon dioxide separation

A thin-film nanocomposite (TFNC) hollow fiber membrane with high CO2 permeability and selectivity was synthesized for the separation of carbon dioxide, a major greenhouse gas. A highly porous polyethersulfone (PES) hollow fiber membrane support with a porous structure was first fabricated using heat and pressure treatments, and a thin film was prepared via interfacial polymerization by reacting polyethylenimine (PEI) with 1,3,5-benzenetricarbonyl trichloride (TMC) on the surface of the PES support. A metal–organic framework (MOF)-covalent organic polymer (COP) complex, obtained via polycondensation between an UiO-66-NH2 based MOF and a piperazine- and cyanuric chloride-based COP, was then added to the TFNC to prepare the mixed matrix membrane. The complex contributed to reducing defects between the porous support and the coating layer and additionally led to high CO2 permselectivity by providing a CO2 permeation pathway within the support. The newly prepared TFNC hollow fiber membrane contributed to its excellent separation performance, as evidenced by a CO2 permeability of 352 GPU and a CO2/N2 ideal selectivity of 75 after optimization of the MOF-COP content.

Torrefaction of Cassia fistula seeds for sequestration of aqueous and gaseous pollutants: Experimental and computational approach

Contamination of water bodies due to pharmaceutical pollutants including antibiotics is growing day by day due to enhanced consumption of these molecules. Biochar is a competent material for wastewater treatment due to ease of preparation as well as high adsorption capability towards desired pollutants. Cassia fistula biochar (CFB) was prepared by torrefaction process in an inert atmosphere. Owing to a large surface area of 672.3 m2/g, the purpose of this work is to carry out adsorption studies of three antibiotics, namely, ciprofloxacin (CFX), levofloxacin (LVX) and diclofenac sodium (DFC) in aqueous phase as well as for the sequestration of carbon dioxide in gaseous phase. The batch adsorption studies were carried and effects of various operational conditions were studied. The maximum adsorption capacities for CFX, LVX, and DFC were found to be 607.86 mg/g, 68.27 mg/g and 160.51 mg/g respectively under the optimum pH 6.0 for all the three adsorbates, contact time of 60 minutes for CFX, LVX and 20 minutes for DFC at room temperature condition of 298 K. Various operational parameters were optimized using Response Surface Methodology (RSM). Isotherm and kinetics studies for the adsorption of all three drugs followed Langmuir model (R2 >0.99) and pseudo-second order kinetics (R2 >0.95). Thermodynamic studies show the adsorption of all three drugs were enthalpy driven spontaneous processes. Fixed bed studies were performed showing the applicability of CFB for larger sample volumes. DFT calculations showed strong attractive interaction of CFB with all the three drug molecules. The same material has been applied for capture of carbon dioxide at different temperatures. The CO2 capture studies showed maximum adsorption capacity of 64.78 cc/g at 273 K owing to activation of CFB with high CO2 selectivity of 14.29 with respect to nitrogen. Hence, a multipurpose adsorbent has been thoroughly studied with environmental sustainability factor of 0.03.

Molecular Engineering of Porous Fe-N-C Catalyst with Sulfur Incorporation for Boosting CO2 Reduction and Zn-CO2 Battery.

Transition metal-nitrogen-carbon (M-N-C) catalysts have emerged as promising candidates for electrocatalytic CO2 reduction reaction (CO2RR) due to their uniform active sites and high atomic utilization rate. However, poor efficiency at low overpotentials and unclear reaction mechanisms limit the application of M-N-C catalysts. In this study, Fe-N-C catalysts are developed by incorporating S atoms onto ordered hierarchical porous carbon substrates with a molecular iron thiophenoporphyrin. The well-prepared FeSNC catalyst exhibits superior CO2RR activity and stability, attributes to an optimized electronic environment, and enhances the adsorption of reaction intermediates. It displays the highest CO selectivity of 94.0% at -0.58V (versus the reversible hydrogen electrode (RHE)) and achieves the highest partial current density of 13.64mA cm-2 at -0.88V. Furthermore, when employed as the cathode in a Zn-CO2 battery, FeSNC achieves a high-power density of 1.19mW cm-2 and stable charge-discharge cycles. Density functional theory calculations demonstrate that the incorporation of S atoms into the hierarchical porous carbon substrate led to the iron center becoming more electron-rich, consequently improving the adsorption of the crucial reaction intermediate *COOH. This study underscores the significance of hierarchical porous structures and heteroatom doping for advancing electrocatalytic CO2RR and energy storage technologies.

Hierarchically porous carbon foams coated with carbon nitride: Insights into adsorbents for pre-combustion and post-combustion CO2 separation

Adsorption is fundamental to many industrial processes, including separation of carbon dioxide from other gases in pre- or post-combustion gas mixtures. Adsorbents should have high capacity and selectivity, which are both intimately linked with surface area, pore size distribution, and surface energy. Porous carbons are cheap and scalable adsorbents, but greater understanding of how their textural properties and surface chemistry affects their performance is needed. Here, we investigate the effect of nitrogen doping on CO2 adsorption. Microporous carbon foams with large surface area (>2500 m2 g−1) and pore volume (1.6 cm3 g−1) are synthesized, then coated with varying amounts of carbon nitride (up to 17 at% nitrogen) to achieve high CO2 uptake (25.5 mmol g−1) and selectivity (CO2:N2 = 21), whilst also giving insights into the relationship between structure and function. At low pressure (relevant to post-combustion capture), moderate carbon nitride loading leads to enhanced uptake and selectivity by combining large ultramicropore volume with the introduction of Lewis base sites, leading to high isosteric heat of adsorption. Higher carbon nitride loading further increases selectivity but lowers uptake by blocking micropores. Conversely, at high pressure (relevant to pre-combustion capture) the uncoated carbon foam displays superior uptake, because mesoporosity is the dominant factor in this regime, rather than the presence of ultramicropores. Finally, the samples displayed excellent regeneration under repeated adsorption–desorption cycles, and breakthrough curves were measured. These results underscore the delicate balance required for optimal material design when applying porous carbon adsorbents to CO2 separation processes. Moving forward, improved adsorbents will contribute to the proliferation of carbon capture and storage (CCS) and carbon capture and utilisation (CCU) technologies, ultimately contributing reduced anthropogenic CO2 emissions.

Efficient Preparation and Optimization of Activated Carbon Monoliths from Resorcinol-Formaldehyde Resins for CO2 Capture

Activated carbon monoliths with developed porosity, high surface area and excellent adsorption properties were successfully prepared from resorcinol-formaldehyde resins using a physical activation method. The primary objective of this study was to examine the impact of key parameters, namely hexamethylenetetramine content (0.08–0.2 g), pyrolysis heating rate (5–20 °C/min) and activation time (1–7 h), on the final characteristics of the activated carbon in order to identify the optimal operating conditions to achieve the desired properties. All the cured resin samples were pyrolyzed at 900 °C under a nitrogen atmosphere, while the activation process took place in the presence of CO2. The evaluation of the activated carbon materials was based on the CO2 adsorption capacity and BET surface area, micropore area and total pore volume, which were employed as the criteria for selecting the optimal activated carbon. The synthesized porous carbon monoliths exhibited good properties: high BET surface area (900 m2/g), high CO2 adsorption capacity (5.33 mmol/g at 0 °C and 1 bar, 3.8 mmol/g at 25 °C and 1 bar) and good CO2 selectivity for CO2/N2 and CO2/CH4 mixtures. These results were obtained with a pyrolysis heating rate of 5 °C/min and a 3 h activation period.

Surface oxygen vacancy regulation and active metal doping for Cu-Al based spinel catalysts synthesis toward high-efficiency reverse water-gas shift reaction

The reverse water-gas shift (RWGS) reaction is of great significance to convert CO2 to valuable feedstocks. Reasonable design and preparation of catalysts is necessary to achieve high CO2 conversion and CO selectivity. In this study, a series of Cu-Al based spinel catalysts were synthesized by coprecipitation-calcination method or A-site doped with active metal (Co, Zn, Mg, and Fe) for the RWGS reaction. The results indicated that the surface oxygen vacancies and crystal structure of CuAl2O4 can be regulated by calcination temperature. Remarkably, the CuAl-800 catalyst exhibits the highest CO2 conversion rate (62.7 %) with 100 % CO selectivity at 500 °C. Excessive calcination temperatures (> 800 °C) resulted in a well-defined spinel structure, but decreased surface oxygen vacancies and CO2 conversion rate. At calcination temperatures < 800 °C, surface oxygen vacancies increased, but the formation of CuO impurities which irreversibly converted to Cu2O during reduction, decreased catalytic activity. Compared with Zn, Mg and Fe, Co doping can significantly improved the reactivity of CuAl2O4 catalyst in RWGS reaction at 500 °C, increasing the CO2 conversion rate by 8 % while maintaining 100 % CO selectivity. The main reason is that Co doping not only effectively improves the integrity and stability of spinel structure of CuAl2O4, but also enhances its ability to dissociate and activate H species through interfacial sites of CuO-OV-CuXCo1-XAl2O4, thus further enhancing its catalytic conversion ability of CO2 to CO. These results enrich the understanding of surface chemistry of CuAl2O4 spinel and lay an important theory foundation for design of spinel-based catalysts for RWGS reaction.

Evaluating the selectivity of CO2 reduction reaction on elementary metal particles with DFT calculations

Electrocatalytic CO2 reduction reaction (CO2RR) towards two-electron products is a competent technique to convert renewable electricity into chemical energy at ambient conditions. Poly-crystalline metals are well-known electrocatalysts for CO2RR. However, no theoretical research was reported to date that evaluates the selectivity of two-electron CO2RR on metal particles. In this work, we proposed a paradigm to evaluate the product selectivity of CO2RR on metal particles. The product selectivity on three low-index surfaces of six metals (In, Pb, Ag, Au, Ni, and Pt) was firstly determined based on the detailed reaction mechanisms established for CO2RR to products of HCOOH and CO. Then, the product selectivity of CO2RR on the first four metal particles was evaluated using the effective free energy barrier which accounts for the facet dependence of CO2RR on the metal particles. The computational results well rationalize the experimental observations, namely preference of HCOOH to CO on the In and Pb particles with higher HCOOH selectivity on the Pb particle, while CO preferred to HCOOH on the Ag and Au particles with higher CO selectivity on the Au particle.

Comparative simulations of methanol steam reforming on PdZn alloy using kinetic Monte Carlo and mean-field microkinetic model.

Methanol steam reforming (MSR) is an attractive route for producing clean energy hydrogen. PdZn alloys are extensively studied as potential MSR catalysts for their stability and high CO2 selectivity. Here, we investigated the reaction mechanism using density functional calculations, mean-field microkinetic modeling (MF-MKM), and kinetic Monte Carlo (kMC) simulations. To overcome the over-underestimation of CO2 selectivity by log-kMC, an ads-kMC algorithm is proposed in which the adsorption/desorption rate constants were reduced under certain requirements and the diffusion process was treated by redistributing surface species each time an event occured. The simulations show that the dominant pathway to CO2 at low temperatures is CH3OH → CH3O → CH2O → H2COOH → H2COO → HCOO → CO2. The ads-kMC predicted OH coverage is 2-3 times that of MF-MKM, while they produce similar coverage for other species. Analyses indicate that surface OH promotes the dehydrogenation of CH3OH, CH3O, and H2COOH significantly and plays a key role in the MSR process. The dissociation of water/methanol is the most important rate-limiting/rate-inhibiting step. The CO2 selectivity obtained by the two methods is close to each other and consistent with the experimental trend with temperature. Generally, the ads-kMC results agree with the MF-MKM ones, supporting the previous finding that kMC and MF-MKM predict similar results if the diffusion is very fast and adsorbate interactions are neglected. The present study sheds light on the MSR process on PdZn alloys, and the proposed scheme to overcome the stiff problems in kMC simulations is worthy of being extended to other systems.

Constructing bio-inspired anion channels by dual-ligand MOF in membranes for efficient CO2 separation

One of the biggest challenges of Pebax-based membranes is how to simultaneously achieve high CO2 permeability and selectivity. Hence, three-dimensional L-histidine@zeolitic imidazole framework-8 (His@ZIF-8 (X)) was synthesized as dual-ligand metal-organic framework (MOF), and it was incorporated into the Pebax 1657 matrix to fabricate mixed matrix membranes (MMMs) for efficient CO2 separation. The three-dimensional His@ZIF-8 (X) with abundant His mimicked anion transport protein, and it constructed bio-inspired anion transport channels. His@ZIF-8 (X) played important functions when it was incorporated into the MMMs: the bio-inspired active sites of His@ZIF-8 with the Zn2+ bonded to three Hmim and one water molecule had similar function with the active sites in carbonic anhydrase (CA), which can catalyze CO2 into water-soluble bicarbonate (HCO3−). Subsequently, the bio-inspired anion transport channels allowed HCO3− to rapidly transport, because they had His residues that can form anion-dipole interactions with HCO3− in His@ZIF-8 (X). Therefore, Pebax 1657/His@ZIF-8 (X) MMMs were endowed with the excellent separation performance due to the bio-inspired anion transport channels constructed by His@ZIF-8 (X). In particularly, MMM contained 4 wt% His@ZIF-8 (12.5) achieved the optimal separation performance with a CO2 permeability of 541 ± 9 Barrer and CO2/CH4 selectivity of 35 ± 0.6. The work implies that the construction of the bio-inspired anion transport channels within MMMs was a potential strategy for efficient CO2 separation.

Understanding Limitations in Electrochemical Conversion to CO at Low CO2 Concentrations.

Low-temperature electrochemical CO2 reduction has demonstrated high selectivity for CO when devices are operated with pure CO2 streams. However, there is currently a dearth of knowledge for systems operating below 30% CO2, a regime interesting for coupling electrochemical devices with CO2 point sources. Here we examine the influence of ionomer chemistry and cell operating conditions on the CO selectivity at low CO2 concentrations. Utilizing advanced electrochemical diagnostics, values for cathode catalyst layer ionic resistance and electrocatalyst capacitance as a function of relative humidity (RH) were extracted and correlated with selectivity and catalyst utilization. Staying above 20% CO2 concentration with at least a 50% cathode RH resulted in >95% CO/H2 selectivity regardless of the ionomer chemistry. At 10% CO2, however, >95% CO/H2 selectivity was only obtained at 95% RH under scenarios where the resulting electrode morphology enabled high catalyst utilization.

Optimizing Mo2C-based catalytic system for efficient CO2 conversion and CO selectivity through carbon-nitrogen supporting and potassium promotion

Preparing highly active, stable, and selective catalysts for the reverse water gas shift (RWGS) reaction is challenging because of the aggregation of the active catalyst at high RWGS reaction temperatures and deactivation of the active sites. Herein, we present a comparative evaluation and optimization of a molybdenum carbide system using a carbon-nitrogen (CN) support and alkali promotion. Hydrothermally prepared MoO3 nanorods were carburized at 700 °C using H2:CO (4:1) to prepare unsupported Mo2C, while CN-supported Mo2C (Mo2C@CN) was prepared using Mo-based metal-organic framework (Mo-MOF) as a sacrificial template. The as-prepared Mo2C@CN catalytic system was found to be highly active in the RWGS reaction in comparison with the unsupported Mo2C, where CO2 conversion percentage was around 76 % at 700 °C, combined with high CO selectivity (87 %) and very reduced CH4 selectivity (2 %). The addition of potassium as a promoter enhanced CO selectivity (99 %). The active catalyst performance was stable during the catalysis process and for up to 100 h, which imposes the effect of the CN support in preventing the aggregation of Mo2C and keeping its active sites in direct contact with the reactant. This work presents an effective strategy for improving the active catalyst dispersion and reducibility in synergy with the promoter effect to optimize the RWGS reaction output.

Efficient electroreduction of CO2 into CO in flow cell with a metal-free ternary-doped porous carbon

Herein, a series of metal-free N, P, and Se ternary-doped porous carbon electrocatalysts, referred as "SePNC" as metal-free electrocatalysts, was prepared. This study shows that, the optimal electrocatalyst of SePNC-1050, which prepared at 1050 ℃, has high CO selectivity with Faraday efficiency of 94.8% for CO, and a byproduct of 5.2% H2. After continuous electrolysis for 12 h, the Faraday efficiency and current density remained relatively high, around 95.9% and 80.2% of the initial values, respectively, indicating it has long-term operation stability. This mainly due to the synergistic effect of doped N, P, and Se, as well as the high specific surface area of SePNC-1050 (970.0 m2g−1). This work would provide a good reference to develop high-performance metal-free CO2 reduction reaction (CO2RR) electrocatalysts in future.