The construction of high-performance photocatalyst has always been explored. Covalent organic frameworks (COFs), especially keto-amine-linked COFs, have many advantages, such as adjustable bandgaps, π-π stacking structure, excellent response ability to visible light, high specific surface area, high mobility of carrier carriers, good physical and chemical stability, and so on, showing strong potential applications in photocatalytic solar energy conversion and hydrogen production. Two analogous covalent triazine frameworks (CTFs), T3H-CTF and T3N-CTF, have been synthesized via Schiff-base condensation reactions between 2,4,6-trihydroxybenzene-1,3,5-tricarbalehyde (MOP) and the corresponding triazine-based aromatic amines under solvothermal condition. For T3N-CTF, the peripheral aromatic linker to the central triazine unit was the pyridine unit, instead of the benzene unit in the T3H-CTF unit. T3N-CTF had a hydrogen production rate (HPR) of 6485.05 μmol g-1  h-1 , much higher than that of T3H-CTF (2028.06 μmol g-1  h-1 ). Accordingly, T3N-CTF had a much higher apparent quantum yield (AQY) of 12.2 % than that of T3H-CTF (4.12 %) at 405 nm. The experimental and theoretical results showed that the extended light absorption range, enlarged surface area, and enhanced separation and transportation efficiencies of charge carriers of T3N-CTF compared with T3H-CTF were uniformly induced by the introduction of peripheral nitrogen atoms into the skeleton of former CTF, which eventually boosted the visible-light induced hydrogen evolution reaction (HER). The work suggests a new method for enhancing the intrinsic HER activity by modulating the electronic features of the conjugated COFs by the introduction of pyridinic N atoms.

This study is devoted to optimization synthesis conditions of the N, S co-doped porous graphene via a single step thermal chemical activation process from agricultural wastes such as cabbage waste. To this end, the response surface method (RSM) was considered, and the synthesis parameters were varied in specific ranges. By doing so, the optimum conditions in terms of the best performance in mercury removal was determined which was characterized by TEM, SEM, BET, XRD, XPS, and FTIR techniques. The chosen key process parameters were Activation agent to carbon precursor ratio (A: KOH/C), Reaction time (B: Time), Activation temperature (C: Temperature), and (Dopant to carbon precursor ratio (D: Dopant/C). Each parameter was investigated in 3 levels with lower and upper bounds being A: 2-6; B:30-90 min.; C: 600-800 ˚C; D:2-10. The optimum conditions of the process were determined to be as: A: 2; B: 30 min.; C: 600 ˚C and D: 2. The optimized sample was prepared in repeated runs with reproducible results with Hg vapor adsorption capacity of 2100 µg/g at 40 ˚C and 2266 µg/g at 90 ˚C. In addition to the experiments, DFT calculations were also carried out which elucidated the positive role of N and S co-doping in improving the mercury adsorption intensity.
BACKGROUND: The online version contains supplementary material available at 10.1007/s40201-021-00712-y.

In practice, modifying the fundamental properties of low-dimensional materials should be realized before incorporating them into nanoscale devices. In this paper, we systematically investigate the nitrogen (N) doping and oxygen vacancy (OV) effects on the electronic and magnetic properties of the beryllium oxide (BeO) monolayer using first-principles calculations. Pristine BeO single layer is a non-magnetic insulator with an indirectK-Γ gap of 5.300 eV. N doping induces a magnetic semiconductor nature, where the spin-up and spin-down band gaps depend on the dopant concentration and N-N separation. Creating one OV leads to the energy gap reduction of 31.06% with no spin-polarization, which is due to the abundant 2p electrons of the Be atoms nearest the OV site. The further increase to two OVs and varying the OV-OV distance affect the band gap values, however the spin independence is retained. The magnetic semiconducting behavior is also obtained by the simultaneous N doping and OV presence. Calculations reveal significant magnetization of the BeO@1N, BeO@2N-n, BeO@NOV-nsystems, which is produced mainly by the spin-up N-2p state. Except for the BeO@NOV-1 and BeO@NOV-2, whose magnetic properties are created by the spin-up 2p state of the Be atoms closest to the OV site. The variation of the N-N and N-OV distances keeps the ferromagnetic ordering in the BeO@2N and BeO@NOV layers. Results presented herein may propose efficient methods to artificially modify the physical properties of BeO monolayer, leading to the formation of novel two-dimensional (2D) materials for optoelectronic and spintronic applications.

Two conditions are important to obtain appropriate substances for hydrogen storage; high surface area and fitting binding energy (BE). Doping is a key strategy that improves BE. We investigated hydrogen adsorption onto twenty six nitrogen disubstituted isomers of sumanene (C19N2H12) by MP2/6-311++G(d,p)//B3LYP/6-31+G(d) and M06-2X/6-31+G(d) levels of theory. Effect of nitrogen doping in different positions of sumanene was checked. To obtain better BE, basis set superposition error (BSSE) and zero point energy (ZPE) corrections were used. Anticipating of adsorption sites and extra details about adsorption process was done by molecular electrostatic potential (MEP) surfaces. Various types of density of state (DOS) diagrams such as total DOS (TDOS), projected DOS (PDOS) and overlap population DOS (OPDOS) and natural bond orbital (NBO) analysis were used to find better insight on the adsorption properties. In addition of temperature depending of the BE, HOMO-LUMO gap (HLG), dipole moment, reactivity and stability, bowl depth and natural population analysis (NPA) of the isomers were studied. A physisorption mechanism for adsorption was proposed and a trivial change was seen. Place of nitrogen atoms in sumanene frame causes to binding energy increases or decreases compared with pristine sumanene. The best and the worst isomers and category of isomers were suggested.

This work reported on the synthesis of a series of nitrogen doped Ca2Nb2O7 with tunable nitrogen content that were found to be efficient and green noble-metal-free catalysts toward catalytic reduction of p-nitrophenol. XPS and ESR results indicated that the introduction of nitrogen in Ca2Nb2O7 gave rise to a large number of defective nitrogen and oxygen species. Defective nitrogen and oxygen species were found to play synergetic roles in the reduction of p-nitrophenol. The underlying mechanism is completely different from those reported for metallic nanoparticles. Moreover, the more negative conduction band edge potential enabled nitrogen doped Ca2Nb2O7 to show photo-synergistic effects that could accelerate the reduction rate toward p-nitrophenol under UV light irradiation. This work may provide a strategy for tuning the catalytic performance by modulating the chemical composition, electronic structure as well as surface defect chemistry.