Unveiling the role of silicon in boosting electrochemical carbon dioxide reduction via carbon nanotubes@bismuth silicates.

Electrochemical CO2 reduction reaction (CO2RR) is one of the most attractive measures to achieve the carbon neutral goal by converting CO2 into high-value chemicals such as formate. Si in Bi silicates is promising to enhance CO2 adsorption and activation due to its strong oxygenophilicity. Whereas, its role in boosting CO2RR via the cheap Bi-based catalysts is still not clear. Herein, we design CNT@Bi silicates catalyst, demonstrating the highest FEHCOOH of 96.3 % at -0.9 V vs. reversible hydrogen electrode with good stability. Through X-ray photoelectron spectroscopy (XPS), in-situ Attenuated Total Reflectance-Fourier Transform Infrared (In-situ ATR-SEIRAS) experiments, and Density Functional Theory (DFT) calculations, the role of Si in Bi silicates was unveiled: tuning the electronic structure of Bi, weakening the Bi-O bond, and strengthening electron transfer from Bi to CO2, thereby promoting the generation of CO2*- and *OCHO intermediates. Additionally, carbon nanotubes (CNTs) promote not only the conductivity but also the generation of abundant oxygen vacancies in CNT@Bi silicates evidenced by the electron transfer from CNT to Bi silicates from XPS results. Further, the CNT@Bi silicates endows it with the highest electrochemical activation area. These findings suggest the effectiveness of Si in Bi silicates and structure tuning to design highly selective CO2RR catalyst for HCOOH production.

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

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

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.

Nanoporous Metatitanic acid on γ-Al2O3 aerogel for higher CO2 adsorption capacity and lower energy consumption.

Carbon dioxide capture has become an important issue in reducing atmospheric heat these days. In this study, adsorption of carbon dioxide by aerogel Gamma Alumina-Metatitanic Acid has been investigated and optimized. Morphological and structural analyses such as BET, FESEM, FT-IR, and XRD have also been conducted. In addition, Response surface methodology has been applied in order to achieve the optimal conditions, using a five-level Central composite design. The highest amount of adsorption, 12.874 (mmol/g), was recorded at a temperature of 20 (°C), pressure of 7 (bar), and 25 (%wt) of Metatitanic Acid. This was approximately 11.46% and 4.84% higher than those of mesoporous MgO and 4Azeolite, respectively. Regeneration of the adsorbent was also studied at different temperatures and process durations. Metatitanic acid, as a catalyst, reduces the temperature and regeneration time of the adsorbent by creating active sites and surface hydroxyl groups. It also lowers the required activation energy and enhances the thermal conductivity of the composite material. The optimal result was achieved at a temperature of 100 (°C) and a duration of 30 (min). Finally, isothermal and thermodynamic experiments were conducted to establish the most accurate predictive model and conditions, including Enthalpy, Entropy, and Gibbs free energy. The results indicate that the Freundlich model aligned well with the laboratory findings. Additionally, the negative values of Enthalpy, Entropy, and Gibbs free energy suggested that the adsorption process was physical, exothermic, and spontaneous.

Synthesis of nanoporous carbon from Ulva lactuca activated by eggshell for CO2 capture: a novel approach to waste valorization.

Facing the daunting challenge of climate change, driven by escalating greenhouse gas concentrations, our research introduces an innovative solution for CO2 capture. We explore a novel nanoporous carbon derived from Ulva lactuca, activated with eggshell waste, spotlighting waste valorization in mitigating atmospheric CO2. Through a systematic methodology encompassing variable carbonization temperatures (700-900 °C) and nitrogen flow rates (2-4 ml/min), complemented by a suite of characterization techniques, we unveil the synthesis of this pioneering adsorbent. Our study not only presents a novel, sustainable pathway for CO2 capture but also demonstrates superior performance, particularly with the NC800-4 sample, achieving a CO2 capture capacity of 1.40 mmol/g at 30 °C, alongside demonstrating consistent adsorption efficiency over four successive adsorption/desorption cycles. This breakthrough underscores the potential of leveraging waste for environmental remediation, offering a dual solution to waste management and carbon capture, utilization, and storage (CCUS) applications.

Tailoring tea residue-derived nitrogen-doped activated carbon for CO2 adsorption: influence of activation temperature and activating agents.

Embracing CO2 mitigation strategies, such as state-of-the-art CO2 capture technologies, is essential for effectively reducing atmospheric carbon levels and advancing global efforts toward a more sustainable future. In this context, adsorption sequestering techniques utilising carbon materials have emerged as promising candidates for CO2 capture. These materials have been extensively researched with a range of tuning methods to optimise their physicochemical features. In this study, an alteration of the N-doped activated carbon was successfully performed, utilizing tea residue as the carbon precursor and ammonia as the nitrogen source, facilitated through an impregnation procedure. With the objective of discovering the effect of diverse activation parameters on prepared adsorbent physicochemical properties, several selections of activating agents (AA) were investigated: KOH, H3PO4, ZnCl2, and NaOH, together with broad thermal activation temperature from 873 to 1173 K. The best-performed adsorbents from the respective AC group were subjected to several characterisation analyses and found to the enhanced structural features, heteroatom doped-rich surface (i.e. N and O); together with AA-induced metal/mineral functionalization, the NaOH-used AC (NAC-N-1173) was the optimum-performed adsorbent with a promising 4.12 mmol/g CO2 uptake capacity, higher than other prepared adsorbent including N-doped tea residue-derived char and commercialized AC with 175 and 325% higher, respectively.

Strategy in Promoting Visible Light Absorption, Charge Separation, CO2 Adsorption and Proton Production for Efficient Photocatalytic CO2 Reduction with H2O.

Solar-energy-driven photocatalytic CO2 reduction by H2O to high-valuable carbon-containing chemicals has become one of the greatest concerns in both scientific and industrial communities, due to its potential in solving energy and environmental problems. However, efficiency of photocatalytic CO2 reduction by H2O is still far below the needs of large-scale applications. The reduction efficiency is closely related to ability of photocatalysts in absorbing visible light which is the main part of sunlight (44 %), separating photogenerated electron-hole pairs, adsorbing CO2 and producing protons for reducing CO2. Thus, photocatalysts with enhanced visible light absorption, electron-hole separation, CO2 adsorption and proton production are highly desired. Herein, we aim to provide a picture of recent progresses in improving ability of photocatalysts in visible light absorption, electron-hole separation, CO2 adsorption and proton production, and give an outlook for future researches associated with photocatalytic CO2 reduction by H2O.

Nanoscale Understanding on CO2 Diffusion and Adsorption in Clay Matrix Nanopores: Implications for Carbon Geosequestration.

Carbon capture and storage (CCS) in subsurface reservoirs represents a highly promising and viable strategy for mitigating global carbon emissions. In the context of CCS implementation, it is particularly crucial to understand the complex molecular diffusive and adsorptive behaviors of anthropogenic carbon dioxide (CO2) in the subsurface at the nanoscale. Yet, conventional molecular models typically represent only single-slit pores and overlook the complexity of interconnected nanopores. In this work, finite kaolinite lamellar assemblages with abundant nanopores (r < 2 nm) were used. Molecular dynamics simulations were performed to quantify the spatial distribution correlations, adsorption preference, diffusivity, and residence time of the CO2 molecules in kaolinite nanopores. The movement of the CO2 molecules primarily occurs in the central and proximity regions of the siloxane surfaces, progressing from larger to smaller nanopores. CO2 prefers smaller nanopores over larger ones. The diffusion coefficients increase, while residence times decrease, with the pore size increasing, differing from typical slit-pore models due to the pore shape and interconnectivity. The perspectives in this study, which would be challenging in conventional slit-pore models, will facilitate our comprehension of the CO2 molecular behaviors in the complex subsurface clay sediments for developing quantitative estimation techniques throughout the CCS project durations.

Facile synthesis and biomimetic amine-functionalization of chitosan foam for CO2 capture.

A high-performance biomass-based adsorption materials could be the promising trend for CO2 capture and storage technology. However, the direct application of biomass-based porous materials as a CO2 adsorbent with enhanced performance is an emerging issue. Herein, a facile synthesis and a biomimetic strategy were combined to prepare amine-functionalized chitosan foam for CO2 capture, and then a porous biomass is achieved for the application on the environment protection field. Firstly, the chitosan foam was synthesized by the emulsion-templating method at room temperature. Depended on stabilizing n-octane in the chitosan hydrogel with Span 80, a tunable three-dimensional network porous structure was obtained. Subsequently, co-deposition with dopamine (DA) and polyethyleneimine (PEI) was applied to load abundant amine content on the surface of chitosan foam and thereby improving CO2 adsorption capacity. Finally, the as-prepared amine-functionalized chitosan foam exhibited the impressive adsorption capacity of 3.59 mmol/g at 333 K and atmospheric pressure, and the better adsorption selectivity and stability. The results extend the preparation approach of biomass porous materials, and also its application in CO2 adsorption technology.

Controllable Regulation of CO2 Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO2 Electroreduction to Formic Acid.

The synthesis of value-added products via CO2 electroreduction (CO2ER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of CO2ER selectivity through the modulation of CO2 adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU-339), CO2 adsorption behavior is controllably changed from *CO2 to CO2* via the precise ligand-to-metal charge donation (LTMCD) regulation. It is confirmed that the high electronegativity of the coordinate ligand directly restricts the LTMCD, reduces the charge density on the metal sites, lowers the Gibbs free energy for CO2* adsorption, and leads to the transformation of CO2 adsorption mode from *CO2 to CO2*. Owing to the modulated CO2 adsorption behavior and regulated kinetics, SNNU-339 exhibits superior HCOOH selectivity (≈330% promotion, 85.6% Faradaic efficiency) and high CO2ER activity. The wide applicability of the proposed approach sheds light on the efficient CO2ER. This study provides a competitive strategy for rational catalyst design and underscores the significance of adsorption behavior tuning in electrocatalysis.

Reversed Mg-Based Smectites: A New Approach for CO2 Adsorption.

Addressing climate change requires transitioning to cleaner energy sources and adopting advanced CO2 capture techniques. Clay minerals are effective in CO2 adsorption due to their regenerative properties. Recent advancements in nanotechnology further improve their efficiency and potential for use in carbon capture and storage. This study examines the CO2 adsorption properties of montmorillonite and saponite, which are subjected to a novel microwave-assisted acid treatment to enhance their adsorption capacity. While montmorillonite shows minimal changes, saponite undergoes significant alterations. Furthermore, the addition of silica pillars to smectites results in a new nanomaterial with a higher surface area (653 m2 g-1), denoted as reversed smectite, with enhanced CO2 adsorption capabilities, potentially useful for electrochemical devices for converting captured CO2 into value-added products.

CO2 Dynamics in a Flexible Metal-Organic Framework with Gate-Opening Phenomenon.

As a promising porous material for CO2 adsorption and storage, elastic layer-structured metal-organic framework-11 (ELM-11) has attracted significant attention owing to its distinct gate-opening phenomenon. There is a sharp increase in CO2 uptake once reaching the gate-opening threshold pressure. To better understand this gate-opening mechanism, we investigated its transition process from the perspective of CO2 dynamics and its interaction with the framework via variable-temperature 13C solid-state nuclear magnetic resonance spectroscopy. Our findings revealed that during the gate-opening process, CO2 is initially strongly adsorbed at one site when the gate only slightly opens, while two distinct types of CO2 molecules exist when the gate fully opens. 11B, 13C, and 19F magic-angle spinning NMR, in conjunction with in-situ XANES experiments, were also conducted to probe the location of adsorption sites.

Carbon Dioxide Adsorption over Activated Biocarbons Derived from Lemon Peel.

The rising concentration of CO2 in the atmosphere is approaching critical levels, posing a significant threat to life on Earth. Porous carbons derived from biobased materials, particularly waste byproducts, offer a viable solution for selective CO2 adsorption from large-scale industrial sources, potentially mitigating atmospheric CO2 emissions. In this study, we developed highly porous carbons from lemon peel waste through a two-step process, consisting of temperature pretreatment (500 °C) followed by chemical activation by KOH at 850 °C. The largest specific surface area (2821 m2/g), total pore volume (1.39 cm3/g), and micropore volume (0.70 cm3/g) were obtained at the highest KOH-to-carbon ratio of 4. In contrast, the sample activated with a KOH-to-carbon ratio of 2 demonstrated the greatest micropore distribution. This activated biocarbon exhibited superior CO2 adsorption capacity, reaching 5.69 mmol/g at 0 °C and 100 kPa. The remarkable adsorption performance can be attributed to the significant volume of micropores with diameters smaller than 0.859 nm. The Radke-Prausnitz equation, traditionally employed to model the adsorption equilibrium of organic compounds from liquid solutions, has been shown to be equally applicable for describing the gas-solid adsorption equilibrium. Furthermore, equations describing the temperature dependence of the Radke-Prausnitz equation's parameters have been developed.

Pore structure and mineral composition characteristics of coal slime before and after ashing and the effects on CO2 adsorption.

To realize the resource utilization of solid waste (coal slime) and further the dual carbon goals, utilizing coal slime and coal ash as adsorbates for CO2 capture is crucial. This study employed low-temperature N2 adsorption, low-pressure CO2 adsorption, X-ray diffraction, X-ray fluorescence, and isothermal adsorption tests to assess coal slime and coal ash's pore/mineral composition characteristics. Subsequently, the influence on CO2 adsorption was analyzed to reveal the CO2 adsorption mechanisms of pores and clay minerals, and CO2 molecule adsorption behavior. The results showed that: (1) ashing led to reductions in total pore volume, specific surface area, micropore volume, and micropore specific surface area, accompanied by substantial decreases in micropores and mesopores; (2) ashing generated high-temperature stable mineral species, including quartz, andalusite, hematite, and gypsum, while all calcite decomposed into CaO; (3) coal slime exhibited greater CO2 adsorption capacity than coal ash, influenced by pore structure and clay minerals; (4) the adsorption behavior of coal slime and coal ash likely aligns with micropore filling theory, suggesting CO2 is adsorbed within the 0.30-1.47 nm pore structure. This research contributes to optimizing coal by-product utilization in mining areas and exploring adsorbate materials for CO2 sequestration in abandoned goaf.

Integrated "Two-in-One" Strategy for High-Rate Electrocatalytic CO2 Reduction to Formate.

The electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial-relevant current densities. Herein, we report a "two-in-one" catalyst, defective Bi nanosheets modified by CrOx (Bi-CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi-CrOx exhibits an excellent Faradaic efficiency (≈100 %) in a wide potential range from -0.4 to -0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm-2 at a moderate potential of -0.9 V without iR compensation, the highest value at -0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time.

Reversible Multi-Complexation of CO2 to Alkaline Earth Metal Ion-Pair at 400 ppm and 298 K.

The efficient capture of low-pressure CO2 remains a significant challenge due to the lack of established multi-complexation of CO2 to active sites in microporous materials. In this study, we introduce a novel concept of reversible multi-complexation of CO2 to alkaline earth metal (AEM) ion pairs, utilizing a host site in ferrierite-type zeolite (FER). This unique site constrains two AEM ions in proximity, thereby enhancing and isotopically spreading their electrostatic potentials within the zeolite cavity. This electrostatic potential-engineered micropore can trap up to four CO2 molecules, forming M2+-(CO2)n-M2+ (n=0-4, M=Ca, Sr, Ba) complexes, where each CO2 molecule is stabilized by interactions between terminal oxygen (Ot) in CO2 and the AEM ions. Notably, the Ba2+ pair site exhibits higher thermodynamic stability for multiple adsorptions due to the optimal binding mode of Ba2+-Ot-Ba2+. Through high-accuracy energy calculations, we have established the relationship among structure, CO2 uptake, and operating temperature/pressure, demonstrating that the Ba2+ pair site can capture four CO2 molecules even at concentrations as low as 400 ppm and at 298 K. Three of the four molecules of CO2 trapped were removable at room temperature and under vacuum. The findings in the present study provide a new direction for developing efficient CO2 adsorbents.

Effects of pore characteristics on CO2 adsorption performance of coal slime with different metamorphic degrees.

With the rapid development of Carbon Capture, Utilization and Storage (CCUS) technology, it is necessary to explore the feasibility of coal slime as a porous carbon material for CO2 capture. In this paper, scanning electron microscopy (SEM) was used to observe the morphological characteristics of coal slime samples with different metamorphic degrees, and the pore structure of coal slime was explored by low temperature N2 adsorption and low-pressure CO2 adsorption experiments. The pore distribution characteristics were analyzed, and the adsorption law of different metamorphic degrees were summarized through CO2 isothermal adsorption experiments. The results showed that: The specific surface area (SSA) and pore volume (PV) of the mesopores of the coal slime exhibited a U-shaped distribution with coal rank, and are much smaller than that of its micropores. Micropores less than 2 nm are the main adsorption space of coal slime, its PV accounted for 59%, 60%, 71%, and SSA accounted for 92%, 93%, 95%, obviously, which are dominant at all stages. The linear correlation fitting coefficients R2 between the limiting adsorbed amount a of CO2 and the micropores PV and the SSA were up to 0.830 and 0.887, respectively. The coal slime has good adsorption performance for CO2. Based on the Langmuir model to fit the limit adsorption amount, a-value can reach 41.774 cm3 g-1, 32.072 cm3 g-1, 38.457 cm3 g-1 at 303 K with the increase of Rmax. Studying the impact of coal slime on CO2 adsorption performance provides a theoretical basis for the subsequent preparation of energy storage materials and is of great significance for the safe, efficient and economic capture and sequestration of CO2, to alleviate the serious situation of the environment and realizing the dual-carbon goal.

Hierarchical porous MOF-199 mediated cellulosic paper for selective CO2 capture.

MOF-199 is considered to be an excellent CO2 adsorbent owing to its substantial specific surface area, suitable pore structure and abundant sorption sites. However, powdered MOF-199 is prone to agglomeration and has poor recyclability. Herein, we proposed a MOF-199-based adsorbent by combining the MOF synthesis process with traditional papermaking process. Through such a design, MOF-199 particles are adhered on the surface of wood pulp fiber. The sufficient hydroxyl groups and electrostatic forces of cellulose facilitates the homogeneous and tight adhesion of MOF crystals. The optimal MP-4 sample demonstrated a high CO2 adsorption capacity (1.80 mmol·g--1 at 25 °C) and good CO2/N2 selectivity (30.06). Moreover, the composite sorbent can be easily regenerated. The adsorption mechanism was analyzed by the density functional theory approach. The simulation results showed that the carboxyl functional groups with a large number of oxygen atoms and active metal sites are the key to boost the CO2 adsorption performance.

Activated Carbon for CO2 Adsorption from Avocado Seeds Activated with NaOH: The Significance of the Production Method.

The rise in atmospheric greenhouse gases like CO2 is a primary driver of global warming. Human actions are the primary factor behind the surge in CO2 levels, contributing to two-thirds of the greenhouse effect over the past decade. This study focuses on the chemical activation of avocado seeds with sodium hydroxide (NaOH). The influence of various preparation methods was studied under the same parameters: carbon precursor to NaOH mass ratio, carbonization temperature, and nitrogen flow. For two samples, preliminary thermal treatment was applied (500 °C). NaOH was used in the form of a saturated solution as well as dry NaOH. The same temperature of 850 °C of carbonization combined with chemical activation was applied for all samples. The applied modifications resulted in the following textural parameters: specific surface area from 696 to 1217 m2/g, total pore volume from 0.440 to 0.761 cm3/g, micropore volume from 0.159 to 0.418 cm3/g. The textural parameters were estimated based on nitrogen sorption at -196 °C. The XRD measurements and SEM pictures were also performed. CO2 adsorption was performed at temperatures of 0, 10, 20, and 30 °C and pressure up to 1 bar. In order to calculate the CO2 selectivity over N2 nitrogen adsorption at 20 °C was investigated. The highest CO2 adsorption (4.90 mmol/g) at 1 bar and 0 °C was achieved.

Computational and Machine Learning Methods for CO2 Capture Using Metal-Organic Frameworks.

Machine learning (ML) using data sets of atomic and molecular force fields (FFs) has made significant progress and provided benefits in the fields of chemistry and material science. This work examines the interactions between chemistry and materials computational science at the atomic and molecular scales for metal-organic framework (MOF) adsorbent development toward carbon dioxide (CO2) capture. Herein, a connection will be drawn between atomic forces predicted by ML algorithms and the structures of MOFs for CO2 adsorption. Our study also takes into account the successes of atomic computational screening in the field of materials science, especially quantum ML, and its relationship to ML algorithms that clarify advancements in the area of CO2 adsorption by MOFs. Additionally, we reviewed the processes for supplying data to ML algorithms for algorithm training, including text mining from scientific articles, and MOF's formula processing linked to the chemical properties of MOFs. To create ML algorithms for future research, we recommend that the digitization of scientific records can help efficiently synthesize advanced MOFs. Finally, a future vision for developing pioneer MOF synthesis routes for CO2 capture is presented in this review article.