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Various Cu-based materials in diverse forms have been investigated as efficient catalysts for electrochemical reduction of CO2; however, they suffer from issues such as higher over potential and poor selectivity. The activity and selectivity of CO2 electro reduction have been shown to change significantly when the surface morphology (steps, kinks, and edges) of these catalysts is altered. In light of this, size and morphology dependent activity of selected copper clusters, Cun (n=2-20) have been evaluated for the activation and reduction of CO2 molecule. The phase-space of these copper clusters is rich in conformations of distinct morphologies starting from planar, 2D geometries to prolate-shaped geometries and also high-symmetry structures. The binding efficiency and the activation of CO2 are highest for medium sized clusters (n=9-17) with prolate-morphologies as compared to small or larger sized CunCO2 clusters that are existing mainly as planar (triangular, tetragonal etc.) or highly-symmetric geometries (icosahedron, capped-icosahedron etc.), respectively. The best performing (prolate-shaped) CunCO2 conformations are quite fluxional and also they are thermally stable, as demonstrated by the molecular dynamics simulations. Furthermore, on these CunCO2 conformations, the step-by-step hydrogenation pathways of CO2 to produce value-added products like methanol, formic acid, and methane are exceptionally favorable and energy-efficient.

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Sequestering carbon dioxide (CO2) from the atmosphere is necessary to achieve a sustainable environment. The emergence of frustrated Lewis pairs (FLPs) has opened a new dimension in the development of organocatalysts for CO2 sequestration. To date, various FLPs have been developed for CO2 sequestration, yet the quest for robust FLPs continues. Based on the intriguing electronic effects of the carborane polyhedral, o-carboranes can be projected as a versatile bridging unit for intramolecular FLPs (IFLPs). In the present work, o-carborane based IFLPs AlP, BP, AlN and BN have been proposed for the activation of CO2 molecule. The density functional theory (DFT) based calculations and thorough orbital analysis have been carried out to extensively study the electronic structure of the o-carborane unit. The proposed IFLPs were systematically compared with their corresponding phenyl bridged analogues to assess the effect of o-carborane bridging unit on the reactivity of the acidic and basic sites. The results show that the o-carborane supported IFLPs are more reactive towards CO2 than the phenyl bridged IFLPs. Also, placing the basic site on the B atom at the 4th position of the o-carborane bridge rather than the C atom at the 2nd position results in more reactive IFLPs.

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High efficiently photocatalytic CO2 reduction (CO2RR) into liquid fuels in pure water system remains challenged. Iron polyphthalocyanine (FePPc) with strong light harvesting, unique Fe-N4 structure, abundant pores, and good stability could serve as a promising catalyst for CO2 photoreduction. To further improve the catalytic efficiency, herein, symmetry-breaking Fe sites are constructed by coupling with atomically precise M1Ag24 (M=Ag, Au, Pt) series clusters. Especially, the introduction of Pt1Ag24 causes the most asymmetric charge distribution of Fe in FePPc (followed by Au1Ag24 and Ag25), leading to the favorable CO2 adsorption and activation. In addition, Pt1Ag24-FePPc exhibits the most effective photogenerated carriers transfer and separation. As a result, Pt1Ag24-FePPc shows the methanol/ethanol yield of 48.55/32.97 µmol·gcat-1·h-1 in H2O-CO2 system under visible light irradiation, ~ 1.65/1.25-fold, 1.83/1.37-fold, and 3.6/1.61-fold higher than that of Au1Ag24-FePPc, Ag25-FePPc, and FePPc, respectively. This work provides a concept for precisely construction and regulation symmetry-breaking sites of cluster-based catalysts for effective CO2 conversion.

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The incorporation of hydrophilic and basic sites from phosphotriazaadamantane and saccharine in a water-soluble Pd complex and the subsequent confinement into mesoporous silica support increases the activity and stability of the palladium catalytic species for the room-temperature aqueous hydrogenation of either bicarbonate or CO2 into formic acid. The use of low Pd loadings (<0.1mmolPd·g-1) of the well-dispersed complex on SBA-15 mesoporous silica allows performing the reaction under room temperature, and aqueous conditions, exhibiting TON of ca. 40-100, for the CO2 or bicarbonate hydrogenation, respectively, which is one order of magnitude higher than the homogeneous case, allowing the easy isolation and recycling of the solid catalyst.

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We investigate the interaction of CO2 with metallic and oxidized Cu(110) surfaces using a combination of near-ambient pressure scanning tunneling microscopy (NAP-STM) and theoretical calculations. While the Cu(110) and full CuO films are inert, the interface between bare Cu(110) and the CuO film is observed to react instantly with CO2 at a 10 mbar pressure. The reaction is observed to proceed from the interfacial sites of CuO/Cu(110). During reaction with CO2, the CuO/Cu(110) interface releases Cu adatoms which combine with CO3 to produce a variety of added Cu-CO3 structures, whose stability depends on the gas pressure of CO2. A main implication for the reactivity of Cu(110) is that Cu adatoms and highly undercoordinated CuO segments are created on the Cu(110) surface through the interaction with CO2, which may act as reaction-induced active sites. In the case of CO2 hydrogenation to methanol, our theoretical assessment of such sites indicates that their presence may significantly promote CH3OH formation. Our study thus implies that the CuO/Cu(110) interfacial system is highly dynamic in the presence of CO2, and it suggests a possible strong importance of reaction-induced Cu and CuO sites for the surface chemistry of Cu(110) in CO2-related catalysis.

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The reed straw is assessed as a potential source of widely available renewable biomass for biochar production and compared with two other waste-based biomasses, namely fruit stones blend, and brewery spent grains. The biochars were activated via steam and CO2. While steam activation yielded 12 % carbon from reed biomass, CO2 activation resulted in biomass degradation. The characterization of reed biochar showed a mesoporous structure and a high surface area of 514 m2/g. The adsorption tests displayed a decent adsorption capacity of biochar, with values of 92.6 mg/g for methylene violet dye and 35.7 mg/g for acid green dye. Only 1 g/L dosage of reed biochar was able to remove 99 % of the 50 mg/L methylene violet solution in 15 min and 60 % of the 50 mg/L acid green solution in 10 min. The obtained results demonstrate reed biomass as a suitable source for biochar production as well as reed-based biochar as a promising dye adsorbent.

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Nickel complexes with a two-electron reduced CO2 ligand (CO2 2-, "carbonite") are investigated with regard to the influence alkali metal (AM) ions have as Lewis acids on the activation of the CO2 entity. For this purpose complexes with NiII(CO2)AM (AM=Li, Na, K) moieties were accessed via deprotonation of nickel-formate compounds with (AM)N(iPr)2. It was found that not only the nature of the AM ions in vicinity to CO2 affect the activation, but also the number and the ligation of a given AM. To this end the effects of added (AM)N(R)2, THF, open and closed polyethers as well as cryptands were systematically studied. In 14 cases the products were characterized by X-ray diffraction and correlations with the situation in solution were made. The more the AM ions get detached from the carbonite ligand, the lower is the degree of aggregation. At the same time the extent of CO2 activation is decreased as indicated by the structural and spectroscopic analysis and reactivity studies. Accompanying DFT studies showed that the coordinating AM Lewis acidic fragment withdraws only a small amount of charge from the carbonite moiety, but it also affects the internal charge equilibration between the LtBuNi and carbonite moieties.

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A heteroleptic amino(imino)stannylene (TMS2 N)(It BuN)Sn: (TMS=trimethylsilyl, It Bu=C[(N-t Bu)CH]2 ) as well as two homoleptic NHI-stabilized tetrylenes, (It BuN)2 E: (NHI=N-heterocyclic imine, E=Ge, Sn) are presented. VT-NMR investigations of (It BuN)2 Sn: (2) reveal an equilibrium between the monomeric stannylene at room temperature and the dimeric form at -80 °C as well as in the solid state. Upon reaction of the homoleptic tetrylenes with CO2 , both compounds insert two equivalents of CO2 , however differing bonding modes can be observed. (It BuN)2 Sn: (2) inserts one equivalent of CO2 into each Sn-N bond, giving carbamato groups coordinated κ2 O,O' to the metal center. With (It BuN)2 Ge: (3), the Ge-N bonds stay intact upon activation, being bridged by one molecule of CO2 respectively, forming 4-membered rings. Furthermore, the reactivity of 2 towards N2 O was investigated, resulting in partial oxidation to form stannylene dimer [((It BuN)3 SnO)(It BuN)Sn:]2 (6).

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Here we systematically investigate the CO2 and H2 activation and dissociation on small Cun Zn0/+ (n=3-6) clusters using Density Functional Theory. We show that Cu6 Zn is a superatom, displaying an increased HOMO-LUMO gap and is inert towards CO2 or H2 activation or dissociation. While other neutral clusters weakly activate CO2 , the cationic clusters preferentially bind the CO2 in monodentate nonactivated way. Notably, Cu4 Zn allows for the dissociation of activated CO2 , whereas larger clusters destabilize all activated CO2 binding modes. Conversely, H2 dissociation is favored on all clusters examined, except for Cu6 Zn. Cu3 Zn+ and Cu4 Zn, favor the formation of formate through the H2 dissociation pathway rather than CO2 dissociation. These findings suggest the potential of these clusters as synthetic targets and underscore their significance in the realm of CO2 hydrogenation.

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The facile fabrication of low-cost adsorbents possessing high removal efficiency and convenient separation property is an urgent need for water treatment. Herein, magnetic activated carbon was synthesized from spent coffee grounds (SCG) by Fe-catalyzed CO2 activation at 800 °C for 90 min, and magnetization and pore formation were simultaneously achieved during heat treatment. The sample was characterized by N2 adsorption-desorption, XRD, VSM, SEM, and FTIR. Batch adsorption experiments were conducted using lomefloxacin (LMO) as the probing pollutant. Preparation mechanism was revealed by TG-FTIR and XRD. Experimental results showed that Fe3O4 derived from Fe species can be reduced to Fe by carbon at high temperatures, followed by subsequent reoxidation to Fe3O4 by CO2, and the redox cycle between Fe and Fe3O4 favored the formation of pores. The promotion effects of Fe species on CO2 activation can be quantitatively reflected by the yield of CO as the signature gaseous product, and the suitable activation temperate range was determined to be 675 to 985 °C. The BET surface area, total pore volume, and saturated magnetization value of the product were 586 m2 g-1, 0.327 cm3 g-1, and 11.59 emu g-1, respectively. The Langmuir model was applicable for the adsorption isotherm data for LMO with the maximum adsorption capacity of 95 mg g-1, and thermodynamic analysis revealed that the adsorption process was endothermic and spontaneous. This study demonstrated that Fe-catalyzed CO2 activation was an effective method of converting SCG into magnetic separable adsorbent for LMO removal from aqueous medium.

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The aim of the current study was to produce biocarbons through the activation of carbon dioxide with the extraction residues of the fungus Inonotus obliquus. To achieve this goal, a microwave oven was used to apply three different activation temperatures: 500, 600, and 700 °C. Low-temperature nitrogen adsorption/desorption was employed to determine the elemental composition, acid-base properties, and textural parameters of the resulting carbon adsorbents. Subsequently, the produced biocarbons were evaluated for their efficiency in removing malachite green and NO2. The adsorbent obtained by activation of the precursor in 700 °C had a specific surface area of 743 m2/g. In the aqueous malachite green solution, the highest measured sorption capacity was 176 mg/g. Conversely, under dry conditions, the sorption capacity for NO2 on this biocarbon was 21.4 mg/g, and under wet conditions, it was 40.9 mg/g. According to the experimental findings, surface biocarbons had equal-energy active sites that interacted with the dye molecules. A pseudo-second-order kinetics model yielded the most accurate results, indicating that the adsorption of malachite green was driven by chemisorption. Additionally, the study demonstrates a clear correlation between the adsorption capacity of the biocarbons and the pH level of the solution, as it increases proportionately.

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CONTEXT: The efficient catalysis of CO2 adsorption and activation presents a formidable challenge due to its pronounced thermodynamic stability and kinetic inertia. Previous experiments have left gaps in understanding the promotional effects and underlying mechanism of potassium. In this study, we systematically investigate CO2 adsorption and activation on clean and potassium-preadsorbed low index surfaces of transition metals. Theoretical results reveal a substantial augmentation in CO2 binding strength when potassium is introduced, concomitant with a general reduction in activation energies. Notably, linear correlations are significant on close-packed metal surfaces without and with potassium additive. Through a comprehensive analysis encompassing geometric parameters, electronic structures, and energy decomposition, we discern the physical underpinnings of the potassium effect. This enhancement is primarily ascribed to direct electron transfer and dipole-dipole interactions. Furthermore, we scrutinize the impact of an external electric field, demonstrating that the application of a negative electric field accelerates CO2 activation, mirroring the effects observed with potassium. METHODS: All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave method (PAW). Throughout the entire work, the Bayesian error estimation functional (BEEF) was used.

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The development of an efficient bio-char used to remove phenol from wastewater holds great importance for environmental protection. In this work, wheat straw bio-char (BC) was acid-washed by HF and activated at 900 °C with 10% CO2 to obtain bio-char (B-Ⅲ-0.1D900). Adsorption experiments revealed that B-Ⅲ-0.1D900 achieved a remarkable phenol removal efficiency of 90% within 40 min. Despite its relatively low specific surface area of 492.60 m2/g, it exhibited a high maximum adsorption capacity of 471.16 mg/g. Furthermore, B-Ⅲ-0.1D900 demonstrated a good regeneration capacity for at least three cycles (90.71%, 87.54%, 84.36%). It has been discovered that HF washing, which removes AAEM and exposes unsaturated functional groups, constitutes one of the essential prerequisites for enhancing CO2 activation efficiency at high temperatures. After 10% CO2 activation, the mesoporous structure exhibited substantial development, facilitating enhanced phenol infiltration into the pores when compared to untreated BC. The increased branching of the bio-char culminated in a more complete aromatic system, which enhances the π-π forces between the bio-char and the phenol. The presence of tertiary alcohol structure enhances the hydrogen bonding forces, thereby promoting intermolecular multilayer adsorption of phenol. With the combination of various forces, B-Ⅲ-0.1D900 has a good removal capacity for phenol. This work provides valuable insights into the adsorption of organic pollutants using activated bio-char.

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Carbonylation of ethanol with CO2 as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO2 in that the harsh conditions result in undesired activation of α-C-H and even cleavage of C-C bond in ethanol to deteriorate the specific activation of O-H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO2 , in which CO2 is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O-H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO3-x supported Cu2 O (Cu2 O-SrTiCuO3-x ) has been designed. A production of up to 320 µmol g-1 h-1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O-H activation has been afforded in photo-thermal assisted gas-solid process under 3.29 W cm-1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO2 . In the photo-driven activation of CO2 and following carbonylation, CO2 activation energy decreases to 12.6 kJ mol-1 , and the cleavage of alcoholic α-C-H bond has been suppressed.

RESUMEN

The synthesis and characterization of (tBu PBP)Ni(OAc) (5) by insertion of carbon dioxide into the Ni-C bond of (tBu PBP)NiMe (1) is presented. An unexpected CO2 cleavage process involving the formation of new B-O and Ni-CO bonds leads to the generation of a butterfly-structured tetra-nickel cluster (tBu PBOP)2 Ni4 (µ-CO)2 (6). Mechanistic investigation of this reaction indicates a reductive scission of CO2 by O-atom transfer to the boron atom via a cooperative nickel-boron mechanism. The CO2 activation reaction produces a three-coordinate (tBu P2 BO)Ni-acyl intermediate (A) that leads to a (tBu P2 BO)-NiI complex (B) via a likely radical pathway. The NiI species is trapped by treatment with the radical trap (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) to give (tBu P2 BO)NiII (η2 -TEMPO) (7). Additionally, 13 C and 1 H NMR spectroscopy analysis using 13 C-enriched CO2 provides information about the species involved in the CO2 activation process.

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Fusing high-throughput quantum mechanical screening techniques with modern artificial intelligence strategies is among the most fundamental ─yet revolutionary─ science activities, capable of opening new horizons in catalyst discovery. Here, we apply this strategy to the process of finding appropriate key descriptors for CO2 activation over two-dimensional transition metal (TM) carbides/nitrides (MXenes). Various machine learning (ML) models are developed to screen over 114 pure and defective MXenes, where the random forest regressor (RFR) ML scheme exhibits the best predictive performance for the CO2 adsorption energy, with a mean absolute error ± standard deviation of 0.16 ± 0.01 and 0.42 ± 0.06 eV for training and test data sets, respectively. Feature importance analysis revealed d-band center (εd), surface metal electronegativity (χM), and valence electron number of metal atoms (MV) as key descriptors for CO2 activation. These findings furnish a fundamental basis for designing novel MXene-based catalysts through the prediction of potential indicators for CO2 activation and their posterior usage.

RESUMEN

The development of photocatalytic reduction of CO2 is hindered by slow surface reaction kinetics due to the high activation barrier of CO2 and the lack of activation centers in the photocatalyst. To overcome these limitations, this study focuses on enhancing the photocatalytic performance through incorporating Cu atoms into BiOCl. By introducing a minute amount of Cu (0.18 wt%) into BiOCl nanosheets, significant improvements were achieved, with a CO yield of 38.3 µmol g-1 from CO2 reduction, surpassing that of pristine BiOCl by 50%. To explore the surface dynamics of CO2 adsorption, activation and reactions, in situ DRIFTS was employed. Theoretical calculations were further performed to elucidate the role of Cu in the photocatalytic process. The results demonstrate that the incorporation of Cu into BiOCl induces surface charge redistribution, which facilitates efficient trapping of photogenerated electrons and accelerates the separation of photogenerated charge carriers. Furthermore, Cu modification on BiOCl effectively lowers the activation energy barrier by stabilizing the COOH* intermediate, thereby turning the rate-limiting step from COOH* formation to CO* desorption and boosting the CO2 reduction process. This work unveils the atomic-level role of modified Cu in enhancing the CO2 reduction reaction and presents a novel concept for achieving highly efficient photocatalysts.

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Lithium-sulfur (Li-S) batteries have high theoretical energy density but low sulfur utilization due to the inherent insulating nature of sulfur and the shuttle effect of polysulfides. Herein, the CO2-activation carbon paper was prepared by poly(p-phenylenebenzobisoxazole) (PBO) nanofiber and was first applied as an interlayer for efficiently alleviating the shuttle effect of polysulfides in Li-S batteries. This interlayer exhibits good flexibility and strength with rich -C═O and -COOH functional groups on the three-dimensional porous structure, which improves chemical adsorption on Li2Sx species and ion rapid diffusion via interconnected diffusion channels and thus enhances the electrochemical kinetics. The initial specific capacity is 1367.4 mAh g-1 and remains 999.8 mAh g-1 after 200 cycles at 0.2C and 780.1 mAh g-1 at 5C, and the Coulombic efficiency is high, up to 99.8%, which is much better than that for the carbon paper without CO2 activation. The highly conductive flexible PBO carbon paper may bring breakthroughs in performance and thus lead to more practical applications of Li-S batteries.

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CO2 adsorption and activation on Cu single atom catalysts and Cu nanoclusters supported on the (110) surface of rutile and on the (101) surface of anatase TiO2 have been investigated by means of first principles electronic structure calculations. The role of oxide reduction associated to the presence of oxygen vacancies has been considered. Five main messages emerge from this study. (1) CO2 activation on Cu/TiO2 nanostructures is surface sensitive, as the rutile and anatase surfaces can exhibit different behaviors; (2) the surface morphology is essential since CO2 is activated only when the molecule can simultaneously bind to at least two active sites, such as a Cu atom on one side and an oxide ion on the other site; (3) Cu atoms on TiO2 are in the +I oxidation state and can bind and activate CO2 via charge transfer from the oxide; (4) on supported Cu clusters CO2 activation occurs mostly at the metal/oxide interface; (5) the presence of O vacancy sites facilitates the spontaneous dissociation of CO2 to CO, or increases the electron density of the metal catalyst, two effects that can influence the mechanism of CO2 reduction to methanol or other chemicals.

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Frustrated Lewis pairs (FLPs), discovered in the last few decades for homogeneous catalysts and in the last few years also for heterogeneous catalysts, are stimulating the scientific community's interest for their potential in small-molecule activation. Nevertheless, how an FLP activates stable molecules such as CO2 is still undefined. Through a careful spectroscopic study, we here report the formation of FLPs over a highly defective CeO2 sample prepared by microwave-assisted synthesis. Carbon dioxide activation over FLP is shown to occur through a bidentate carbonate bridging the FLP and implying a Ce3+-to-CO2 charge transfer, thus enhancing its activation. Carbon dioxide reaction with methanol to form monomethylcarbonate is here employed to demonstrate active roles of FLP and, eventually, to propose a reaction mechanism clarifying the role of Ce3+ and oxygen vacancies.