rGO supported self-assembly of 2D nano sheet of (g-C3N4) into rod-like nano structure and its application in sonophotocatalytic degradation of an antibiotic

Graphitic carbon nitride (g-C₃N₄) is an analog of graphite due to its unique electronic structure. g-C₃N₄ based materials have been used in photocatalytic applications. However, pure g-C₃N₄ suffers from major shortcomings which include poor disparity, low surface area and a high recombination rate of photo generated electron-hole pairs that significantly reduce its photocatalytic activity. In this work, self-assembly of g-C₃N₄ sheet into rod shaped g-C₃N₄ was developed via a simple polymerisation method. A composite made of g-C₃N₄ nanorods and rGO (rGO-RCN) was also prepared. The band gap g-C₃N₄ was shifted from 2.77 to 2.6 eV evidented by UV-DRS data. As a result, rGO-RCN showed a relatively high absorption in the visible region. Moreover, a fast electron transfer rate was observed with rGO-RCN composite as conformed from PL analysis and photocurrent measurement. The formation of nanorod and sheet morphologies was confirmed via TEM analysis. The photocatalytic activities of prepared sheet-g-C₃N₄ (SCN)_, Rod g-C₃N₄ (RCN), reduced graphene oxide supported sheet-g-C₃N₄ (rGO-SCN) and reduced graphene oxide supported Rod-g-C₃N₄ (rGO-RCN) were evaluated using a commonly used antibiotic (tetracycline). Among these catalysts, rGO-RCN nanocomposite showed sonophotocatalytic activity 3 times higher compared to pure g-C₃N₄. This superior sonophotocatalytic activity could be due to enhanced visible light absorption of the material, active sites generated by ultrasound, and the high electron transport property of rGO.     

Preparation of graphitic carbon nitride with large specific surface area and outstanding N2 photofixation ability via a dissolve-regrowth process

Nitrogen fixation is the second most important chemical process in nature next to photosynthesis. Here, we report a convenient dissolve-regrowth method for synthesizing graphitic carbon nitride (g-C₃N₄) with a large surface area and nitrogen vacancies by HCl treatment. XRD, N₂adsorption, SEM, TEM, UV–Vis spectroscopy, EPR, N₂-TPD, Photoluminescence and Photocurrent were used to characterize the prepared catalysts. The results indicate that HCl treatment does not influence the crystal phase of g-C₃N₄ but change the morphology and optical property, leading to the smaller particle size, larger surface area and increased bang gap energy. It is deduced by N₂-TPD, Photoluminescence, Photocurrent and DFT simulations that the nitrogen vacancies formed by the HCl treatment not only serve as active sites to adsorb and activate N₂ molecules but also promote interfacial charge transfer from g-C₃N₄to N₂ molecules. The HCl treated g-C₃N₄ catalyst exhibits outstanding nitrogen photofixation ability under visible light, which is 13.4-fold higher than that of bulk g-C₃N₄ without nitrogen vacancy. The possible reaction mechanism is proposed.     

A first-principles study of gas molecule adsorption on hydrogen-substituted graphdiyne

Hydrogen-substituted graphdiyne (HsGDY) is a novel alkynyl carbon material with a structure similar to that of graphene. In this paper, the adsorption of four gas molecules (NO, NO₂, NH₃, and N₂) on HsGDY and B-doped HsGDY (B-HsGDY) was studied using density functional theory. The results show that the adsorption of NO and NO₂ on HsGDY and B-HsGDY is characterized by a larger charge transfer, stronger interaction, and higher adsorption energy compared with that of NH₃ and N₂. Based on the doping with B atoms, the adsorption energies of the gas molecules on HsGDY significantly improve, especially that of NO and NO₂. The gas molecule adsorption on both HsGDY and B-HsGDY is physical adsorption and the adsorption selectivity is good and thus may be applied for gas-sensitive NO and NO₂ materials.     

Theoretical analysis of oxygen reduction reaction and H2O2 formation and the impact of CF3SO3H coverage on Pt (111)

Theoretical analysis of ORR on Pt (111) was carried out with the combined technique of DFT calculation and the UBI-QEP method in order to understand the overall ORR pathways, behavior of H₂O₂ formation, and the impact of trifluoromethane sulfonic acid (CF₃SO₃H and TfOH) coverage, the alternative material of Nafion^®, on the reactivity on the Pt surface. The ORR scheme consisting of elementary reactions was then modeled to determine the dominant path and the limiting step based on their activation energies. The results showed that the dominant ORR path included the H₂O₂ formation step and OOH formation step was limiting. When TfOH covered the Pt surface, it was revealed that the adsorption energy of an O₂ molecule on Pt (111) was decreased due to the lower Fermi level and the d-band center, resulting in decreasing the activation energy of the limiting step. TfOH, however, could suppress the O₂ adsorption on the Pt surface. In addition, with the TfOH coverage, it was indicated that the limiting step of ORR was shifted to H₂O-production step which was after the H₂O₂ production, resulting in the enhancement of the H₂O₂ formation.     

A DFT study of formaldehyde adsorption on functionalized graphene nanoribbons

Density functional theory (DFT) based ab initio calculations were done to monitor the formaldehyde (CHOH) adsorptive behavior on pristine and Ni-decorated graphene sheet. Structural optimization indicates that the formaldehyde molecule is physisorbed on the pristine sheet via partly weak van der Waals attraction having the adsorption energy of about −15.7 kcal/mol. Metal decorated sheet is able to interact with the CHOH molecule, so that single Ni atoms prefer to bind strongly at the bridge site of graphene and each metal atom bound on sheet may adsorb up to four CHOH. The findings also show that the Ni decoration on graphene surface results in some changes in electronic properties of the sheet and its E_g is remained unchanged after adsorption of CHOH molecules. It is noteworthy to say that no bond cleavage was observed for the adsorption of CHOH on Ni-decorated graphene.     

N-doped graphene as a nanostructure adsorbent for carbon monoxide: DFT calculations

ABSTRACT

This work reports the physisorption of carbon monoxide (CO) on the surface of N-doped graphene. To study the adsorption of CO on N-doped graphene, some quantum chemical calculations were used through density functional theory. Based on our results, it can be found that the CO molecule could be adsorbed on the surface of N-doped graphene physically with the adsorption energies (E_ads) of ?2.9 and ?0.8 kcal mol^?1 (depends on the kind of configuration) while positive adsorption energies were calculated upon adsorption of CO on pristine graphene. We used the charge analysis for calculation of the net transferred charge of adsorbed CO on pristine and N-doped graphene sheets to evaluate the sensing ability of surface. The global indices of reactivity were calculated from the differences of the lowest unoccupied molecular orbital and highest occupied molecular orbital energies. Graphs for density of states point to some orbital hybridisation between CO molecule and N-doped graphene. Consequently, the N-doped graphene transforms the existence of CO molecules into electrical signal, and it may be potentially used as a sensor for CO.     

First-principles study of O2 adsorption on the α-U(001) surface

First-principles calculations based on density functional theory (DFT) have been performed to investigate the adsorption structures and electronic properties for O₂ on the α-U(001) surface. It was found that O₂ tends to dissociate with significant energetic preference compared to molecular adsorption. When approaching the surface perpendicularly along top site, the O₂ adsorbates were found to remain as molecule on the surface. The density of states of the system showed strong hybridization features for O2p, U6d and U5f states in the case of dissociative adsorption which is weaker for molecular adsorption. Further electronic properties analysis demonstrated that the bonding character of U–O bond is related to the symmetry of the adsorption site. Top site configuration showed stronger covalent component for the U–O bond, while the ionic character was found to be more obvious for hollow site adsorption.     

Influence of nano-AL2O3-catalyst sizes on hydrogen formation at the water radiolysis under ionizing radiation

The aim of this study was to investigate the regularities of molecular hydrogen formation from water dispersing Al₂O₃ nanoparticles irradiated with gamma ray. It was established that formed molecular hydrogen’s yield changed depending on the size of the catalyst, so that yield of molecular hydrogen formed on the surface with small size is 1.4–1.6 times greater than the one with big size. Equal distribution of nanocatalyst in water medium and much more adsorption of water molecule on the catalyst surface result in more efficient radiolysis process.     

Fourier transform infrared studies of cyclohexane and benzene adsorbed on Pt/Al2O3: Evidence for π- and σ-bonded chemisorbed species

Fourier transform infrared spectroscopy has been applied to the study of cyclohexane adsorbed on Al₂O₃ and Pt/Al₂O₃ surfaces. Earlier studies of benzene on these same materials have also been extended to include benzene adsorbed on a Pt/Al₂O₃ surface which contains structured carbon residues. The data provide indirect evidence for the formation of a carbon residue on Pt/Al₂O₃ which retains the six-membered cyclic structure of the parent adsorbates. The carbon residue can be formed upon vacuum heating of the parent C₆ ring molecules chemiorbed on Pt/Al₂O₃. There is spectroscopic evidence that cyclohexane dehydrogenates on Pt/Al₂O₃ at 300 K to form two different chemisorbed species; a π-bonded benzene and a dissociated σ-bonded benzene. These two chemisorbed species have CH stretching vibrations centered at 3030 and 2947 cm^?1, respectively. Benzene added to a clean catalyst surface forms only a π-bonded benzene. However, benzene added to Pt/Al₂O₃ with ordered carbon residues forms both π- and σ-bonded benzenes. The addition of H₂ at 300 K to any of the π- or σ-bonded benzenes or to the carbon residue results in the formation of cyclohexane physisorbed on the catalyst. The absence of CH₃ groups upon hydrogenation suggests the lack of CC bond breaking during adsorption or hydrogenation. Simultaneous infrared and thermal desorption studies on chemisorbed deuterated benzene (from C₆D₁₂) indicate that the a-bonded species exchange H from the surface OH groups of the alumina support more readily than does the π-bonded benzene. In addition to hydrogen exchange with the support, thermal desorption experiments indicate the oxidation of a portion of the chemisorbed hydrocarbons and/or carbon residue by oxygen from the alumina support. Therefore, the support is capable of playing a direct role in reactions occurring on the catalyst surface.     

A search for precursor states to molecular nitrogen chemisorption on Ni(100), Re(0001) and W(100) surfaces at ∼ 20 K

We have studied adsorption and condensation of molecular nitrogen on Ni(100), Re(0001) and W(100) surfaces by XPS at surface temperatures ? 20 K in order to search for a precursor state to the linearly bonded chemisorbed state (γ-state). Our data however show XPS spectra only from γ-N₂ at low exposures and from physisorbed and condensed N₂ at higher exposures. No intrinsic precursor is found, allowing an upper bound of approximately 3 kJ/mol to be placed on the activation barrier between any such state and the chemisorbed state. The physisorbed N₂ observed on top of γ-N₂ covered patches acts as an extrinsic precursor to chemisorption.     

A-Z-A型石墨烯场效应晶体管吸附 效应的第一性原理研究

利用第一性原理的计算方法, 研究了A-Z-A型GNR-FET的电子结构和输运性质及其分子吸附效应. 得到了以下结论: 纯净的A-Z-A型GNR-FET具有典型的双极型晶体管特性, 吸附分子的存在会使纳米带能隙变小. 对于吸附H, H₂, H₂O, N₂, NO, NO₂, O₂, CO₂和SO₂分子的情况, A-Z-A型GNR-FET仍然保持着场效应晶体管的基本特征, 但吸附不同类型的分子会使GNR-FET的输运特性发生不同程度的改变; 对于吸附OH分子的情况, 输运特性发生了本质的改变, 完全不具有场效应晶体管的特性. 这些研究结果将有助于石墨烯气体探测器的工程实现, 并对应用于不同环境中GNR-FET的设计具有重要指导意义.     

Selectively strong molecular adsorption on boron nitride monolayer induced by transition metal substrate

We studied adsorption of several molecules (CO, CO₂, H₂O, N₂O, NO, NO₂, and O₂) on hexagonal boron nitride (h-BN) monolayers supported on transition metal (TM) surfaces, using density functional calculations. We observed that all the molecules bind very weakly on the pristine h-BN, with binding energies in the range of 0.02–0.03 eV. Interestingly, however, when h-BN is supported on the TM surface, NO₂ and O₂ become strongly chemisorbed on h-BN, with binding energies of >1 eV, whereas other molecules still physisorbed, with binding energies of ～0.1 eV at most. The electron transfer from TM to p_z states of h-BN played a substantial role in such strong bindings of NO₂ and O₂ on h-BN, as these molecules possess unpaired electrons that can interact with p_z states of h-BN. Such selective molecular binding on h-BN/TM originates from the peculiar distribution of the spin-polarized highest occupied and lowest unoccupied molecular orbitals of NO₂ and O₂. Strong molecular adsorption and high selectivity would make the h-BN/TM system possible for a variety of applications such as catalysts and gas sensors.     

First principles computational investigation on the possibility of Pt-decorated SiC hexagonal sheet as a suitable material for oxygen reduction reaction

First principles calculations play a significant role in developing and optimizing new energy storage and conversion materials especially at the nanoscale. In this work, the structural, energetics and, electronic properties of adsorbed Pt atom onto two-dimensional graphene, hexagonal BN (h-BN) and SiC (h-SiC) sheets have been investigated at DFT–B3LYP level of theory using coronene molecule as a suitable model. Spin-polarization and model size effects on the Pt adsorption properties have also been evaluated. Various positions for establishing Pt atom on the selected substrates have been considered and full structural optimization was carried out for all selected systems. The adsorption energies, electronic structures and charge population analysis indicated that in all the studied structures there were strong interaction between two interacting entities. It was also found that the adsorption ability of h-SiC is much stronger than the other counterparts with adsorption energy of −3.828 eV.We have also examined the O₂ adsorption properties of Pt-decorated graphene, h-BN and h-SiC sheets for possible tunability of O₂ adsorption strength of systems under study. We found that h-SiC sheet possess a weakened O₂ adsorption energy among the selected substrates. In view of the strong stability of adsorbed Pt atom on h-SiC sheet and relatively weaker O₂ adsorption energy, one can expect that h-SiC might be a promising material for support assistant as well as increasing the catalytic activity of Pt atoms compared to graphene and h-BN substrates. This may attribute to preventing aggregating of Pt atoms due to the strong fastening nature of the h-SiC sheet and also by affording a balance in the O₂ adsorption strength that lead to enhanced catalyst turnover. Therefore, our first principles findings offer a unique opportunity for design and applications of SiC-based nanoscale supports in fuel cell technology.     

An oxygen reduction catalytic process through superoxo adsorption states on n-type doped h-BN: A first-principles study

Dioxygen adsorption and activation on metal-ligand systems are the key elements for biological oxidative metabolisms and also catalyst design for the oxygen reduction reaction (ORR). We show, through first-principles calculations, that similar dioxygen adducts can form on metal-free n-type doped hexagonal boron nitride (h-BN) nanostructures. The density of electron donors determines the charge state of dioxygen, either in superoxo and peroxo, which exactly correlates with the ‘end-on’ and ‘side-on’ configurations, respectively. Activated O₂ in the superoxo state shows a better catalytic performance possibly mediating the direct four-electron reduction. The formation of hydrogen peroxide (H₂O₂) is practically eliminated, and thus we suggest that a surface coated with the n-type doped h-BN can be the basis for an ORR catalyst with increased stability.     

基于密度泛函理论研究掺杂Pd石墨烯吸附O2及CO

基于第一性原理的密度泛函理论研究了单个O₂和CO气体分子吸附于本征石墨烯和掺杂钯(Pd)的石墨烯的体系, 通过石墨烯掺Pd前后气体分子的吸附能、电荷转移及能带和态密度的计算, 发现掺Pd后气体分子吸附能和电荷转移显著增大, 这是由于Pd的掺杂, 在本征石墨烯能带中引入了杂质能级, 增强了石墨烯和吸附气体分子间的相互作用; 氧化性气体O₂和还原性气体CO吸附对石墨烯体系能带结构和态密度的影响明显不同, 本征石墨烯吸附O₂后, 费米能级附近态密度变大, 掺Pd后在一定程度变小; 吸附还原性的CO后, 石墨烯费米能级附近态密度几乎没有改变, 表明掺杂Pd不会影响石墨烯对CO的气体灵敏度, 但由于CO对石墨烯的吸附能增大, 可以提高石墨烯对还原性气体的气敏响应速度.     

Oxygen reduction activity of N-doped carbon-based films prepared by pulsed laser deposition

Carbon-based films with nitrogen species on their surface were prepared on a glassy carbon (GC) substrate for application as a non-platinum cathode catalyst for polymer electrolyte fuel cells. Cobalt and carbon were deposited in the presence of N₂ gas using a pulsed laser deposition method and then the metal Co was removed by HCl-washing treatment. Oxygen reduction reaction (ORR) activity was electrochemically determined using a rotating disk electrode system in which the film samples on the GC substrate were replaceable. The ORR activity increased with the temperature of the GC substrate during deposition. A carbon-based film prepared at 600 °C in the presence of N₂ at 66.7 Pa showed the highest ORR activity among the tested samples (0.66 V vs. NHE). This film was composed of amorphous carbons doped with pyridine type nitrogen atoms on its surface.     

Reduction of nitric oxide on the carbon pretreated Rh{331} single crystal surface; evidence for molecular CN− formation

The chemisorption of NO on the carbon pretreated Rh{331} single crystal surface has been investigated by XPS, LEED and SIMS. The carbon overlayer was prepared by dehydrogenation of chemisorbed C₂H₄. Results of NO adsorption at room temperature show that surface carbon blocks adsorption sites that normally coordinate molecular NO_ADS and its dissociated products, N_Ads and O_Ads, as determined by comparing to experiments performed on clean Rh{331}. Heating the surface which contains NO_Ads, n_Ads, O_Ads and C_Ads, induces a series of chemical reactions starting with the dissociation of molecular NO_Ads. Above 400 K, the C_Ads and N_Ads atoms combine to form CN^?. The formation of the latter species is confirmed by the temperature evolution of the Rh₂CN⁺ and CN^? SIMS ion yields. The C_Ads species also reacts with O_Ads to produce CO and/or CO₂. These processes occur preferentially over the desorption of N₂ and O₂. In general, it is demonstrated that by using the XPS and SIMS methods, it is possible to identify the reaction species present on the surface at any given temperature and to unravel rather complex reaction pathways.     

基于第一性原理的锂空气电池钌掺杂石墨烯正极 氧还原反应机理研究

双电解液锂空气电池因其高理论能量密度受到广泛研究,但电池正极侧氧还原反应(ORR)速率低,其反应速率是限制锂空气电池发展的主要因素之一.本文提出了以钌(Ru)掺杂单层石墨烯作为正极ORR催化剂,采用第一性原理计算nRu (n=1～3)掺杂石墨烯的电子结构和氧气在Ru掺杂石墨烯表面的吸附性能,并以过渡态搜索方法获得ORR反应路径,研究碱性溶液中Ru掺杂单层石墨烯作用下的ORR机理.研究结果表明,经Ru原子掺杂后,石墨烯能够获得稳定的掺杂结构,且电导率显著提升.同原始单层石墨烯相比,Ru掺杂石墨烯增强了对O₂的吸附能力.在三Ru(n=3)掺杂石墨烯表面进行的ORR无需克服任何能垒.此外,三Ru掺杂石墨烯表面对OH基团的吸附能最低,有利于ORR的连续进行.研究表明三Ru掺杂石墨烯有望成为一种新型的ORR催化剂以提高双电解液锂空气电池的性能.     

Ultrasound wave assisted removal of Ceftriaxone sodium in aqueous media with novel nano composite g-C3N4/MWCNT/Bi2WO6 based on CCD-RSM model

The aim of this study was ultrasound assisted removal of Ceftriaxone sodium (CS) based on CCD model. Using sonochemical synthesized Bi₂WO₆ implanted on graphitic carbon nitride/Multiwall carbon nanotube (g-C₃N₄/MWCNT/Bi₂WO₆). For this purpose g-C₃N₄/MWCNT/Bi₂WO₆ was synthesized and characterized using diverse approaches including XRD, FE-SEM, XPS, EDS, HRTEM, FT-IR. Then, the contribution of conventional variables including pH, CS concentration, adsorbent dosage and ultrasound contact time were studied by central composite design (CCD) under response surface methodology (RSM). ANOVA was employed to the variable factors, and the most desirable operational conditions mass provided. Drug adsorption yield of 98.85% obtained under these defined conditions. Through conducting five experiments, the proper prediction of the optimum point were examined. The respective results showed that RSD% was lower than 5% while the t-test confirmed the high quality of fitting. Langmuir isotherm equation fits the experimental data best and the removal followed pseudo-second order kinetics. The estimation of the experimentally obtained maximum adsorption capacities was 19.57 mg.g⁻ of g-C₃N₄/MWCNT/Bi₂WO₆ for CS. Boundary layer diffusion explained the mechanism of removal via intraparticle diffusion.     

First-principles study of dissociation processes of O2 molecular on the Al (111) surface

The trajectories of adsorption and dissociation process of O₂ on the Al (111) surface were studied by the spin-polarized ab initio molecular dynamics method, and the adsorption activation energy was clarified by the NEB method with hybrid functionals. Three typical dissociation trajectories were found through simulation of O₂ molecule at different initial positions. When vertically approaches to the Al surface, the O₂ molecule tends to rotate, and the activation energy is 0.66eV. If O₂ molecule does not rotate, the activation energy will increase to 1.43 eV, and it makes the O atom enter the Al sublayer eventually. When the O₂ molecules parallel approach to the Al surface, there is no activation energy, due to the huge energy released during the adsorption process.