Xiaoguang Duan

Nitrogen-doped graphene for generation and evolution of reactive radicals by metal-free catalysis.

N-Doped graphene (NG) nanomaterials were synthesized by directly annealing graphene oxide (GO) with a novel nitrogen precursor of melamine. A high N-doping level, 8-11 at. %, was achieved at a moderate temperature. The sample of NG-700, obtained at a calcination temperature of 700 °C, showed the highest efficiency in degradation of phenol solutions by metal-free catalytic activation of peroxymonosulfate (PMS). The catalytic activity of the N-doped rGO (NG-700) was about 80 times higher than that of undoped rGO in phenol degradation. Moreover, the activity of NG-700 was 18.5 times higher than that of the most popular metal-based catalyst of nanocrystalline Co3O4 in PMS activation. Theoretical calculations using spin-unrestricted density functional theory (DFT) were carried out to probe the active sites for PMS activation on N-doped graphene. In addition, experimental detection of generated radicals using electron paramagnetic resonance (EPR) and competitive radical reactions was performed to reveal the PMS activation processes and pathways of phenol degradation on nanocarbons. It was observed that both (•)OH and SO4(•-) existed in the oxidation processes and played critical roles for phenol oxidation.

Sulfur and nitrogen co-doped graphene for metal-free catalytic oxidation reactions

Sulfur and nitrogen co-doped reduced graphene oxide (rGO) is synthesized by a facile method and demonstrated remarkably enhanced activities in metal-free activation of peroxymonosulfate (PMS) for catalytic oxidation of phenol. Based on first-order kinetic model, S-N co-doped rGO (SNG) presents an apparent reaction rate constant of 0.043 ± 0.002 min(-1) , which is 86.6, 22.8, 19.7, and 4.5-fold as high as that over graphene oxide (GO), rGO, S-doped rGO (S-rGO), and N-doped rGO (N-rGO), respectively. A variety of characterization techniques and density functional theory calculations are employed to investigate the synergistic effect of sulfur and nitrogen co-doping. Co-doping of rGO at an optimal sulfur loading can effectively break the inertness of carbon systems, activate the sp(2) -hybridized carbon lattice and facilitate the electron transfer from covalent graphene sheets for PMS activation. Moreover, both electron paramagnetic resonance (EPR) spectroscopy and classical quenching tests are employed to investigate the generation and evolution of reactive radicals on the SNG sample for phenol catalytic oxidation. This study presents a novel metal-free catalyst for green remediation of organic pollutants in water.

Low temperature combustion synthesis of nitrogen-doped graphene for metal-free catalytic oxidation

Nitrogen-doped reduced graphene oxide (N-rGO) was prepared by a simple process of simultaneous reduction and nitrogen doping on graphene oxide (GO) at low temperatures using ammonium nitrate as a N precursor. Characterization techniques indicated that N-rGO materials with a high N loading (5–8 at%) can be easily produced and that the crystal/micro-structures and chemical compositions of N-rGO materials are dependent on the calcination conditions. The metal-free catalysis of N-rGO was investigated by catalytic activation of peroxymonosulfate (PMS) for phenol oxidative degradation in water. It was found that N-rGO samples are promising green catalysts for phenol degradation. Kinetic studies showed that phenol degradation follows first order reaction kinetics on N-rGO-350 with an activation energy of 31.6 kJ mol−1. The mechanism of PMS activation and phenol oxidation was elucidated by employing both electron paramagnetic resonance (EPR) studies and quenching tests with ethanol and tert-butanol.

Insights into N-doping in single-walled carbon nanotubes for enhanced activation of superoxides: a mechanistic study.

Emerging characteristics upon nitrogen-doping were differentiated in the activation of superoxides over single-walled carbon nanotubes. Both experimental and theoretical studies revealed that enhanced peroxymonosulfate (PMS) activation is ascribed to a nonradical process while persulfate (PS) activation is accelerated via directly oxidizing water, yet hydrogen peroxide (H2O2) activation is inert to N-doping. This study details the first insights into versatile N-doping in carbocatalysis for organic oxidation in sustainable remediation.

Nitrogen- and Sulfur-Codoped Hierarchically Porous Carbon for Adsorptive and Oxidative Removal of Pharmaceutical Contaminants

Heteroatom (nitrogen and sulfur)-codoped porous carbons (N-S-PCs) with high surface areas and hierarchically porous structures were successfully synthesized via direct pyrolysis of a mixture of glucose, sodium bicarbonate, and thiourea. The resulting N-S-PCs exhibit excellent adsorption abilities and are highly efficient for potassium persulfate activation when employed as catalysts for the oxidative degradation of sulfachloropyridazine (SCP) solutions. The adsorption capacities of N-S-PC-2 (which contains 4.51 atom % nitrogen and 0.22 atom % sulfur and exhibits SBET of 1608 m(2) g(-1)) are 73, 7, and 3 times higher than those of graphene oxide, reduced graphene oxide, and commercial single-walled carbon nanotube, respectively. For oxidation, the reaction rate constant of N-S-PC-2 is 0.28 min(-1). This approach not only contributes to the large-scale production and application of high-quality catalysts in water remediation but also provides an innovative strategy for the production of heteroatom-doped PCs for energy applications.

An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants: formation mechanism and generation of singlet oxygen from peroxymonosulfate

The synthesis of carbonaceous materials from a metal organic framework (MIL-100), organic linker and N-precursor was comprehensively investigated, and the structures of the products were characterized. It was found that simple pyrolysis of mixed MIL-100 (Fe)/dicyandiamide (DCDA) could produce nitrogen-doped graphene (N-graphene). The N-graphene showed excellent performances in peroxymonosulfate (PMS) activation, which were superior to those of counterparts of graphene, iron(II, III) oxide, manganese(IV) oxide and cobalt(II, III) oxide. With PMS activation, N-graphene exhibited efficient catalytic degradation of various organic pollutants such as phenol, 2,4,6-trichlorophenol (TCP), sulfachloropyridazine (SCP) and p-hydroxybenzoic acid (PHBA). Electron paramagnetic resonance (EPR) spectroscopy and radical quenching tests were employed to investigate the PMS activation and organic degradation processes. It was found that singlet oxygen (1O2) was mainly produced during the activation of PMS by N-graphene, and contributed to the catalytic oxidation instead of sulfate and/or hydroxyl radicals. These findings provide new insights into PMS activation by metal-free carbon catalysis.

Novel polyoxometalate@g-C3N4 hybrid photocatalysts for degradation of dyes and phenolics

Graphitic carbon nitride (g-C3N4) is an emerging metal-free catalyst, and has attracted considerate research interests in photocatalysis. For improving the low photocatalytic activity due to the polymeric nature, a variety of methods have been developed. In this study, polyoxometalate (POMs) functionalized g-C3N4 were synthesized using a facile hydrothermal method as novel photocatalysts. The photocatalysts were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), N2 sorption isotherms, thermogravimetric analysis (TGA), and UV-vis diffusion reflectance spectroscopy (UV-vis DRS). The photocatalytic properties were evaluated in photodecomposition of aqueous methylene blue (MB) and phenol under UV-visible light irradiations. Compared to pristine g-C3N4, POMs modified samples demonstrated enhanced efficiencies in photodegradation of MB and phenol. It was suggested that increased specific surface area, porous volume and efficient charge transfer would be responsible for the improved photocatalysis. This study proves the promising role of POMs in modification of novel photocatalysts.

Ultra-sustainable Fe 78 Si 9 B 13 metallic glass as a catalyst for activation of persulfate on methylene blue degradation under UV-Vis light

Stability and reusability are important characteristics of advanced catalysts for wastewater treatment. In this work, for the first time, sulfate radicals (SO4∙−) with a high oxidative potential (Eo = 2.5–3.1 V) were successfully activated from persulfate by a Fe78Si9B13 metallic glass. This alloy exhibited a superior surface stability and reusability while activating persulfate as indicated by it being used for 30 times while maintaining an acceptable methylene blue (MB) degradation rate. The produced SiO2 layer on the ribbon surface expanded strongly from the fresh use to the 20th use, providing stable protection of the buried Fe. MB degradation and kinetic study revealed 100% of the dye degradation with a kinetic rate k = 0.640 within 20 min under rational parameter control. The dominant reactive species for dye molecule decomposition in the first 10 min of the reaction was hydroxyl radicals (∙OH, Eo = 2.7 V) and in the last 10 min was sulfate radicals (SO4∙−), respectively. Empirical operating variables for dye degradation in this work were under catalyst dosage 0.5 g/L, light irradiation 7.7 μW/cm2, and persulfate concentration 1.0 mmol/L. The amorphous Fe78Si9B13 alloy in this work will open a new gate for wastewater remediation.

Heterogeneous activation of peroxymonosulfate by amorphous boron for degradation of bisphenol S.

Recently, tremendous efforts have been devoted to developing carbon-based metal-free catalysts as an alternative to metal-based catalysts for remediation of emerging contaminants. However, further investigations have demonstrated that the durability of carbocatalysts is poor. Therefore, it is extremely desirable to seek a novel metal-free catalyst with high efficiency and superb stability. Herein, we first discovered that amorphous boron (A-boron) can be used as a metal-free catalyst for peroxymonosulfate (PMS) activation to produce free radicals for effective degradation of bisphenol S (BPS), which is a newly-occurring estrogenic endocrine-disrupting chemical. It exhibited outstanding catalytic activity and superior stability as comparing to metal-based and metal-free carbon-based catalysts. Moreover, many other typical organic pollutants in water such as bisphenol F, sulfamethoxazole, rhodamine B and methyl orange can also be effectively decomposed in A-boron/PMS oxidative system. The effects of reaction parameters on BPS degradation were systematically investigated. The catalytic oxidation mechanism was proposed. The intriguing catalytic feature of A-boron discovered in this study will provide new opportunities for the future development of A-boron based materials with promising applications in water remediation.

Oxygen Vacancies in Shape Controlled Cu2O/Reduced Graphene Oxide/In2O3 Hybrid for Promoted Photocatalytic Water Oxidation and Degradation of Environmental Pollutants

A novel shape controlled Cu2O/reduced graphene oxide/In2O3 (Cu2O/RGO/In2O3) hybrid with abundant oxygen vacancies was prepared by a facile, surfactant-free method. The hybrid photocatalyst exhibits an increased photocatalytic activity in water oxidation and degradation of environmental pollutants (methylene blue and Cr6+ solutions) compared with pure In2O3 and Cu2O materials. The presence of oxygen vacancies in Cu2O/RGO/In2O3 and the formation of heterojunction between In2O3 and Cu2O induce extra diffusive electronic states above the valence band (VB) edge and reduce the band gap of the hybrid consequently. Besides, the increased activity of Cu2O/RGO/In2O3 hybrid is also attributed to the alignment of band edge, a process that is assisted by different Fermi levels between In2O3 and Cu2O, as well as the charge transfer and distribution onto the graphene sheets, which causes the downshift of VB of In2O3 and the significant increase in its oxidation potential. Additionally, a built-in electric field is generated on the interface of n-type In2O3 and p-type Cu2O, suppressing the recombination of photoinduced electron-hole pairs and allowing the photogenerated electrons and holes to participate in the reduction and oxidation reactions for oxidizing water molecules and pollutants more efficiently.