Investigation on cost-effective composites for CO2 adsorption from post-gasification residue and metal organic framework.

Cost-effective CO2 adsorbents are gaining increasing attention as viable solutions for mitigating climate change. In this study, composites were synthesized by electrochemically combining the post-gasification residue of Macadamia nut shell with copper benzene-1,3,5-tricarboxylate (CuBTC). Among the different composites synthesized, the ratio of 1:1 between biochar and CuBTC (B 1:1) demonstrated the highest CO2 adsorption capacity. Under controlled laboratory conditions (0°C, 1 bar, without the influence of ambient moisture or CO2 diffusion limitations), B 1:1 achieved a CO2 adsorption capacity of 9.8 mmol/g, while under industrial-like conditions (25°C, 1 bar, taking into account the impact of ambient moisture and CO2 diffusion limitations within a bed of adsorbent), it reached 6.2 mmol/g. These values surpassed those reported for various advanced CO2 adsorbents investigated in previous studies. The superior performance of the B 1:1 composite can be attributed to the optimization of the number of active sites, porosity, and the preservation of the full physical and chemical surface properties of both parent materials. Furthermore, the composite exhibited a notable CO2/N2 selectivity and improved stability under moisture conditions. These favorable characteristics make B 1:1 a promising candidate for industrial applications.

Carbon emissions in China's steel industry from a life cycle perspective: Carbon footprint insights.

China is the most important steel producer in the world, and its steel industry is one of the most carbon-intensive industries in China. Consequently, research on carbon emissions from the steel industry is crucial for China to achieve carbon neutrality and meet its sustainable global development goals. We constructed a carbon dioxide (CO2) emission model for China's iron and steel industry from a life cycle perspective, conducted an empirical analysis based on data from 2019, and calculated the CO2 emissions of the industry throughout its life cycle. Key emission reduction factors were identified using sensitivity analysis. The results demonstrated that the CO2 emission intensity of the steel industry was 2.33 ton CO2/ton, and the production and manufacturing stages were the main sources of CO2 emissions, accounting for 89.84% of the total steel life-cycle emissions. Notably, fossil fuel combustion had the highest sensitivity to steel CO2 emissions, with a sensitivity coefficient of 0.68, reducing the amount of fossil fuel combustion by 20% and carbon emissions by 13.60%. The sensitivities of power structure optimization and scrap consumption were similar, while that of the transportation structure adjustment was the lowest, with a sensitivity coefficient of less than 0.1. Given the current strategic goals of peak carbon and carbon neutrality, it is in the best interest of the Chinese government to actively promote energy-saving and low-carbon technologies, increase the ratio of scrap steel to steelmaking, and build a new power system.

Facile construction of heterogeneous dual-ionic poly(ionic liquid)s for efficient and mild conversion of CO2 into cyclic carbonates.

In the context of peaking carbon dioxide emissions and carbon neutrality, development of feasible methods for converting CO2 into high value-added chemicals stands out as a hot subject. In this study, P[D+COO-][Br-][DBUH+], a series of novel heterogeneous dual-ionic poly(ionic liquid)s (PILs) were synthesized readily from 2-(dimethylamino) ethyl methacrylate (DMAEMA), bromo-substituted aliphatic acids, organic bases and divinylbenzene (DVB). The structures, compositions and morphologies were characterized or determined by nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), infrared spectroscopy (IR), scanning electron microscopes (SEM), and Brunauer-Emmett-Teller analysis (BET), etc. Application of the P[D+COO-][Br-][DBUH+] series as catalysts in converting CO2 into cyclic carbonates showed that P[D+COO-][Br-][DBUH+]-2/1/0.6 was able to catalyze epiclorohydrin-CO2 cycloaddition the most efficiently. This afforded chloropropylene carbonate (CPC) in 98.4% yield with ≥ 99% selectivity in 24 hr under solvent- and additive-free conditions at atmospheric pressure. Reusability experiments showed that recycling of the catalyst 6 times only resulted in a slight decline in the catalytic performance. In addition, it could be used for the synthesis of a variety of differently substituted cyclic carbonates in good to excellent yields. Finally, key catalytic active sites were probed, and a reasonable mechanism was proposed accordingly. In summary, this work poses an efficient strategy for heterogenization of dual-ionic PILs and provides a mild and environmentally benign approach to the fixation and utilization of carbon dioxide.

Real-road NOx and CO2 emissions of city and highway China-6 heavy-duty diesel vehicles.

The emission of heavy-duty vehicles has raised great concerns worldwide. The complex working and loading conditions, which may differ a lot from PEMS tests, raised new challenges to the supervision and control of emissions, especially during real-world applications. On-board diagnostics (OBD) technology with data exchange enabled and strengthened the monitoring of emissions from a large number of heavy-duty diesel vehicles. This paper presents an analysis of the OBD data collected from more than 800 city and highway heavy-duty vehicles in China using remote OBD data terminals. Real-world NOx and CO2 emissions of China-6 heavy-duty vehicles have been examined. The results showed that city heavy-duty vehicles had higher NOx emission levels, which was mostly due to longer time of low SCR temperatures below 180°C. The application of novel methods based on 3B-MAW also found that heavy-duty diesel vehicles tended to have high NOx emissions at idle. Also, little difference had been found in work-based CO2 emissions, and this may be due to no major difference were found in occupancies of hot running.

Hydrogen production from dry reforming of methane, using CO2 previously chemisorbed in the Li6Zn1-xNixO4 solid solution.

Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.

Tailored design of novel Co0-Coδ+ dual phase nanoparticles for selective CO2 hydrogenation to ethanol.

Catalytic hydrogenation of CO2 to ethanol is a promising solution to address the greenhouse gas (GHG) emissions, but many current catalysts face efficiency and cost challenges. Cobalt based catalysts are frequently examined due to their abundance, cost-efficiency, and effectiveness in the reaction, where managing the Co0 to Coδ+ ratio is essential. In this study, we adjusted support nature (Al2O3, MgO-MgAl2O4, and MgO) and reduction conditions to optimize this balance of Co0 to Coδ+ sites on the catalyst surface, enhancing ethanol production. The selectivity of ethanol reached 17.9% in a continuous flow fixed bed micro-reactor over 20 mol% Co@MgO-MgAl2O4 (CoMgAl) catalyst at 270 °C and 3.0 MPa, when reduced at 400 °C for 8 h. Characterisation results coupled with activity analysis confirmed that mild reduction condition (400 °C, 10% H2 balance N2, 8 h) with intermediate metal support interaction favoured the generation of partially reduced Co sites (Coδ+ and Co0 sites in single atom) over MgO-MgAl2O4 surface, which promoted ethanol synthesis by coupling of dissociative (CHx*)/non-dissociative (CHxO*) intermediates, as confirmed by density functional theory analysis. Additionally, the CoMgAl, affordably prepared through the coprecipitation method, offers a potential alternative for CO2 hydrogenation to yield valuable chemicals.

Effects of atmospheric CO2 concentration on transpiration and leaf elongation responses to drought in Triticum aestivum, Lolium perenne and Festuca arundinacea.

BACKGROUND AND AIMS: Leaf elongation is vital for Poaceae species' productivity, influenced by atmospheric CO2 concentration ([CO2]) and climate-induced water availability changes. Although [CO2] mitigates the effects of drought on reducing transpiration per unit leaf area, it also increases total leaf area and water use. These complex interactions associated with leaf growth pose challenges in anticipating climate change effects. This study aims to assess [CO2] effects on leaf growth response to drought in perennial ryegrass (Lolium perenne), tall fescue (Festuca arundinacea) and wheat (Triticum aestivum). METHODS: Plants were cultivated in growth chambers with [CO2] at 200 or 800 ppm. At leaf six to seven unfolding, half of the plants were subjected to severe drought treatment. Leaf elongation rate (LER) was measured daily, whereas plant transpiration was continuously recorded gravimetrically. Additionally, water-soluble carbohydrate (WSC) content along with water and osmotic potentials in the leaf growing zone were measured at drought onset, mid-drought and leaf growth cessation. KEY RESULTS: Elevated [CO2] mitigated drought impacts on LER and delayed growth cessation across species. A positive correlation between LER and soil relative water content (SRWC) was observed. At the same SRWC, perennial grasses exhibited a higher LER with elevated [CO2], likely due to enhanced stomatal regulation. Despite stomatal closure and WSC accumulation, CO2 did not influence nighttime water potential or osmotic potential. The marked increase in leaf area across species resulted in similar (wheat and tall fescue) or higher (ryegrass) total water use by the experiment's end, under both watered and unwatered conditions. CONCLUSIONS: In conclusion, elevated [CO2] mitigates the adverse effects of drought on leaf elongation in three Poaceae species, due to its impact on plant transpiration. Overall, these findings provide valuable insights into CO2 and drought interactions that may help anticipate plant responses to climate change.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets.

Product selectivity of solar-driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100%, and the selectivity of the (110) and (111) facets towards CH4 is 33.5% and 97.6%, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 µmol/g/h, and the solar-to-chemical energy efficiency of 0.23% is 33.8 times higher than that under non-concentrated solar irradiation. The impacts of high-density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.

Fabrication of rGO-bridged TiO2/g-C3N4 Z-scheme Nanocomposites via Pulsed Laser Ablation for Efficient Photocatalytic CO2 Reduction.

Highly efficient photocatalysts can be fabricated using favorable charge transfer nanocomposite channel structures. This study adopted pulsed laser ablation in liquid (PLAL) to obtain rGO-bridged TiO2/g-C3N4 (rGO-TiO2/g-C3N4) photocatalytic Z-scheme without the need for noble metals. In addition to evaluating the resulting nanocomposite's (comprising rGO nanosheets, TiO2 nanotubes, and g-C3N4 nanosheets) CO2 reduction effectiveness, its chemical, morphological, structural, and optical characteristics were examined using various analytical techniques. The findings revealed a synergistic interaction between g-C3N4 and TiO2, suggesting the presence of unique interfacial bonding, as well as enhanced visible light absorption. Notably, the ternary rGO-TiO2/g-C3N4 Z-scheme exhibits an excellent photocatalytic performance by photocatalytically converting CO2 into CO and CH4, with 81% selectivity towards the CO and 1.91% apparent quantum efficiency at 420 nm. Thus, the findings can pave the way for various Z-scheme systems in wide photocatalytic applications.

Visible Light-sensitized CO2 Methanation along a Relaxed Heat Available Route.

In photocatalysis, the resulted heat by the relaxation of most of incident light no longer acts as the industrially favorite driving force back to the target photo-reaction due to more or less the negative relation between photocatalytic efficiency and temperature. Here, we reported a visible light-sensitized protocol that completely reversed the negatively temperature-dependent efficiency in photo-driven CO2 methanation with saturated water vapor. Uniform Pt/N-TiO2/PDI self-assembly material decisively injects the excited electron of PDI sensitizer into N-TiO2 forming Ti-H hydride which is crucially temperature-dependent nucleophilic species to dominate CO2 methanation, rather than conventionally separated and trapped electrons on the conductor band. Meanwhile, the ternary composite lifts itself temperature from room temperature to 305.2 °C within 400s only by the failure excitation upon simulated sunlight of 2.5 W/cm2, and smoothly achieves CO2 methanation with a record number of 4.98 mmol g-1 h-1 rate, compared to less than 0.02 mmol g-1 h-1 at classic Pt/N-TiO2/UV photocatalysis without PDI sensitization. This approach can reuse ~53.9% of the relaxed heat energy from the incident light thereby allow high-intensity incident light as strong as possible within a flowing photo-reactor, opening the most likely gateways to industrialization.

Electron-Efficient Co-electrosynthesis of Formates from CO2 and Methanol Feedstocks.

The electrochemical conversion of CO2 into valuable chemicals using renewable electricity shows significant promise for achieving carbon neutrality and providing alternative energy storage solutions. However, its practical application still faces significant challenges, including high energy consumption, poor selectivity, and limited stability. Here, we propose a hybrid acid/alkali electrolyzer that couples the acidic CO2 reduction reaction (CO2RR) at the cathode with alkaline methanol oxidation reaction (MOR) at the anode. This dual electro-synthesis cell is implemented by developing Bi nanosheets as cathode catalysts and oxide-decorated Cu2Se nanoflowers as anode catalysts, enabling high-efficiency electron utilization for formate production with over 180% coulombic efficiency and more than 90% selectivity for both CO2RR and MOR conversion. The hybrid acid/alkali CO2RR-MOR cell also demonstrates long-term stability exceeding 100 hours of continuous operation, delivers a formate partial current density of 130 mA cm-2 at a voltage of only 2.1 V, and significantly reduces electricity consumption compared to the traditional CO2 electrolysis system. This study illuminates an innovative electron-efficiency and energy-saving techniques for CO2 electrolysis, as well as the development of highly efficient electrocatalysts.

Translational insights into the hormetic potential of carbon dioxide: from physiological mechanisms to innovative adjunct therapeutic potential for cancer.

Background: Carbon dioxide (CO2), traditionally viewed as a mere byproduct of cellular respiration, plays a multifaceted role in human physiology beyond simple elimination through respiration. CO2 may regulate the tumor microenvironment by significantly affecting the release of oxygen (O2) to tissues through the Bohr effect and by modulating blood pH and vasodilation. Previous studies suggest hypercapnia (elevated CO2 levels) might trigger optimized cellular mechanisms with potential therapeutic benefits. The role of CO2 in cellular stress conditions within tumor environments and its impact on O2 utilization offers a new investigative area in oncology. Objectives: This study aims to explore CO2's role in the tumor environment, particularly how its physiological properties and adaptive responses can influence therapeutic strategies. Methods: By applying a structured translational approach using the Work Breakdown Structure method, the study divided the analysis into six interconnected work packages to comprehensively analyze the interactions between carbon dioxide and the tumor microenvironment. Methods included systematic literature reviews, data analyses, data integration for identifying critical success factors and exploring extracellular environment modulation. The research used SMART criteria for assessing innovation and the applicability of results. Results: The research revealed that the human body's adaptability to hypercapnic conditions could potentially inform innovative strategies for manipulating the tumor microenvironment. This could enhance O2 utilization efficiency and manage adaptive responses to cellular stress. The study proposed that carbon dioxide's hormetic potential could induce beneficial responses in the tumor microenvironment, prompting clinical protocols for experimental validation. The research underscored the importance of pH regulation, emphasizing CO2 and carbonic acid's role in modulating metabolic and signaling pathways related to cancer. Conclusion: The study underscores CO2 as vital to our physiology and suggests potential therapeutic uses within the tumor microenvironment. pH modulation and cellular oxygenation optimization via CO2 manipulation could offer innovative strategies to enhance existing cancer therapies. These findings encourage further exploration of CO2's therapeutic potential. Future research should focus on experimental validation and exploration of clinical applications, emphasizing the need for interdisciplinary and collaborative approaches to tackle current challenges in cancer treatment.

Study of different pre-treatments in the comparison of the efficacy of photodynamic therapy for moderate to severe acne vulgaris.

OBJECTIVE: To evaluate the efficacy of CO2 fractional laser and microneedling pretreatment combined with ALA-PDT for moderate-to-severe acne, aiming to optimize clinical treatment. METHODS: Patients were randomly divided into three groups: Group A (CO2 fractional laser + ALA-PDT), Group B (microneedling + ALA-PDT), and Group C (ALA-PDT). Each group underwent photodynamic therapy once a week for 3 weeks. Efficacy was assessed at the end of the 4th week, and recurrence was assessed at the end of the 12th week. RESULTS: A total of 150 patients with moderate to severe acne were included in this study, with 50 patients in each group. Four weeks after the end of treatment, the effective rates were 88% for Group A, 62% for Group B, and 36% for Group C. Statistically significant differences were found between the groups (P < 0.05), with Group A showing superior efficacy compared to Group B (P < 0.05). No serious systemic or local adverse reactions were observed in any group. No recurrence was seen in any group 12 weeks after the end of treatment, and some patients continued to show improvement in skin lesions over time. CONCLUSION: Both the CO2 fractional laser group and the microneedling group improved the efficacy of photodynamic therapy for moderate to severe acne compared to the control group, with the CO2 fractional laser group demonstrating better efficacy and fewer adverse effects.

Anionic Metal-Organic Framework Derived Cu Catalyst for Selective CO2 Electroreduction to Hydrocarbons.

Metal-organic frameworks (MOFs)-related Cu materials are promising candidates for promoting electrochemical CO2 reduction to produce valuable chemical feedstocks. However, many MOF materials inevitable undergo reconstruction under reduction conditions; therefore, exploiting the restructuring of MOF materials is of importance for the rational design of high-performance catalyst targeting multi-carbon products (C2). Herein, a facile solvent process is choosed to fabricate HKUST-1 with an anionic framework (a-HKUST-1) and utilize it as a pre-catalyst for alkaline CO2RR. The a-HKUST-1 catalyst can be electrochemically reduced into Cu with significant structural reconstruction under operating reaction conditions. The anionic HKUST-1 derived Cu catalyst (aHD-Cu) delivers a FEC2H4 of 56% and FEC2 of ≈80% at -150 mA cm-2 in alkaline electrolyte. The resulting aHD-Cu catalyst has a high electrochemically active surface area and low coordinated sites. In situ Raman spectroscopy indicates that the aHD-Cu surface displays higher coverage of *CO intermediates, which favors the production of hydrocarbons.

Regulating Local Electron Density of Cyano Sites in Graphitic Nitride Carbon by Giant Internal Electric Field for Efficient CO2 Photoreduction to Hydrocarbons.

Selective photocatalytic CO2 reduction to high-value hydrocarbons using graphitic carbon nitride (g-C3N4) polymer holds great practical significance. Herein, the cyano-functionalized g-C3N4 (CN-g-C3N4) with a high local electron density site is successfully constructed for selective CO2 photoreduction to CH4 and C2H4. Wherein the potent electron-withdrawing cyano group induces a giant internal electric field in CN-g-C3N4, significantly boosting the directional migration of photogenerated electrons and concentrating them nearby. Thereby, a high local electron density site around its cyano group is created. Moreover, this structure can also effectively promote the adsorption and activation of CO2 while firmly anchoring *CO intermediates, facilitating their subsequent hydrogenation and coupling reactions. Consequently, using H2O as a reducing agent, CN-g-C3N4 achieves efficient and selective photocatalytic CO2 reduction to CH4 and C2H4 activity, with maximum rates of 6.64 and 1.35 µmol g-1 h-1, respectively, 69.3 and 53.8 times higher than bulk g-C3N4 and g-C3N4 nanosheets. In short, this work illustrates the importance of constructing a reduction site with high local electron density for efficient and selective CO2 photoreduction to hydrocarbons.

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 -0.58 V (versus the reversible hydrogen electrode (RHE)) and achieves the highest partial current density of 13.64 mA cm-2 at -0.88 V. Furthermore, when employed as the cathode in a Zn-CO2 battery, FeSNC achieves a high-power density of 1.19 mW 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.

Response of photosynthetic characteristics and yield of grape to different CO2 concentrations in a greenhouse.

Due to the enclosed environment of greenhouse grape production, the supply of CO2 required for photosynthesis is often insufficient, leading to photosynthetic downregulation and reduced yield. Currently, the optimal CO2 concentration for grape production in greenhouses is unknown, and the precise control of actual CO2 levels remains a challenge. This study aims to investigate the effects of different CO2 concentrations on the photosynthetic characteristics and yield of grapes, to validate the feasibility of a CO2 gas irrigation system, and to identify the optimal CO2 concentration for greenhouse grape production. In this study, a CO2 gas irrigation system combining CO2 enrichment and gas irrigation techniques was used with a 5-year-old Eurasian grape variety (Vitis vinifera L.) 'Flame Seedless.' Four CO2 concentration treatments were applied: 500 ppm (500 ± 30 µmol·mol-1), 700 ppm (700 ± 30 µmol·mol-1), 850 ppm (850 ± 30 µmol·mol-1), and 1,000 ppm (1,000 ± 30 µmol·mol-1). As CO2 concentration increased, chlorophyll a, chlorophyll b, and carotenoids in grape leaves all reached maximum values at 700 ppm and 850 ppm during the same irrigation cycle, while the chlorophyll a/b ratio was lower than at other concentrations. The net photosynthetic rate (Pn) and water use efficiency (WUE) of grape leaves were the highest at 700 ppm. The transpiration rate and stomatal conductance at 700 ppm and 850 ppm were significantly lower than those at other concentrations. The light saturation point and apparent quantum efficiency reached their maximum at 850 ppm, followed by 700 ppm. Additionally, the maximum net photosynthetic rate, carboxylation efficiency, electron transport rate, and activities of SOD, CAT, POD, PPO, and RuBisCO at 700 ppm were significantly higher than at other concentrations, with the highest yield recorded at 14.54 t·hm-2. However, when the CO2 concentration reached 1,000 ppm, both photosynthesis and yield declined to varying degrees. Under the experimental conditions, the optimal CO2 concentration for greenhouse grape production was 700 ppm, with excessive CO2 levels gradually inhibiting photosynthesis and yield. The results provide a theoretical basis for the future application of CO2 fertilization and gas irrigation techniques in controlled greenhouse grape production.

A Synopsis on CO2 Capture by Synthetic Hydrogen Bonding Receptors.

Carbon dioxide (CO2) is one of the most abundant greenhouse gases in Earth's atmosphere and responsible for global warming. Therefore, aerial CO2 capture and sequestration has become a major task for human community. Though several adsorbents for CO2 including activated carbon, zeolites, metal-organic frameworks (MOFs), and other surface-modified porous materials are well developed, the supramolecular approaches using synthetic hydrogen-bonding receptors are less explored. This review article highlights the synthetic development of various artificial receptors and their properties toward fixation of aerial CO2 as carbonate (CO32-), bicarbonate (HCO3-), or carbamate (-NHCOO-/>NCOO-) ions, induced by excess fluoride (F-) or hydroxide (OH-) ions as their tetrabutylammonium salts. The utilization of encapsulated carbonate/bicarbonate/carbamate complexes in anion exchange metathesis for separation of oxyanions from aqueous solutions are also discussed. In addition, the release of CO2 and regeneration of receptor molecules are described in a number of occasions. Most importantly, the formation of anion complexes as crystalline materials in solid-state is described in terms of supramolecular chemistry and correlated with their solution-state properties. Finally, the types of receptors containing various functional groups are scrutinized in CO2 uptake, storage, and release processes and hints of endeavours for future research are delineated.

Steering the Site Distance of Atomic Cu-Cu Pairs by First-Shell Halogen Coordination Boosts CO2-to-C2 Selectivity.

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C-C coupling to unravel their structure-performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu-Cu dual sites with different site distance coordinated by halogen at the first-shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long-range Cu-Cu (Cu-I-Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long-range Cu-Cu dual site is accelerated to C2H4 generation and short-range Cu-Cu (Cu-Cl-Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long-range Cu-Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C-C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site-distance-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu-Cu dual sites.

Deep-root respiration: The unknown CO2 removed from the atmosphere.

Carbon (C) sequestration in soils is a promising CO2 removal approach. So far, the focus has been on how to increase the content of soil organic C (SOC), while the management soil inorganic C (SIC), i.e. carbonate minerals, has received little attention, because SIC is thought to be much less involved in biotic C cycling than SOC. However, in principle SIC management potentially provides a long-term solution, with a much greater capacity for C sequestration than SOC. The forgotten link is the dissolved inorganic carbon (DIC), i.e. CO2 species dissolved in soil solution, and its fate throughout the unsaturated zone (USZ). The return of CO2 respired by deep roots to the atmosphere, either directly through CO2 degassing or indirectly through DIC leaching, may not necessarily take place over decades or centuries. CO2 diffusion decreases sharply with depth due to reduced porosity of the subsoil and more water-filled pores. The downward water percolation rate is often only a few centimeters per year, and the large amount of respired CO2 compared to the leached DIC results in a relatively small amount of CO2 being transferred to the groundwater. Therefore, respired CO2 at deeper soil depth can be defined as a hitherto unknown ecosystem service of deep-rooted plants i.e. providing a net C sink as inorganic C in the USZ. A conservative estimation suggests a C sink as SIC of at least 80 kg C ha-1 y-1, comparable to reported annual C sequestration as SOC in temperate grasslands.