Photocatalytic degradation of methylene blue over MIL-100(Fe)/GO composites: a performance and kinetic study

Adsorption coupled with photocatalytic degradation is proposed to fulfill the removal and thorough elimination of organic dyes.Herein,we report a facile hydrothermal synthesis of MIL-100(Fe)/GO photocatalysts.The adsorption and photocatalytic degradation process of methylene blue(MB)on MIL‐100(Fe)/GO composites were systematically studied from performance and kinetic perspectives.A possible adsorption‐photocatalytic degradation mechanism is proposed.The optimized 1M8G composite achieves 95%MB removal(60.8 mg/g)in 210 min and displays well recyclability over ten cycles.The obtained MB adsorption and degradation results are well fitted onto Langmuir isotherm and pseudo‐second order kinetic model.This study shed light on the design of MOFs based composites for water treatment.

Study of Manganese Promoter on a Precipitated Iron-Based Catalyst for Fischer-Tropsch Synthesis

The effects of Manganese （Mn） incorporation on a precipitated iron-based Fischer-Tropsch synthesis （FTS） catalyst were investigated using N2 physical adsorption, air differential thermal analysis （DTA）, H2 temperature-programmed reduction （TPR）, and Mǒssbauer spectroscopy. The FTS performances of the catalysts were tested in a slurry phase reactor. The characterization results indicated that Mn increased the surface area of the catalyst, and improved the dispersion of （α-Fe2O3 and reduced its crystallite size as a result of the high dispersion effect of Mn and the Fe-Mn interaction. The Fe-Mn interaction also suppressed the reduction of （α-Fe2O3 to Fe3O4, stabilized the FeO phase, and （or） decreased the carburization degree of the catalysts in the H2 and syngas reduction processes. In addition, incorporated Mn decreased the initial catalyst activity, but improved the catalyst stability because Mn restrained the reoxidation of iron carbides to Fe3O4, and improved further carburization of the catalysts. Manganese suppressed the formation of CH4 and increased the selectivity to light olefins （C2-4^=）, but it had little effect on the selectivities to heavy （C5＋） hydrocarbons. All these results indicated that the strong Fe-Mn interaction suppressed the chemisorptive effect of the Mn as an electronic promoter, to some extent, in the precipitated iron-manganese catalyst system.

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorporation manner on the textural properties, bulk and surface phase compositions, reduction/carburization behaviors, and surface basicity of an iron-based Fischer-Tropsch synthesis （FTS） catalyst. The catalyst samples were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, CO2 temperature-programmed desorption （TPD）, and M5ssbauer spectroscopy. The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor （CSTR）. The characterization results indicated that the manganese promoter incorporated by using the coprecipitation method could improve the dispersion of iron oxide, and decrease the size of the iron oxide crystallite. The manganese incorporated with the impregnation method is enriched on the catalyst＇s surface. The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H2, CO, and syngas because of the excessive enrichment of manganese on the catalyst surface. The catalyst added manganese using the coprecipitation method has the highest CO conversion （51.9%） and the lowest selectivity for heavy hydrocarbons （C12＋）.

Effect of Sulfate on an Iron Manganese Catalyst for Fischer-Tropsch Synthesis

The effect of sulfate on Fischer-Tropsch synthesis performance was investigated in a slurryphase continuously stirred tank reactor （CSTR） over a Fe-Mn catalyst. The physiochemical properties of the catalyst impregnated with different levels of sulfate were characterized by N2 physisorption, X-ray photoelectron spectroscopy （XPS）, H2 （or CO） temperature-programmed reduction （TPR）, Mossbauer spectroscopy, and CO2 temperature-programmed desorption （TPD）. The characterization results indicated that the impregnated sulfate slightly decreased the BET surface area and pore volume of the catalyst, suppressed the catalyst reduction and carburization in CO and syngas, and decreased the catalyst surface basicity. At the same time, the addition of small amounts of sulfate improved the activities of FischerTropsch synthesis （FTS） and water gas shift （WGS）, shifted the product to light hydrocarbons （C1-C11） and suppressed the formation of heavy products （C12＋）. Addition of SO4^2- to the catalyst improved the FTS activity at a sulfur loading of 0.05-0.80 g per 100 g Fe, and S-05 catalyst gave the highest CO conversion （62.3%）, and beyond this sulfur level the activity of the catalyst decreased.

Single-atom Pd anchored in the porphyrin-center of ultrathin 2D-MOFs as the active center to enhance photocatalytic hydrogen-evolution and NO-removal

Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis.However,how to prevent the aggregation of single atoms during the preparation and catalytic processes remained a great challenge.Herein,a novel ultrathin two-dimensional porphyrin-based single-atom photocatalyst Ti-MOF(abbreviated as TMPd)obtained through a simple hydrothermal synthesis strategy was used for photocatalytic hydrogen evolution and NO removal,in which the singleatom Pd tightly anchored in the center of porphyrin to ensure single-atom Pd stable existence.Compared with most reported MOFs-based photocatalysts,the TMPd showed an excellent hydrogen evolution rate(1.32 mmol g^(-1)h^(-1))and the NO removal efficiency(62%)under visible light irradiation.Aberrationcorrected high-angle annular dark-field scanning transmission electron microscope(HAADF-STEM)and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy(XAFS)proved that pd in TMPd existed in an isolated state,and the atomic force microscope(AFM)proved the ultrathin morphology of TMPd.DFT calculations had demonstrated that single-atom Pd could serve as the active center and more effectively achieve electron transfer,indicating that single-atom Pd played a vital role in photocatalytic hydrogen evolution.In addition,a possible photocatalytic pathway of NO removal was proposed based on ESR and in-situ infrared spectra,in which the catalysts anchored with single-atom Pd could produce more active substances and more effectively oxidize NO to NO_(2)^(-)or NO_(3)^(-).The results suggested that coordinating single-atom metal species as the active site in the center of porphyrin could be a feasible strategy to obtain various ultrathin porphyrin-based single-atom photocatalysts to acquire excellent photocatalytic performance further.

In-situ fabrication of TiO_(2)/NH_(2)-MIL-125(Ti) via MOF-driven strategy to promote efficient interfacial effects for enhancing photocatalytic NO removal activity

Deep oxidation of NO molecules to nitrate species by photocatalysis with virtually no toxic byproduct NO_(2)generation is a challenging task.In this study,Ti O_(2)in-situ grows based on NH_(2)-MIL-125(Ti)(NM-125)not only inhibited TiO 2agglomeration,but also contacted more tightly to obtain efficient interfacial effects,thus displaying excellent photocatalytic NO removal activity(68.08%).The formation of Ti O_(2) is directly confirmed by characterizations such as X-ray diffraction(XRD),transmission electron microscope(TEM),X-ray photoelectron spectroscopy(XPS).Meanwhile,UV–vis,photoluminescence,and photoelectrochemical analysis indicate that TiO_(2) formation effectively improves the optical properties.Moreover,the strong electron interaction and electron transport direction between NM-125 and Ti O_(2) are investigated by density functional theoretical(DFT)calculation.Finally,combined with the results of electron spin resonance(ESR)and in-situ FT-IR test,the intermediate processes of NO adsorption and photocatalytic oxidation reaction are discussed in depth,where the production of reactive oxygen species(ROS)under light is the key factor in the successful degradation of NO.Compared with NM-125 which can only produce·OH through photogenerated electrons since the lower valence band position,NMT-2 can directly produce·OH through photogenerated holes,thereby relieving the pressure on photogenerated electrons and producing more ROS.This study will provide reasonable guidance for the modification of NM-125 for photocatalytic removal of ppb-level NO.

Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction

Nitrogen-doped graphene is a promising candidate for the replacement of noble metal-based electrocatalysts for oxygen reduction reactions （ORRs）. The addition of pores and holes into nitrogen-doped graphene enhances the ORR activity by introducing abundant exposed edges, accelerating mass transfer, and impeding aggregation of the graphene sheets. Herein, we present a straightforward but effective strategy for generating porous holey nitrogen-doped graphene （PHNG） via the pyrolysis of urea and magnesium acetate tetrahydrate. Due to the combined effects of the in situ generated gases and MgO nanoparticles, the synthesized PHNGs featured not only numerous out-of-plane pores among the crumpled graphene sheets, but also interpenetrated nanoscale （5-15 nm） holes in the assembled graphene. Moreover, the nitrogen doping configurations of PHNG were optimized by post-thermal treatments at different temperatures. It was found that the overall content of pyridinic and quaternary nitrogen positively correlates with the ORR activity; in particular, pyridinic nitrogen generates the most desirable characteristics for the ORR. This work reveals new routes for the synthesis of PHNG-based materials and elucidates the contributions of various nitrogen species to ORRs.