Surface Oxygen Groups Research Articles

Moisture dependence of responses in physical–chemical property and CH4 ad-/desorption capability of coals to microwave radiation

For purpose of understanding feasibility of coalbed methane (CBM) production in practical water (H2O)-containing reservoirs by using microwave radiation, the dielectric property highly associated with microwave-absorbing and resultant temperature-rising capabilities of coals were addressed primarily; afterward, the temperature-rising rule of coals and its dependence on moisture were examined; finally, the impacts of moisture on changes about main physical–chemical property and resultant CH4 ad-/desorption performance of coals were investigated under microwave field. Results indicated that the coals display microwave-absorbing potential to raise temperature. The moisture initially increases the temperature-rising rate owing to its strong microwave-absorbing capability while decreases the final bulk temperature because of its endothermal evaporation. The resultant rising temperature decomposes and transforms minerals. Moreover, the temperature rise upgrades crystallite structure of the dried coals. As for the wetted coals, the rapid temperature rise disorders crystallite structure of the Sihe and Yima coals due to potential steam explosion. Furthermore, the radiation decreases the aromaticity and the total surface oxygenic groups of the dried coals; the moisture whittles down these decreasing trends. In general, the micro- and mesopore surface area and volume of the coals drops after radiation. The microwave radiation smooths pore surface of the wetted coals while roughens that of the dried coals. The complexity of the coal pore structure almost reduces after radiation. Besides, the microwave radiation significantly reduces the CH4 adsorption capability of the dried coals by 6.74–36.69 %; the moisture further reduces the CH4 adsorption capability by 20.48–43.03 %. Ultimately, the microwave radiation almost enhances the ad-/desorption hysteresis of CH4 on the dried coals while weakens that of the wetted coals. Such alterations depend on the responses of pore abundance and pore surface roughness to microwave. These findings confirm that microwave radiation is a promising option to produce CBM, particularly for H2O-bearing CBM reservoirs.

The role of carbon textile surface functionalities in reactive adsorption of vapor and liquid 2-chloroethyl ethyl sulfide: Evaluating interactions at the interface

A carbon textile (CT) was chemically modified to increase its surface activity and promote the adsorption and degradation of 2-chloroethyl ethyl sulfide (CEES) - a surrogate for mustard gas. CT was initially subjected to oxidation (CTO), and then heated under ammonia (CTON) or hydrogen sulfide (CTOS) atmosphere to incorporate nitrogen or sulfur functionalities, respectively. Detoxification experiments were performed in closed vials using either vapor or liquid forms of CEES. The maximum vapor weight uptakes on CT, CTO, CTOS, and CTON were 399, 372, 434, and 489 mg/g, respectively. All textiles were able to prevent the vaporization of CEES liquid droplets. Although similar reaction products were detected in both vapor and liquid systems, the marked differences in the extent of CEES chemical transformation on the surfaces of the textiles indicate distinct detoxification pathways influenced by surface chemistry. Even though the heterogeneous surface of CTO, enriched with oxygen surface groups, facilitated various reactions, hydrolysis was the predominant pathway. The thermal treatment, regardless of the atmosphere, reduced the oxygen content, decreasing the extent of hydrolysis. However, incorporating basic surface groups such as pyridines, amines, or weak acids such as thiols promoted dehydrohalogenation as the main detoxification pathway on these samples.

A computational study of adsorption on activated carbons containing basic oxygenated surface groups of two priority organochlorine pesticides from water

In previous work, molecular modeling was used to investigate how acidic and nitrogen-containing surface groups (SG) on an activated carbon (AC) model affect the adsorption of chlordecone (CLD) and β-hexachlorocyclohexane (β-HCH), considering the effects of pH and hydration. Interactions involving acidic SGs at neutral pH indicated chemisorption, while interactions with nitrogen basic SGs suggested physisorption. This study presents a theoretical investigation of the interactions between these pesticides and oxygenated SGs on AC. A coronene molecule with functional groups—specifically pyrone, chromene, or ketone at the edges was used as a simplified model of AC. The Multiple Minima Hypersurface methodology was employed to study the interactions between CLD and β-HCH with SGs on AC using the PM7 semi-empirical Hamiltonian. Further re-optimization of the obtained structures for pesticide-AC complexes was performed using Density Functional Theory. The Quantum Theory of Atoms in Molecules was applied to characterize the interaction types using the Nakanishi criteria. No interactions were observed at acidic pH for both pollutants, whereas dispersive interactions were found at neutral and basic pH, indicating a physisorption process. Molecular dynamics simulations were also conducted to illustrate these findings. Ultimately, our previous studies showed that the adsorption process of CLD and β-HCH on AC is more effectively enhanced with acidic SGs rather than basic SGs. Moreover, MD simulations of β-HCH and CLD pesticides at concentrations higher than their solubilities reveal aggregation in both pure aqueous solutions and those containing AC. Analysis of MD trajectories and RDFs shows that hydrophobic interactions lead to aggregation of these molecules. RDFs indicate that β-HCH aggregates more in the solution due to its lower solubility compared to CLD. This aggregation reduces pesticide adsorption on AC surfaces, with β-HCH showing a more significant decrease in adsorption, dropping by more than half. Similar effects were observed with other biochar models for both pesticides.

Enhanced performance of coal-based adsorbents in removing phenols from highly concentrated coking wastewater: Targeting large-scale applications

Coking wastewater threatens the ecology and environment significantly, but it still has challenges in the efficient removal of organic contaminants due to its complex composition and inadequate biochemical properties. Low-cost coal-based material has potential in treating coking wastewater due to its special structure and surface oxygenic functional groups. In this work, gangue-based materials were modified in different ways and applied to coking wastewater treatment. Combined with the comprehensive analysis of the adsorbents' morphology, structure, and composition with SEM, XRD, FT-IR, XPS, etc., the adsorption behaviors and regeneration properties were extensively investigated. Notably the adsorption and regeneration capacity of the adsorbents are significantly enhanced after modification, BY-C2 exhibits a remarkable COD removal rate of 90.2 % from real coking wastewater, which remains stable at 72.0 % even after 10 cycles. The pseudo-second-order kinetic model and Freundlich isotherm model are found to fit well with the adsorption processes of phenolic compounds in coking wastewater. The adsorption mechanism involves hydrogen bonding, van der Waals' force, capillary forces and electrostatic attraction. This work paves the way for the large-scaled application of coal-based adsorbents in coking wastewater treatment and the subsequent recycling of high-valued organic pollutants.

Modified Cellulose-Based Waste for Enhanced Adsorption of Selected Heavy Metals from Wastewater.

Due to industrial growth and its impact on the environment, the increasing amount of industrial waste requires a comprehensive approach aligned with the principles of sustainable development. The main goals are not only to preserve natural resources but also to encourage innovation in the reuse of waste materials. In an attempt to reduce the problems regarding waste disposal and wastewater treatment in the textile industry, fibrous textile waste was used as a starting material to obtain carbon adsorbents for the removal of pollutants from wastewater. Waste cotton and mixed yarns, mainly consisting of polysaccharide cellulose, were hydrothermally carbonized and activated with KOH to convert them into efficient carbon adsorbents for heavy metal removal from water. Characterization of carbonized material showed that after activation, an increase in specific surface area (up to 872 m2/g) and content of surface oxygen groups (6.04 mmol/g) leads to a higher affinity towards heavy metal ions, especially lead ions, and high adsorption capacity of 19.98 mg/g obtained for activated cotton yarns. The results of this research represent a contribution to the reduction of waste materials by modifying them into adsorbents, while the regeneration of adsorbents is an example of the practical application of polysaccharide-based materials in the purification of wastewater containing various heavy metal ions.

Deepening the Understanding of Carbon Active Sites for ORR Using Electrochemical and Spectrochemical Techniques.

Defect-containing carbon nanotube materials were prepared by subjecting two commercial multiwalled carbon nanotubes (MWCNTs) of different purities to purification (HCl) and oxidative conditions (HNO3) and further heat treatment to remove surface oxygen groups. The as-prepared carbon materials were physicochemically characterized to observe changes in their properties after the different treatments. TEM microscopy shows morphological modifications in the MWCNTs after the treatments such as broken walls and carbon defects including topological defects. This leads to both higher surface areas and active sites. The carbon defects were analysed by Raman spectroscopy, but the active surface area (ASA) and the electrochemical active surface area (EASA) values showed that not all the defects are equally active for oxygen reduction reactions (ORRs). This suggests the importance of calculating either ASA or EASA in carbon materials with different structures to determine the activity of these defects. The as-prepared defect-containing multiwalled carbon nanotubes exhibit good catalytic performance due to the formation of carbon defects active for ORR such as edge sites and topological defects. Moreover, they exhibit good stability and methanol tolerances. The as-prepared MWCNTs sample with the highest purity is a promising defective carbon material for ORR because its activity is only related to high concentrations of active carbon defects including edge sites and topological defects.

Systematic Investigations of Surface Oxygen Functional Groups on Spherical Hard Carbon for Sodium-Ion Batteries

The surface activity of hard carbons and its effect on the formation of a stable solid electrolyte interface (SEI) in sodium ion batteries has gained significant interest in the scientific community over the last years. The surface of hard carbons thus plays a pivotal role within the cell, as it constitutes the interface between the bulk material and the electrolyte. Following pyrolysis of the carbon-rich precursor at high temperatures, various oxygen functional groups (OFGs) and defects, such as five- or seven-membered rings, are present on the surface of the resulting hard carbons. The influence of OFGs on the surface is however controversially discussed. On the one hand, irreversible reactions of sodium ions with OFGs lower the initial coulombic efficiency (ICE), which leads to a decreased energy density. On the other hand, OFGs may also serve as nucleation sites for the SEI leading to a more conductive interfacial phase for sodium ions. Although many approaches of additional oxygen functionalization on the surface of hard carbons have already been reported, they mostly employ harsh reaction conditions disregarding the morphological impact on the carbon surface.In our studies, oxo-functionalized polycyclic aromatic hydrocarbons (PAHs) are adsorbed on the surface to serve as model OFGs on surface oxygen deficient hard carbons. The versatility of functionalized pyrenes in combination with nondestructive adsorption enables independent investigations on the oxygen functionalization of the hard carbon surface. In the first step, native surface oxygen groups are cleaved from the pristine hard carbon through a high-temperature post-treatment in hydrogen atmosphere. Afterwards, selective re-introduction of surface OFGs is achieved through adsorption of oxo-functionalized pyrene derivatives such as 1-hydroxypyrene or 1-pyrenecarboxylic acid to simulate hydroxy or carboxylic surface functionalities. Additionally, various spatially configurations of surface OFGs can be mimicked by elongating the distance between the oxygen functionality and the pyrene backbone through a short alkyl chain (e.g. 1-pyrenebutyric acid).Our systematic approach of selectively re-introducing surface OFGs allows the discrimination between different surface OFGs and their influence on the SEI. The surface of our modified hard carbons is characterized by X-Ray photoelectron spectroscopy (XPS) and Raman spectroscopy to evaluate the oxygen content and determine the defect concentration. The electrochemical performance is assessed by rate performance tests and cyclic voltammetry in three-electrode half-cells with sodium metal as counter and reference electrode. Initial findings validate the correlation between surface oxygen functionalization determined by XPS and the electrochemical formation potential of the SEI during the first cycle. After high-temperature treatment in a hydrogen atmosphere, the surface oxygen content decreases from ~5% to 2%, leading to a significant lowering of the plateau capacity. Simultaneously, the ICE decreases from 79% to 55%. Cyclic voltammetry of deoxygenated hard carbon reveals that the SEI formation potential is shifted from ~1.0 V vs. Na towards lower potentials of ~0.3 V vs. Na indicating that different decomposition products are formed. Furthermore, rate performance is substantially deteriorated by the development of a modified SEI. Ex-situ XPS of cycled electrodes and electrochemical impedance spectroscopy are used to identify differences in the SEI composition and link them to the electrochemical performance of our spherical hard carbons.Figure: 1-Pyrenebutyric acid adsorbed on the surface of hard carbon highlighting the different possible spatially orientations of the oxygen functional group. Figure 1

Enhancing charge storage capacity of cellulose-sweat-based electrolyte flexible supercapacitors with electrochemically exfoliated free-standing carbon yarn electrodes

The Internet of Things (IoT) provides an interface between different electronic devices such as flexible electronics, and e-textiles to capture and receive real-time data and help humans to devise systems that will adequately respond to these environmental stimuli. The main limitations of these devices to work 24/7 are the lack of continuous power supply and easy integration into textiles to perform their functions. The other issues are poor adhesion of active materials with substrates and peeling-off of active material from the electrode substrates and consequently, degradation of electrochemical performance. A potential and evolving strategy is fabricating a current collector-less and integrable carbon yarn-based energy storage device. Herein, we are presenting a facile and novel technique to exfoliate carbon yarn fibers to enhance their electrochemical performance by 3 orders of magnitude. Activated carbon yarn wires acting as current collector-less electrodes along with cellulose acetate-based composite separators offer a large surface area to simulated sweat electrolyte ions and show a gravimetric capacitance of 11.28 Fg−1 at the scan rate of 5 mVs−1. Activated carbon yarn-based symmetric supercapacitor device in a simulated sweat solution electrolyte offers excellent cyclic and bending stability with over 95 % capacitance retention in both tests. Theoretical insightSupercapacitors (SCs) comprise many active and passive elements. The most passive and vital elements are current collectors, separators, binders, electrolytes, and packaging. Two key elements, current collector and binders can be eliminated by developing current collector-free or free-standing electrodes. Carbonaceous materials such as graphene [1,2], carbon nanotubes (CNT) [3], porous carbon [2], and carbon onions[4,5] are common alternatives of active materials for SCs electrodes owing to their low cost, chemical stability, large surface area, and high electrical conductivity. These active materials show exceptional attributes such as long cyclic life, and high-rate capability owing to their intrinsic operation mechanism e.g., surface charge storage due to large surface area. However, they also suffer from low specific capacitance ascribed to low surface area exposed to electrolyte ions and low charge storage due to poor wettability. The most efficient technique to address this problem is to incorporate doped heteroatoms or surface functional groups such as surface oxygen groups present on the surface of carbon yarn. The inclusion of these doped heteroatoms and functional groups boosts the intrinsic properties, such as electrical conductivity, and wettability. The increased electro-active surface area offers more active sites for electrolyte ions, resulting in more charge storage and higher pseudocapacitance [6–8].Carbon yarn comprised of long-chain carbon filaments of 2.5–5 µm in radius, excellent conductivity, high chemical and mechanical stability, and light weightiness make it a potential candidate as an active material or a free-standing electrode for SCs. However, due to its low specific capacitance, limited surface area, and low porosity, carbon yarn failed to be directly exploited as a free-standing or current collector-less electrode for flexible supercapacitor applications.

Nanoarchitectonics of porous carbon derived from urea-impregnated microporous triazine polymer in KOH activator for adsorptive removal of sulfonamides from water

A microporous covalent-organic polymer (triazine polymer, referred to as MCTP), was synthesized and subsequently carbonized, after loading urea and KOH (serving as an additional nitrogen source and activator, respectively), through high-temperature pyrolysis. This process resulted in materials named KUCDCs, which exhibited high porosity and a broader range of pore sizes compared to carbon materials produced without the addition of urea and KOH, referred to as CDC. KUCDCs, CDC, and commercially available activated carbon (AC) were evaluated for their ability to remove sulfonamide drugs, sulfamethoxazole (SMX) and sulfachlorpyridazine (SCP), from aqueous solution. Among these materials, KUCDC-800, which was carbonized at a temperature of 800 °C, demonstrated superior adsorption performances for sulfonamides, attributed to its high porosity, nitrogen content, and presence of surface oxygen groups. The adsorption capacities for SMX and SCP on KUCDC were notably higher than those on AC and MDC, with maximum capacities (Q0) of 619 and 554 mg/g for SMX and SCP, respectively. Notably, KUCDC-800 stands out as a recyclable adsorbent with the highest reported Q0 for SMX to date under near-neutral conditions. The exceptional performance of KUCDC in adsorbing SMX could be explained by its high porosity and surface functionalities for hydrogen bonding interactions with the adsorbate.

Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization.

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon-supported single atom catalysts focused on nitrogen-doped carbons, which, unlike classic carbon materials, have a fairly well-defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting-edge analytical methods.

Removal of Iron and Copper Ions and Phenol from Liquid Phase by Membrane Based on Carbonaceous Materials.

The present work reports an effective method for the removal of inorganic and organic pollutants using membranes based on different carbonaceous materials. The membranes were prepared based on cellulose acetate (18 wt. %), polyvinylpyrrolidone as a pore-generating agent (2 wt. %) and activated carbon (1 wt. %). Activated carbons were developed from residues after extraction of the mushroom Inonotus obliguus using microwave radiation. It has been demonstrated that the addition of activated carbon to the membranes resulted in alterations to their physical properties, including porosity, equilibrium water content and permeability. Furthermore, the chemical properties of the membranes were also affected, with changes observed in the content of the surface oxygen group. The addition of carbon material had a positive effect on the removal of copper ions from their aqueous solutions by the cellulose-carbon composites obtained. Moreover, the membranes proved to be more effective in the removal of copper ions than iron ones and phenol. The membranes were found to show higher effectiveness in copper removal from a solution of the initial concentration of 800 mg/L. The most efficient in copper ions removal was the membrane containing urea-enriched activated carbon.

Promoting the circular economy: Valorization of a residue from industrial char to activated carbon with potential environmental applications as adsorbents

Pyrolysis of residues enriched with carbon, such as in agroforestry or industrial activities, has been postulated as an emerging technology to promote the production of biofuels, contributing to the circular economy and minimizing waste. However, during the pyrolysis processes a solid fraction residue is generated. This work aims to study the viability of these chars to develop porous carbonaceous materials that can be used for environmental applications. Diverse chars discharged by an industrial pyrolysis factory have been activated with KOH. Concretely, the char residues came from the pyrolysis of olive stone, pine, and acacia splinters, spent residues fuel, and cellulose artificial casings. The changes in the textural, structural, and composition characteristics after the activation process were studied by N2 adsorption-desorption isotherms, scanning electron microscopy, FTIR, elemental analysis, and XPS. A great porosity was developed, SBET within 776–1186 m2 g−1 and pore volume of 0.37–0.59 cm3 g−1 with 70–90% of micropores contribution. The activated chars were used for the adsorption of CO2, leading to CO2 maximum uptakes of 90–130 mg g−1. There was a good correlation between the CO2 uptake with microporosity and oxygenated surface groups of the activated chars. Moreover, their ability to adsorption of contaminants in aqueous solution was also evaluated. Concretely, there was studied the adsorption of aqueous heavy metals, i.e., Cd, Cu, Ni, Pb, and Zn, and organic pollutants of emerging concern such as caffeine, diclofenac, and acetaminophen.

Comparison of the Influence of Oxygen Groups Introduced by Graphene Oxide on the Activity of Carbon Felt in Vanadium and Anthraquinone Flow Batteries.

An increasing number of studies focus on organic flow batteries (OFBs) as possible substitutes for the vanadium flow battery (VFB), featuring anthraquinone derivatives, such as anthraquinone-2,7-disulfonic acid (2,7-AQDS). VFBs have been postulated as a promising energy storage technology. However, the fluctuating cost of vanadium minerals and risky supply chains have hampered their implementation, while OFBs could be prepared from renewable raw materials. A critical component of flow batteries is the electrode material, which can determine the power density and energy efficiency. Yet, and in contrast to VFBs, studies on electrodes tailored for OFBs are scarce. Hence, in this work, we propose the modification of commercial carbon felts with reduced graphene oxide (rGO) and poly(ethylene glycol) for the 2,7-AQDS redox couple and to preliminarily assess its effects on the efficiency of a 2,7-AQDS/ferrocyanide flow battery. Results are compared to those of a VFB to evaluate if the benefits of the modification are transferable to OFBs. The modification of carbon felts with surface oxygen groups introduced by the presence of rGO enhanced both its hydrophilicity and surface area, favoring the catalytic activity toward VFB and OFB reactions. The results are promising, given the improved behavior of the modified electrodes. Parallels are established between the electrodes of both FB technologies.

One-step generation of hollow graphitic carbon nanospheres with suitable oxygenated structures as conductive additives for water-soluble binder in highly stable supercapacitor electrodes

Although the weight ratio of electron conductive additives and the binder to porous carbons in the electrode component of electric double-layer capacitors (EDLC) is minimal, however, without them the electrochemical performances of EDLC would decay quickly. In this work, we present a one-step approach for manufacturing a unique conductive carbon material that shows highly connecting hollow structures as well as approximate oxygenated surface groups to create a synergy effect with aqueous binder and the main component, porous carbon. The as-prepared carbon nanospheres (HCNs) were generated from a typical carbon black-PC20 in air (denoted as PC20HT) at mild temperatures ranging from 400 to 700 °C for 2–4 h at a massive scale of approximate 1 kg h−1. The as-prepared PC20HT displays a high specific surface area of 657 m2 g−1 (the pristine PC20 has 112 m2 g−1) with a pore volume of 0.71 cm3 g−1, and an oxygen content of 14.10 wt%. Interestingly, a premixing of PC20HT and porous carbon is required before making the electrode pastes. The well-premixed carbon materials and a water-soluble binder-polyacrylic acid are composed into highly-stable components as EDLC electrodes in an organic electrolyte. As consequently, the PC20HT-assisted electrodes demonstrate highly stable life cycles (charge-discharge behaviors), with a retention rate 82.13 % over 50,000 cycles at a narrow voltage window of 2.5–2.7 V at 0.5 A g−1 when compared to two conventional conductive carbons, BP2000 (68.45 %) and Super P (67.46 %). Thermal annealing at 900 °C in Ar reduces the oxygen content of PC20HT to 4.25 wt% (referred to as TPC20HT), increasing the retention rate of life cycle to 88.89 % after the same cycles. TPC20HT-assisted EDLC electrodes exhibit a superior energy density of 34.76 Wh kg−1, which is higher than CB-BP2000 and Super P-assisted EDLC electrodes. The transforming of structural morphologies as well as the surface oxygenated and graphitic structures of the as-prepared HCS, PC20HT, and TPC20HT were also described before and after long-term cycling. This simple route for producing conductive carbons is applicable in an aqueous binder system for preparing EDLC electrodes with a cost-effective and environmentally friendly approach.

3D/2D MnO/MXene heterostructure with high efficiency for adsorbing uranium

An innovative MnO/Ti3C2 MXene heterostructure, consisting of three-dimensional (3D) MnO nanosheet array directly assembled on two-dimensional (2D) Ti3C2 MXene nanosheets, was synthesized via a simple hydrothermal-annealing strategy for uranium elimination. This unique 3D/2D heterostructure derived substantially high specific surface area (311.9 m2/g) and exposed considerable amount of surface oxygen groups, including surface lattice M–O and adsorbed –OH. Through a comprehensive exploration encompassing adsorbent dosage, pH, ionic strength, initial U(VI) concentration, and environmental conditions, the MnO/Ti3C2 MXene heterostructure demonstrated an extraordinary proficiency and specificity in the removal of U(VI). This composite exhibited an outstanding adsorption capacity of 862.1 mg/g, with a removal efficiency of 99.7 % and rapid kinetics (above 90 % within 20 s). The kinetic study indicated the adsorption process followed chemisorption dynamics and single-layer adsorption behavior. Comprehensive analyses validated the structural integrity and confirmed the successful uranium adsorption via strong interaction between UO22+ and surface unsaturated oxygen groups. Notably, the MnO/Ti3C2 MXene maintained excellent recyclability, highlighting its potential for large-scale applications. It emerges as a promising candidate for uranium removal, offering insights for optimizing composite materials in diverse environmental conditions and fostering advancements in water purification technologies.

Degradation of Graphene in High- and Low-Humidity Air, and Vacuum Conditions at 300-500 K.

Graphene is a fundamental unit of carbon materials and, thus, primary sp2-bonded carbon material. Graphene is, however, easily broken macroscopically despite high mechanical strength, although its natural degradation has rarely been considered. In this work, we evaluate the natural degradation of two-layer graphene in vacuo, in low-humidity air, and in high-humidity air at 300, 400, 450, and 500 K. Over 1000 days of degradation at 300 K, the graphene structure was highly maintained in vacuo, whereas the layer number of graphene tended to decrease in high- and low-humidity air. Water was slightly reacted/chemisorbed on graphene to form surface oxygen groups at 300 K. At 450 and 500 K, graphene was moderately volatilized in vacuo and was obviously oxidized in high- and low-humidity air. Surprisingly, the oxidation of graphene was more suppressed in the high-humidity air than in the low-humidity air, indicating that water worked as an anti-oxidizer of graphene by preventing the chemisorption of oxygen on the graphene surface.

Carboxylated Hexagonal Boron Nitride/Graphene Configuration for Electrosynthesis of High‐Concentration Neutral Hydrogen Peroxide

AbstractThe electrosynthesis of hydrogen peroxide (H2O2) via two‐electron (2e−) oxygen (O2) reduction reaction (ORR) has great potential to replace the traditional energy‐intensive anthraquinone process, but the design of low‐cost and highly active and selective catalysts is greatly challenging for the long‐term H2O2 production under industrial relevant current density, especially under neutral electrolytes. To address this issue, this work constructed a carboxylated hexagonal boron nitride/graphene (h‐BN/G) heterojunction on the commercial activated carbon through the coupling of B, N co‐doping with surface oxygen groups functionalization. The champion catalyst exhibited a high 2e− ORR selectivity (>95 %), production rate (up to 13.4 mol g−1 h−1), and Faradaic efficiency (FE, >95 %). The long‐term H2O2 production under the high current density of 100 mA cm−2 caused the cumulative concentration as high as 2.1 wt %. The combination of in situ Raman spectra and theoretical calculation indicated that the carboxylated h‐BN/G configuration promotes the adsorption of O2 and the stabilization of the key intermediates, allowing a low energy barrier for the rate‐determining step of HOOH* release from the active site and thus improving the 2e− ORR performance. The fast dye degradation by using this electrochemical synthesized H2O2 further illustrated the promising practical application.

Carboxylated Hexagonal Boron Nitride/Graphene Configuration for Electrosynthesis of High-Concentration Neutral Hydrogen Peroxide.

The electrosynthesis of hydrogen peroxide (H2 O2 ) via two-electron (2e- ) oxygen (O2 ) reduction reaction (ORR) has great potential to replace the traditional energy-intensive anthraquinone process, but the design of low-cost and highly active and selective catalysts is greatly challenging for the long-term H2 O2 production under industrial relevant current density, especially under neutral electrolytes. To address this issue, this work constructed a carboxylated hexagonal boron nitride/graphene (h-BN/G) heterojunction on the commercial activated carbon through the coupling of B, N co-doping with surface oxygen groups functionalization. The champion catalyst exhibited a high 2e- ORR selectivity (>95 %), production rate (up to 13.4 mol g-1 h-1 ), and Faradaic efficiency (FE, >95 %). The long-term H2 O2 production under the high current density of 100 mA cm-2 caused the cumulative concentration as high as 2.1 wt %. The combination of in situ Raman spectra and theoretical calculation indicated that the carboxylated h-BN/G configuration promotes the adsorption of O2 and the stabilization of the key intermediates, allowing a low energy barrier for the rate-determining step of HOOH* release from the active site and thus improving the 2e- ORR performance. The fast dye degradation by using this electrochemical synthesized H2 O2 further illustrated the promising practical application.

Transformation of Al Species on Carbon Surfaces: Effects of Al Species and Carbon Surface Oxygen Groups.

Control of residual Al is critical, owing to its high tendency to accumulate in drinking water distribution systems and its potential risks to human health. Herein, the effects of surface properties of activated carbon (AC) on intercepting different Al species (including monomeric Al and polymeric Al species-Al13) are evaluated. The results showed that Al in the form of monomers was considerably adsorbed by AC; whereas Al in the form of polymeric Al13 was held to a much lower degree by AC, and the effluent Al concentration was even higher than that without AC. By comparing virgin AC and hydrogen thermal treated AC, the surface oxygen functional groups on the AC were proposed to play a critical role in the transformation of Al species. The oxygen functional groups on the AC surface can directly form complexes with monomeric Al, thereby inducing the binding of monomeric Al on the AC surface. However, the AC surface oxygen groups could not bind to polymeric Al13, and the interaction between AC surface oxygen groups and polymeric Al13 partially transforms Al13 into monomeric Al species, which inhibited the self-aggregation of Al13. This study aims to provide new insights into the control of residual Al in water treatment plants to ensure drinking water safety.

Interfacial carbonyl groups of propylene carbonate facilitate the reversible binding of nitrogen dioxide.

The interaction of NO2 with organic interfaces is critical in the development of NO2 sensing and trapping technologies, and equally so to the atmospheric processing of marine and continental aerosol. Recent studies point to the importance of surface oxygen groups in these systems, however the role of specific functional groups on the microscopic level has yet to be fully established. In the present study, we aim to provide fundamental information on the interaction and potential binding of NO2 at atmospherically relevant organic interfaces that may also help inform innovation in NO2 sensing and trapping development. We then present an investigation into the structural changes induced by NO2 at the surface of propylene carbonate (PC), an environmentally relevant carbonate ester. Surface-sensitive vibrational spectra of the PC liquid surface are acquired before, during, and after exposure to NO2 using infrared reflection-absorption spectroscopy (IRRAS). Analysis of vibrational changes at the liquid surface reveal that NO2 preferentially interacts with the carbonyl of PC at the interface, forming a distribution of binding symmetries. At low ppm levels, NO2 saturates the PC surface within 10 minutes and the perturbations to the surface are constant over time during the flow of NO2. Upon removal of NO2 flow, and under atmospheric pressures, these interactions are reversible, and the liquid surface structure of PC recovers completely within 30 min.