High CO2 Research Articles

Low-calcium CO2 sequestration materials prepared with full-component solid waste based on lithium slag as crystal regulator

High performance low calcium CO2 sequestration materials (LCCSM) were prepared by using carbide slag (CS), copper tailings (CT) as main raw materials and lithium slag (LS) as crystal regulator at 1260 °C for 1 h. The effects of lithium slag content on the crystal transformation and carbonation hardening behavior of low calcium CO2 sequestration material (LCCSM) were studied. The results show that with the increase of LS content (i.e. from 0 % to 3 %), the C3S2 content was increased continuously, and the sum of C2S (i.e., β-C2S and γ-C2S) content was decreased continuously. Due to the activity energy of β-C2S was lowest in first stage carbonation, which accelerates carbonation reaction of the overall LCCSM clinkers and releasing a large amount of heat. Thereafter, the hydration reaction of β-C2S was accelerated significantly and the hydration products will be further carbonated. The minor LS (i.e., 1 %) significantly improved the carbonation activity of LCCSM clinker. Thus, the compressive strength development and degree of carbonation of carbonated compact made by LS-1% was obviously enhanced than that of other LCCSM clinker during the first 24 h. This finding could provide guidance for the obtaining high performance low-calcium CO2 sequestration material based on multiple solid wastes. And also proposed a new perspective for the mechanism among the multi-phase coexistence, crystal transformation and their synergistic carbonation sequestration of calcium silicate clinkers.

CupAR negatively controls the key protein CupA in the carbon acquisition complex NDH–1MS in Synechocystis sp. PCC 6803

The low CO2-inducible NDH complex (NDH-1MS) plays a crucial role in the cyanobacterial CO2-concentrating mechanism. However, the components in this complex and the regulation mechanism are still not completely understood. Using a mutant only with NDH-1MS as active Ci sequestration system, we identified a functional gene sll1736 named as cupAR (CupA Regulator). The cupAR deletion mutant, ΔcupAR, grew faster than the WT under high CO2 (HC) condition, more evidently at low pH. The activities of O2 evolution, CO2 uptake，NDH-1, and the building up of a transthylakoid proton were stimulated in this mutant under HC conditions. The cupAR gene is cotranscribed with the NDH-1S operon (ndhF3-ndhD3-cupA) and encoded protein, which specifically suppresses the transcription level of this operon under HC conditions. Mutation of cupAR significantly upregulated the accumulation of CupA, the key protein of NDH-1MS, under HC condition. CupAR interacted with NdhD3 and NdhF3, the membrane components of NDH-1MS, while accumulation of CupAR was reduced in the ΔndhD3 mutant. Furthermore, CupAR was colocated with CupA in both NDH-1MS complex and NDH-1S subcomplex. On the other hand, deletion of ndhR, a negative regulator of the NDH-1S operon, increased the accumulation of CupAR, whereas deletion of cupAR significantly lowered NdhR. Based on these results, we concluded that CupAR is a novel subunit of NDH-1MS, negatively regulating the activities of CupA and CO2 uptake dependent on NDH-1MS by positive regulation of NdhR under enriched CO2 conditions.

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.

Corrosion at Top-of-the-Line in High Pressure and Dense CO2 Environments

This study presents unique data on top-of-the-line corrosion (TLC) occurring in high-pressure environments where CO2 was in the gaseous, liquid, or supercritical state. While CO2 is traditionally in a gaseous phase, this form of degradation is referred to as TLC. In this study, similar phenomena with different mechanisms were observed in liquid CO2 and supercritical states all of which are referred to as TLC due to the location of specimens and ease of comprehension. Experiments were conducted to investigate the effect of CO2 partial pressure (ranging from 20 bar to 100 bar) with temperatures (30°C to 50°C) relating to different water condensation rates (0.001 mL/m2/s to 0.1 mL/m2/s). Uniform and localized TLC rates increased with a higher water condensation rate and surface temperature. As long as CO2 remained gaseous, its partial pressure (pCO2) showed a negligible influence on both uniform and localized TLC rates. At the highest gaseous CO2 content tested, the formation of a protective iron carbonate (FeCO3) layer decreased the TLC rate, with this effect being more pronounced at lower water condensation rates. The risk of localized corrosion for specimens exposed to this environment at high and medium water condensation rates remained an issue. In the dense phase CO2 environment, the difference in temperature between the bulk environment and the specimen’s surface caused a similar phenomenon to water condensation, termed water drop-out, which resulted in corrosion. The rate of water drop-out could not be measured experimentally or estimated theoretically but is a complex function of temperature, pCO2, and CO2 physical state. The interplay between high pCO2 and low pH of the dropped-out water led to elevated uniform and localized corrosion rates. The depth of localized corrosion, at the high and medium water drop-out conditions, reached its maximum at the surface temperature of ca. 45°C. At a lower surface temperature of ca. 25°C and a higher surface temperature of ca. 65°C, the maximum penetration rate was decreased due to slower kinetics of reactions and the formation of a more protective FeCO3 layer, respectively. The results presented in this study highlight the significant difference between corrosion rates, especially in the form of localized damage, in gaseous and dense-phase CO2 environments.

Experimental study and thermodynamic modeling of CO2+CH4 gas mixture hydrate phase equilibria for gas separation efficiency

Gas separation is a critical application of gas hydrates, and accurately predicting separation performance is crucial. In this study, we used thermodynamic calculations to predict the equilibrium phase of gas hydrates for various mole fractions of CO2 + CH4 gas mixtures. We also determined the mole fraction of each gas component trapped within the hydrate clathrate. To predict the equilibrium points, we used the Soave–Redlich–Kwong（(SRK) equation of state for the gas phase, the nonrandom two-liquid (NRTL)model for the liquid phase, and the Chen–Guo model for the hydrate phase. We modified the hydrate fugacity formula and introduced a new function to improve the accuracy of the Chen–Guo model. By incorporating experimental equilibrium results from our study and another study, we developed a correlation based on gas mixture composition and temperature, resulting in highly accurate predictions. The use of this new correlation for hydrate fugacity calculation significantly improved precision, as evidenced by an average absolute deviation percent of calculated pressures (AADP) of 1.34% for pure CO2 and 1.25% for CH4. When considering the 27 data points of different CO2 + CH4 mixtures, the AADP% was 1.98%.To implement the model to predict equilibrium phases, we used the Chen–Guo framework to determine the mole fraction of each gas component in the hydrate mixture. Interestingly, we discovered a linear correlation between the CO2 mole fraction in the hydrate and equilibrium pressure, with a slope of approximately 0.001 and a y-intercept of less than one, for all gas compositions. Therefore, we can conclude that low thermodynamic conditions (temperature and pressure) result in a high CO2 mole fraction in the hydrate phase and great separation efficiency.

The influence of mixing on seasonal carbon dioxide and methane fluxes in ponds

Inland waters are important sources of the greenhouse gases carbon dioxide (CO2) and methane (CH4). Ponds have amongst the highest CO2 and CH4 fluxes of all aquatic ecosystems, yet seasonal variation in fluxes remain poorly characterized, creating challenges for accurately estimating annual emissions. Further, ponds can exhibit a range of mixing regimes, yet the impact of mixing regimes on gas emissions remains unclear. Here, we assessed annual dynamics of CO2 and CH4 in four temperate ponds (Minnesota, USA) that varied in mixing regimes. The ponds ranged from annual sinks to sources of CO2 (−1 to 15 mol m−2 yr−1) and were all significant sources of CH4 (4.3–8.2 mol m−2 yr−1), with annual fluxes in CO2 equivalents of 1.8–4.1 kg CO2-eq. m−2 yr−1. Mixing regimes impacted CO2 and CH4 dynamics, as stratified periods were associated with more anoxia, greater accumulation of gases in the bottom waters, higher emissions of CH4, and lower fluxes of CO2. Ponds with stronger summer stratification also had increased CO2 and CH4 fluxes associated with fall turnover. Overall, the two ponds with the strongest stratification had higher annual fluxes (2.6, 4.1 kg CO2-eq. m−2 yr−1) compared to the two ponds that more frequently mixed (1.8, 2.2 kg CO2-eq. m−2 yr−1).

Diaminopropane-Functionalized Metal-Organic Frameworks with Controllable Diamine Loss and One-Channel Flipped CO2 Adsorption Mode.

Diamine-functionalized metal-organic frameworks (MOFs) based on Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobihyenyl-3,3'-dicarboxylate) have been frequently reported as promising CO2 adsorbents due to their characteristic step-shaped adsorption behavior. However, high CO2 desorption temperatures for diamine-Mg2(dobpdc)-based adsorbents led to gradual diamine loss while the existence of an exotic CO2 adsorption mode remains experimentally unanswered. Herein, we present CO2 adsorbents obtained by functionalizing Mn2(dobpdc) with a diaminopropane series. These adsorbents offer low regeneration energies, allowing CO2 desorption at lower temperatures than the reported Mg-based analogs. Our first-principles density functional theory calculations showed that the binding strength between the diamine and Mn ions in Mn2(dobpdc) was stronger than that between the diamine and Mg ions in Mg2(dobpdc), preventing diamine loss even at high temperatures and enabling efficient regeneration. Additionally, the computational and experimental data demonstrated that primary-tertiary diamine-functionalized MOFs exhibit one-channel flipped adsorption structures that have not been experimentally revealed. Our findings provide insights into the role of metal ions in diamine loss for the future development of efficient amine-based CO2 adsorbents.

Early age accelerated carbonation of cementitious materials surface in low CO2 concentration condition

Accelerated carbonation curing contributes to the carbon sequestration effect of cementitious materials and enhances surface density. However, in large-scale applications, traditional high CO2 concentration conditions (>5 % CO2) are constrained by economic costs. This study traces the early-stage accelerated carbonation process of cement mortar under low CO2 concentration (3 % CO2) condition from the perspectives of the evolution of CaCO3 crystal types, phase transformations, and microstructural changes, and compares the results with those under the 20 % CO2 condition. The results show that the carbonation depth of mortar specimens cured under the 3 % CO2 condition is shallower, but the cumulative concentration of CaCO3 within the surface 3 mm is not significantly lower than that under the 20 % CO2 condition; The carbonation zone generates more low-crystalline forms of CaCO3; The accelerated carbonation process does not affect the formation of CH and ettringite. Microscopic results indicate that under the 3 % CO2 condition, the synergistic effects of hydration and carbonation are better, and appropriately extending the curing time helps to refine the pore structure of the carbonation zone and improve the density of the substrate surface.

The Freshwater Cyanobacterium Synechococcus elongatus PCC 7942 Does Not Require an Active External Carbonic Anhydrase.

Under standard laboratory conditions, Synechococcus elongatus PCC 7942 lacks EcaASyn, a periplasmic carbonic anhydrase (CA). In this study, a S. elongatus transformant was created that expressed the homologous EcaACya from Cyanothece sp. ATCC 51142. This additional external CA had no discernible effect on the adaptive responses and physiology of cells exposed to changes similar to those found in S. elongatus natural habitats, such as fluctuating CO2 and HCO3- concentrations and ratios, oxidative or light stress, and high CO2. The transformant had a disadvantage over wild-type cells under certain conditions (Na+ depletion, a reduction in CO2). S. elongatus cells lacked their own EcaASyn in all experimental conditions. The results suggest the presence in S. elongatus of mechanisms that limit the appearance of EcaASyn in the periplasm. For the first time, we offer data on the expression pattern of CCM-associated genes during S. elongatus adaptation to CO2 replacement with HCO3-, as well as cell transfer to high CO2 levels (up to 100%). An increase in CO2 concentration coincides with the suppression of the NDH-14 system, which was previously thought to function constitutively.

Unveiling the inhibition of high-pressure CO2 flow accelerated corrosion at gradual contraction and gradual expansion tubings

The different inhibition behavior of imidazoline quaternary ammonium salt for high-pressure CO2 flow accelerated corrosion of carbon steel gradual contraction and gradual expansion tubings was unveiled combing high pressure dynamic in situ electrochemical methods and microstructure characteristics analysis. It is manifested that there is no noticeable inhibition effect in high CO2 partial pressure environments at extremely low inhibitor concentration. At low inhibitor concentration, the polarization resistance and inhibition efficiency increase firstly and then decrease along the flowing direction of gradual contraction tubing. However, the polarization resistance generally drops along the gradual expansion tubing. As the inhibitor concentration of the corrosion inhibitor is further increased, the polarization resistance and inhibition efficiency are reduced in a whole along the gradual contraction tubing. Nevertheless, the polarization resistance is raised, followed by a fall along the flowing direction of gradual expansion tubing. The inhibition effect at the top and the bottom of gradual contraction tubing exhibits symmetry while it is asymmetrical at the top and the bottom of inclination section in gradual expansion tubing. The distinct inhibition effect at different inhibitor concentration is relevant to flow characteristics of fluid at gradual contraction tubing and gradual expansion tubing. The findings could provide valuable guidance for the protection of flow accelerated corrosion at gradual contraction tubing and gradual expansion tubing under high CO2 partial pressure conditions.

Photocatalytic performance of metal poly(heptazine imide) for carbon dioxide reduction

Poly(heptazine imide) (PHI), a carbon nitride polymer, is a highly efficient visible-light-driven photocatalytic material. We aimed to improve its photocatalytic performance for CO2 conversion. We prepared M-PHIs by encapsulating different metals (M = K, Li, Rb, and Na) and H-PHIs, in which the metal of each M-PHI was ion-exchanged with a proton. We evaluated their photocatalytic activities for CO2 conversion and found that Na-PHI and H-PHI, prepared from Na-PHI (H-PHI(NaCl)), showed more than twice the CO production efficiency of melon and other PHIs.The high CO production efficiency of Na-PHI and H-PHI(NaCl) was attributed to their extremely smaller particle size compared with those of the other PHIs. By closely examining the synthesis conditions of Na-PHI, we have identified a method to intentionally synthesize M-PHI with small particle size. These results provide a new strategy for highly efficient CO2 conversion using PHI.

Co-doped bismuth vanadate/zinc tungstate heterojunction with dual internal electric fields for efficient photocatalytic reduction of carbon dioxide

Enhanced carriers separation on photocatalysts is crucial for improving photocatalytic activity. In this paper, the Co-doped BiVO4/ZnWO4 S-scheme heterojunctions were constructed to induce double internal electric fields (IEFs) for enhancing charges separation and transfer for efficient photocatalytic reduction of CO2. The photocatalytic CO2 reduction efficiencies of the heterojunctions were significantly enhanced as compared with the counterparts. The optimized Co-doped BiVO4/ZnWO4 exhibited the highest CO yield of 138.4 μmol·g−1·h−1, which were 86.5 and 1.4 folds of the BiVO4 and Co-doped BiVO4. Results of X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), and work function demonstrated that charge transfer path of Co-doped BiVO4/ZnWO4 conformed to S-scheme heterojunction mechanism. The kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations of the differential charge distributions confirmed the existence of double IEFs, which accelerated carrier separation and improved CO2 adsorption and activation. In addition, in-situ Fourier transform infrared spectroscopy (ISFT-IR) revealed that HCOO− was the major intermediate during the CO2 reaction. This study provides a feasible means to develop composite photocatalysts with dual IEFs for effective photocatalytic CO2 reduction.

Shaping and Doping Metal-Organic Framework-Derived TiO2 to Steer the Selectivity of Photocatalytic CO2 Reduction toward CH4.

Steering selectivity in photocatalytic conversion of CO2, especially toward deep reduction products, is vital to energy and environmental goals yet remains a great challenge. In this work, we demonstrate a facet-dependent photocatalytic selective reduction of CO2 to CH4 in Cu-doped TiO2 catalysts exposed with different facets synthesized by a topological transformation from MIL-125 (Ti) precursors. The optimized round cake-like Cu/TiO2 photocatalyst mainly exposed with the (001) facet exhibited a high photocatalytic CO2 reduction performance with a CH4 yield of 40.36 μmol g-1 h-1 with a selectivity of 94.1%, which are significantly higher than those of TiO2 (001) (4.70 μmol g-1 h-1 and 52.6%, respectively), Cu/TiO2 (001 + 101) (18.95 μmol g-1 h-1 and 69.6%, respectively), and Cu/TiO2 (101) (14.73 μmol g-1 h-1 and 78.9%, respectively). The results of experimental and theoretical calculations demonstrate that the Cu doping dominating the promoted separation and migration efficiencies of photogenerated charges and the preferential adsorption on (001) facets synergistically contribute to the selective reduction of CO2 to CH4. This work highlights the significance of synergy between facet engineering and ion doping in the design of high-performance photocatalysts with respect to selective reduction of CO2 to multielectron products.

Microstructural evolution of Fe-25 W powder beds during CO2-H2 redox cycling at 800 °C

Fixed powder beds of Fe-25 W at% powders show excellent resistance to degradation during CO2-H2 redox cycling at 800 °C, releasing CO and H2O, respectively, with 100 % metal utilization. During cycling up to 165 full redox cycles (∼500 h), the reaction kinetics improve with cycle number and a stable, hierarchically-porous microstructure forms that shows neither sintering nor densification. The sintering inhibition provided by W addition to Fe stems from the formation of Fe-W mixed phases: as an intermetallic compound (Fe2W) in the reduced state and as a ternary oxide (FeWO4) in the oxidized state. In addition to the large channels running between coarse (100 µm) powder agglomerates, each agglomerate in the powder bed shows both microporosity due to sintering inhibition, and submicron porosity due to a chemical vapor transport reduction mechanism that is active when FeWO4 is reduced by H2 at high temperature. This hierarchical porosity enables fast reactions due to the short diffusion distance to free surfaces, and non-tortuous gas flow through the powder bed. As a result, under high CO2 flow, the CO2:CO ratio is sufficiently high to oxidize Fe3O4 to Fe2O3, improving the CO conversion capability on a per-mole basis.

Features of the Microalgae and Cyanobacteria Growth in the Flue Gas Atmosphere with Different CO2 Concentrations

Nowadays, it is important to create the optimal technology for the absorption of flue gases with high CO2 content. In this regard, the aim of the investigation is to study the five different microalgae strains (Chlorella vulgaris, Chlorella ellipsoidea, Elliptochoris subsphaerica, Gloeotila pulchra, and Arthrospira platensis) under the influence of flue gases. The cultivation of microalgae was carried out in the atmosphere of flue gases with a gas flow rate of approximately 1 L·min−1 at high CO2 concentrations (3, 6, or 8%—from lower to higher concentrations), under continuous (24 h·d−1) illumination intensity of 200 µmol quanta·m−2·s−1 and a constant temperature of 27 ± 1 °C. The duration of the experiments was 12 days. Chlorella vulgaris and Chlorella ellipsoidea demonstrated the highest biomass growth rate at CO2 = 6% (0.79 and 0.74 g·L−1·d−1, respectively). The lowest growth rate (0.21 g·L−1·d−1) was achieved for Arthrospira platensis at CO2 = 3 and 6%. There was no significant drop in pH in the entire series of experiments. The results of microscopy showed a lack or a minimal number of dead cells in the strains under selected conditions. The obtained results can be used for further development of CO2 capture and storage technologies.

CuO@N/C-ZnO nanoflowers with quantum dots derived from ZIF-8 for efficient CO2 photoreduction

In this pioneering work, an innovative photocatalyst, denoted as the porous erythrocytic-like nanoflower derived from zeolitic imidazolate framework (ZIF-8) (CuO@N/C-ZnONF), has been meticulously crafted. This design integrates a porous nanosheet of nitrogen and carbon co-doped ZnO, strategically refined with CuO nanosheets (CuONS) architecture originating from ZIF-8. This innovative nanomaterial serves as a nanoreactor for converting CO2 into CO and CH4. The distinctive porous nanoflower structure facilitates enhanced mobility of charge carriers throughout the accessible framework, maximizes exposure of active sites, and improves the flow of charge carriers while preventing their recombination. Additionally, the porous characteristics facilitate the diffusion of reactants and products. The synthesized 10CuO/N-C-ZnONF demonstrates superior photocatalytic performance, yielding high CO and CH4 outputs of 286.16 and 39.74 µmol g−1h−1, respectively, and exhibits excellent long-term stability.

Recent warming and increasing CO2 stimulate growth of dominant trees under no water limitation in South Korea.

Increases in temperatures and atmospheric CO2 concentration influence the growth performance of trees worldwide. The direction and intensity of tree growth and physiological responses to changing climate do, however, vary according to environmental conditions. Here we present complex, long-term, tree-physiological responses to unprecedented temperature increase in East Asia. For this purpose, we studied radial growth and isotopic (δ13C and δ18O) variations using tree-ring data for the past 100yr of dominant Quercus mongolica trees from the cool-temperate forests from Hallasan, South Korea. Overall, we found that tree stem basal area increment, intercellular CO2 concentration and intrinsic water-use efficiency significantly increased over the last century. We observed, however, short-term variability in the trends of these variables among four periods identified by change point analysis. In comparison, δ18O did not show significant changes over time, suggesting no major hydrological changes in this precipitation-rich area. The strength and direction of growth-climate relationships also varied during the past 100yr. Basal area increment (BAI) did not show significant relationships with the climate over the 1924-1949 and 1975-1999 periods. However, over 1950-1974, BAI was negatively affected by both temperature and precipitation, while after 2000, a temperature stimulus was observed. Finally, over the past two decades, the increase in Q. mongolica tree growth accelerated and was associated with high spring-summer temperatures and atmospheric CO2 concentrations and decreasing intrinsic water-use efficiency, δ18O and vapour pressure deficit, suggesting that the photosynthetic rate continued increasing under no water limitations. Our results indicate that the performance of dominant trees of one of the most widely distributed species in East Asia has benefited from recent global changes, mainly over the past two decades. Such findings are essential for projections of forest dynamics and carbon sequestration under climate change.

An acid-tolerant metal-organic framework for industrial CO2 electrolysis using a proton exchange membrane

Industrial CO2 electrolysis via electrochemical CO2 reduction has achieved progress in alkaline solutions, while the same reaction in acidic solution remains challenging because of severe hydrogen evolution side reactions, acid corrosion, and low target product selectivity. Herein, an industrial acidic CO2 electrolysis to pure HCOOH system is realized in a proton-exchange-membrane electrolyzer using an acid-tolerant Bi-based metal-organic framework guided by a Pourbaix diagram. Significantly, the Faradaic efficiency of HCOOH synthesis reaches 95.10% at a large current density of 400 mA/cm2 with a high CO2 single-pass conversion efficiency of 64.91%. Moreover, the proton-exchange-membrane device also achieves an industrial-level current density of 250 mA/cm2 under a relatively low voltage of 3.5 V for up to 100 h with a Faradaic efficiency of 93.5% for HCOOH production, which corresponds to an energy consumption of 200.65 kWh/kmol, production rate of 12.1 mmol/m2/s, and an energy conversion efficiency of 38.2%. These results will greatly aid the contemporary research moving toward commercial implementation and success of CO2 electrolysis technology.

Effects of flame impingement on the stability and NO/CO emissions of laminar premixed methane-ammonia impinging flame

This study investigates the stable combustion range and CO/NO emissions of laminar premixed CH4-NH3 impinging flames experimentally. Effects of flame impingement on the flame stability and CO/NO formations are analyzed quantitatively. The result shows that the flame impingement improves the flame stability considerably through decelerating the unburned gases velocity in the stagnation region, with smaller nozzle-to-wall distance (H) exerting stronger improvement on the flame stability. The NO emission is increased initially but dropped finally with the increased H. This trend is ascribed to the suppressed NO productions at both small and large H due to the intensive cooling effects of cold wall and ambient air entrainment respectively in consideration of the relatively inferior reactivity of NH3. Additionally, due to the insufficient oxidizer in the fuel-rich flame, the more NH3 molecule can also facilitate the NO destruction via the DeNOx pathways at small or large H. In contrast, the CO emissions show similar variation trends with H like the NO emission for the fuel-lean and stoichiometric flames, while the CO emission has a “N” type variation trend with H for the fuel-rich flames. Since the CH4 reactivity can be improved by the NH3 addition at low temperatures, a low-temperature environment at small H due to the strong cooling effect, as well as more available NH3 in the flame, can effectively highlight the improvement of NH3 on the CH4 reactivity in the fuel-rich flame. This makes for the CO production at small H combined with the insufficient oxidizer and eventually results in the higher CO emission of the fuel-rich flame at small H. Additionally, the decreased CO emission at large H results from the improved CO oxidation that is caused by the increased residence time and more oxidizer from ambient air.