Elucidating the impact of oxygen functional groups on the catalytic activity of M-N4-C catalysts for the oxygen reduction reaction: a density functional theory and machine learning approach.

Efforts to enhance the efficiency of electrocatalysts for the oxygen reduction reaction (ORR) in energy conversion and storage devices present formidable challenges. In this endeavor, M-N4-C single-atom catalysts (MN4) have emerged as promising candidates due to their precise atomic structure and adaptable electronic properties. However, MN4 catalysts inherently introduce oxygen functional groups (OGs), intricately influencing the catalytic process and complicating the identification of active sites. This study employs advanced density functional theory (DFT) calculations to investigate the profound influence of OGs on ORR catalysis within MN4 catalysts (referred to as OGs@MN4, where M represents Fe or Co). We established the following activity order for the 2eORR: for OGs@CoN4: OH@CoN4 > CoN4 > CHO@CoN4 > C-O-C@CoN4 > COC@CoN4 > COOH@CoN4 > CO@CoN4; for OGs@FeN4: COC@FeN4 > CO@FeN4 > OH@FeN4 > FeN4 > COOH@FeN4 > CHO@FeN4 > C-O-C@FeN4. Multiple oxygen combinations were constructed and found to be the true origin of MN4 activity (for instance, the overpotential of 2OH@CoN4 as low as 0.07 V). Furthermore, we explored the performance of the OGs@MN4 system through charge and d-band center analysis, revealing the limitations of previous electron-withdrawing/donating strategies. Machine learning analysis, including GBR, GPR, and LINER models, effectively guides the prediction of catalyst performance (with an R2 value of 0.93 for predicting ΔG*OOH_vac in the GBR model). The Eg descriptor was identified as the primary factor characterizing ΔG*OOH_vac (accounting for 62.8%; OGs@CoN4: R2 = 0.9077, OGs@FeN4: R2 = 0.7781). This study unveils the significant impact of OGs on MN4 catalysts and pioneers design and synthesis criteria rooted in Eg. These innovative findings provide valuable insights into understanding the origins of catalytic activity and guiding the design of carbon-based single-atom catalysts, appealing to a broad audience interested in energy conversion technologies and materials science.

Investigation of the Mechanisms of CO2/O2 Adsorption Selectivity on Carbon Materials Enhanced by Oxygen Functional Groups.

Power plant flue gas and industrial waste gas are produced in large quantities. Using these as feedstocks for CO2 electroreduction has important practical significance for the treatment of excessive CO2 emissions. However, O2 in such sources strongly inhibits the electrochemical conversion of CO2. The inhibitory effect of O2 can be mitigated by constructing CO2-enriched regions on the surface of the cathode. In this study, the reaction zone was controlled by the selective adsorption of CO2 on oxygen-functionalized carbon materials. The results of quantum chemical simulations showed that CO2 adsorption was mainly influenced by electrostatic interactions, whereas O2 adsorption was completely regulated by dispersion interactions. This distinction indicated that introducing polar oxygen functional groups at the edge of the carbon plane can significantly enhance the selectivity for CO2/O2 adsorption. The difference in the adsorption energy between CO2 and O2 increased most noticeably after the carboxyl groups were introduced. The results of the adsorption experiments showed that oxygen-functionalization increased the CO2/O2 selectivity of the carbon material under an atmosphere of multicomponent gases by more than 4.9 times. The carboxyl groups played a dominant role. Our findings might act as a reference for the selective adsorption of polar molecules over nonpolar molecules.

Synergistic mechanism of formaldehyde adsorption by intrinsic defects and carboxyl groups on the surface of carbon materials.

The adsorption of formaldehyde on the original carbon material is limited. Determining the synergistic adsorption of formaldehyde by different defects on the carbon material is necessary for comprehensively understanding the mechanism of formaldehyde adsorption on the surface of the carbon material. The synergistic effect of intrinsic defects and oxygen-containing functional groups on formaldehyde adsorption on the surface of carbon materials was simulated and verified by experiments. Based on the density functional theory, the adsorption of formaldehyde on different carbon materials was simulated by quantum chemistry. The synergistic adsorption mechanism was studied by energy decomposition analysis, IGMH, QTAIM, and charge transfer, and the binding energy of hydrogen bonds was estimated. The results showed that the energy for the adsorption of formaldehyde adsorbed by the carboxyl group on the vacancy defect was the highest, at -11.86 kcal/mol, the hydrogen bond binding energy was -9.05 kcal/mol, and a larger charge transfer was recorded. The mechanism of synergy was studied comprehensively, and the simulation results were verified at multiple scales. This study provides valuable insights into the effect of carboxyl groups on the adsorption of formaldehyde by activated carbon.

Effect of oxygen functional groups on competitive adsorption of benzene and water on carbon materials: Density functional theory study.

It is important to study the effect of oxygen-containing functional groups on the competitive adsorption mechanism of benzene and water on the surface of carbon materials, and to directional modification of activated carbon to improve its selective adsorption of benzene in air. In this study, the adsorption characteristics of benzene and water on original and linked ester, carboxyl, hydroxyl, carbon materials linked by ether groups were calculated by quantum chemical simulation based on density functional theory. The types and proportions of weak interactions in the adsorption process were calculated by energy decomposition analysis, and the adsorption mechanism of carbon materials for water and benzene was described. The influence and contribution of oxygen-containing functional groups on the adsorption of benzene and water were further analyzed by van der Waals potential and electrostatic potential, respectively, so as to determine the difference in the adsorption effect of different types of oxygen-containing functional groups on the two molecules. It was found that the carboxyl group has a great influence on the hydrophilicity of carbon materials, and the electrostatic potential distribution before and after linking the carboxyl group changed significantly. Therefore, they can attract each other with water through hydrogen bonds and occupy the surface adsorption sites of carbon materials, thereby inhibiting the adsorption of benzene on carbon materials. On the contrary, due to its hydrophobic properties, the ether group will free up adsorption space for the adsorption of benzene on the surface of the carbon material, which is beneficial to the adsorption of benzene. The adsorption experiments were carried out, and the results were consistent with the simulation. This study provides an idea for preparing efficient carbonaceous adsorbent of benzene and reducing benzene pollution in industry.

Promotion of formaldehyde degradation by electro-Fenton: Controlling the distribution of ·OH and formaldehyde near cathode to increase the reaction probability.

The mismatch of pollutant concentration and ·OH concentration is the key reason for the inefficient degradation of formaldehyde in the electro-Fenton system. Therefore, formaldehyde and ·OH are adsorbed near the cathode, and the high concentration reaction region is constructed to increase the reaction probability, which is called control of the reaction region. Through nitrogen doping modification of the activated carbon cathode, the adsorption capacity of the modified cathode for formaldehyde and active species, and the selectivity of the two-electron oxygen reduction reaction were deeply analyzed. The results show that the suitable nitrogen doping form of the modified cathode significantly promotes the adsorption capacity of formaldehyde and H2O2, which is beneficial to realizing the promotion of formaldehyde degradation by nitrogen doped cathodes in the electro-Fenton system through control of the reaction region. Graphite nitrogen and pyrrolic nitrogen improve formaldehyde adsorption by enhancing the van der Waals force (8.897 mg g-1), and pyridinic nitrogen improve H2O2 adsorption (1.841 mg g-1) by enhancing the effect of hydrogen bonding interaction. Nitrogen doping enhances Fe2+ regeneration, which contributes to the generation of ·OH at the cathode, and promotes formaldehyde degradation. The control of the reaction region through modification of the electro-Fenton cathode achieved formaldehyde degradation of 35.1 mg L-1 (48.51% higher than that of the unmodified cathode), which provides a promising process for formaldehyde treatment.

Copper ferrite and cobalt oxide two-layer coated macroporous SiC substrate for efficient CO2-splitting and thermochemical energy conversion.

CO2-splitting and thermochemical energy conversion effectiveness are still challenged by the selectivity of metal/metal oxide-based redox materials and associated chemical reaction constraints. This study proposed an interface/substrate engineering approach for improving CO2-splitting and thermochemical energy conversion through CuFe2O4 and Co3O4 two-layer coating SiC. The newly prepared material reactive surface area available for gas-solid reactions is characterized by micro-pores CuFe2O4 alloy easing inter-layer oxygen micro mass exchanges across a highly stable SiC-Co3O4 layer. Through a thermogravimetry analysis, oxidation of the thermally activated oxygen carriers exhibited remarkably CO2-splitting capacities with a total CO yield of 1919.33 µmol/g at 1300 °C. The further analysis of the material CO2-splitting performance at the reactor scale resulted in 919.04 mL (788.94 µmol/g) of CO yield with an instantaneous CO production rate of 22.52 mL/min and chemical energy density of 223.37 kJ/kg at 1000 °C isothermal redox cycles. The reaction kinetic behavior indicated activation energy of 30.65 kJ/mol, which suggested faster CO2 activation and oxidation kinetic on SiC-Co3O4-CuFe2O4 O-deficit surfaces. The underlying mechanism for the remarkable thermochemical performances was analyzed by combining experiment and density functional theory (DFT) calculations. The significance of exploiting the synergy between CuFe2O4 and Co3O4 layers and stoichiometric reaction characteristics provided fundamental insights useful for the theoretical modeling and practical application of the solar thermochemical process.

Activity origin of boron doped carbon cluster for thermal catalytic oxidation: Coupling effects of dopants and edges.

Catalytic oxidation plays important roles in energy conversion and environment protection. Boron-doped crystalline carbocatalyst has been demonstrated effective; however, the application potential of boron-doped amorphous carbocatalyst remains to be explored. For amorphous carbon material, finite-sized carbon clusters are the basic structural units, which exhibit unique activity due to edge and size effect. Herein, using sulfur dioxide (SO2) and carbon monoxide (CO) oxidation as probe thermal-catalysis reactions, we found the distribution and reactivity of active sites in boron-doped carbon clusters are simultaneously determined by dopants and edges. According to comparisons of oxygen (O2) chemisorption energy at different sites of symmetric and non-symmetric carbon cluster, the most active site is found to be the edge carbon atom with high electron donation ability, which can be accurately identified by electrophilic Fukui function. More importantly, the reactivity of boron-doped cluster is simultaneously influenced by doping configuration and the type of edge, based on which -O-B-O- configuration embedded into K-region edge (isolated carbon-carbon double bonds that do not belong to Clar sextet) is predicted to exhibit the highest reactivity among various boron doping configurations. This work clarifies unique activity origin of heteroatom-doped amorphous carbon materials, providing new insights into designing high-performance carbocatalysts.

Understanding the activity origin of oxygen-doped carbon materials in catalyzing the two-electron oxygen reduction reaction towards hydrogen peroxide generation.

Oxygen-doped carbon materials (OCM) have received a lot of attention for catalyzing the two-electron oxygen reduction reaction (2eORR) towards hydrogen peroxide generation, but the origin of their activity is not well understood. Based on density functional theory calculations, we introduce the Fukui function (f0), a more comprehensive and accurate method for identifying active sites and systematically investigating the activity of carbon materials doped with typical oxygen functional groups (OGs). According to the results, only ether or carbonyl has the potential to become the activity origin. The 2eORR activities of carbon materials co-doped by different OGs were then investigated, and a significant synergistic effect was discovered between different OGs (particularly between epoxy and other OGs), which might be the real active centers in OCM. To further understand the cause of the activity, the Fundamental Gap (Eg) was introduced to investigate the ability of various OCM to gain and lose electrons. The results show that the decrease in overpotential after oxygen co-doping can be attributed to the decrease in Eg. This work introduces descriptors (f0 and Eg) that can aid in the efficient design of catalysts and adds to our understanding of the 2eORR activity origin of OCM.

A new insight into the SO2 adsorption behavior of oxidized carbon materials using model adsorbents and DFT calculations.

Heteroatom-doped carbon materials have been proven to be very effective for gas adsorption. Herein, edge-carboxylated graphene nanoplatelets with gradient oxygen contents and consistent pore structures were used as model adsorbents to independently determine the effects of the oxygen functionalization of carbon materials on the SO2 adsorption. The OGnPs were obtained by employing a simple ball milling method using dry ice by which an oxygen content as high as 14.06 wt% could be achieved, resulting in a 20 times increase in SO2 adsorption capacity as compared to that of oxygen-free graphene nanoplatelets. Both the experiments and density functional theory calculations demonstrated that the enhanced SO2 adsorption on the oxygenated carbon surface had a physisorption nature, which provided new insights into the development of advanced carbon materials with heteroatom doping for gas molecule adsorption.