Hollow ZIF-67-derived Co@N-doped carbon nanotubes boosting the hydrogenation of phenolic compounds to alcohols

The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.

Adsorption onto Activated Carbon Fiber Cloth and Electrothermal Desorption of Volatile Organic Compound(VOCs):A Specific Review

A general research program, focusing on activated carbon fiber cloths （ACFC） and felt for environmental protection was performed. The objectives were multiple： （i） a better understanding of the adsorption mecha- nisms of these kinds of materials; （ii） the specification and optimization of new processes using these adsorbents; （iii） the modeling of the adsorption of organic pollutants using both the usual and original approaches; （iv） applications of ACFC in industrial processes. The general question was： how can activated carbon fiber cloths and felts be used in air treatment processes for the protection of environment. In order to provide an answer, different approaches were adopted. The materials （ACFC） were characterized in terms of macro structure and internal porosity. Specific studies were performed to get the air flow pattern through the fabrics. Head loss data were generated and modeled as a fi.mction of air velocity. The performances of ACF to remove volatile organic compounds （VOCs） were approached with the adsorption isotherms and breakthrough curves in various operating conditions. Regenera- tion by Joule effect shows a homogenous heating of adsorber modules with rolled or pleated layers. Examples of industrial developments were presented showing an interesting technology for the removal of VOCs, such as dichloromethane, benzene, isopropyl alcohol and toluene, alone or in a complex mixture.

Adsorption of volatile organic compounds on three activated carbon samples:Effect of pore structure

To investigate the influence of the activated carbon pore structure on the adsorption of volatile organic compounds （VOCs）, three commercial activated carbon samples were chosen. The fixed-bed thermostatic adsorption experiments were conducted under certain conditions, where toluene, acetone, and 1, 2-dichloroethane acted as adsorbents. Then, the incidence relation between the experimental results and the activated carbon pore structure was analyzed. After that, the results of the correlation analysis were verified in accordance with fractal theory and adsorption characteristic curve analysis. The results show that the pore diameter gradient is helpful for strengthening the intemal diffusion. Under the same condition, the adsorption of organic gases tends to be selective, and the positions of toluene, acetone and 1, 2-dichloroethane adsorbed on the activated carbon are mainly in the ranges of 1.27-1.49 nm, 0.67-0.84 nm and 1.39-1.75 nm, respectively. The relationship between adsorption capacity and activated carbon pore volume can accurately explain the spreading process of the adsorbents in the activated carbon.

A mini-review on the modeling of volatile organic compound adsorption in activated carbons: Equilibrium, dynamics, and heat effects

The research on the adsorption equilibria,kinetics,and increase in process temperature of the volatile organic compound(VOC)adsorption in porous materials ensures safe production,thereby reducing production costs and improving separation efficiency.Therefore,it is critical in predicting the entire adsorption process based on minimal or no experimental input of the adsorbate and adsorbent.We discuss,in this review,the factors that affect the adsorption performance of VOCs in activated carbons,including the adsorption equilibrium,adsorption kinetics,and exotherm during adsorption.Subsequently,the existing prediction models are summarized and compared concerning the adsorption equilibrium,adsorption kinetics,and exothermic process of adsorption.We then propose a new prediction model based on intermolecular interaction and provide an outlook toward the design and manipulation of efficient adsorbents for the VOC system.

Hierarchical pore structure of activated carbon fabricated by CO_2/microwave for volatile organic compounds adsorption

An activated carbon pore-expanding technique was achieved through innovative reactivation by CO_2/microwave.The original and modified activated carbons were characterized by nitrogen adsorption–desorption,scanning electron microscopy,transmission electron microcopy,and Fourier transform infrared spectroscopy.The mesopore volume increased from 0.122 cm^3·g^(-1) to 0.270 cm^3·g^(-1),and a hierarchical pore structure was formed.A gradual decrease in the phenolic hydroxyl and carboxyl groups on the surface of activated carbon enhanced the surface inertia of granular activated carbon(GAC).The toluene desorption rate of the modified sample increased by 8.81% compared with that of the original GAC.Adsorption isotherm fittings revealed that the Langmuir model was applicable for the original and modified activated carbons.The isosteric adsorption heat of toluene on the activated carbon decreased by approximately 50%,which endowed the modified sample with excellent stability in application.The modified samples showed an enhanced desorption performance of toluene,thereby opening a way to extend the cycle life and improve the economic performance of carbon adsorbent in practical engineering applications.

Improvement of visible light-induced photocatalytic performance by Cr-doped SrTiO_3-carbon nitride intercalation compound (CNIC) composite

Novel organic-inorganic composite photocatalyst offers new opportunities in the practical applications of photocatalysis. Novel visible light-induced Cr-doped Sr Ti O3–carbon nitride intercalation compound(CNIC) composite photocatalysts were synthesized. The composite photocatalyst was characterized by X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM), high-resolution transmission electron microscopy(HRTEM), Fourier transform infrared(FT-IR) spectroscopy, UV-vis diffuse reflection spectroscopy, photoluminescence(PL) spectroscopy, and BET surface area analyzer. The photocatalytic oxidation ability of the novel composite photocatalyst was evaluated using methyl orange(MO) as a target pollutant. The photocatalysts exhibited a significantly enhanced photocatalytic performance in degrading MO. For maximizing the photodegradation activity of the composite photocatalysts, the optimal CNIC content was determined. The improved photocatalytic activity of the as-prepared Cr-doped Sr Ti O3–CNIC composite photocatalyst may be attributed to the enhancement of photo-generated electron–hole separations at the interface.

New CO_2-philic Compounds: Design, Synthesis and Solubility in Supercritical Carbon Dioxide

A series of gluscose derivatives were designed, synthesized, and their structures were confirmed by IR, NMR and elementary analysis. All new compounds are highly soluble in liquid or supercritical carbon dioxide. The compound with electron-withdrawing substituent on benzene ring had even better solubility than the compounds with electron-donating substituent.

Experimental Observation of Cubic C_3N_4 Compound in Carbon Nitride Thin Films

Cubic C3N4 compound in the C-N thin films on Si and NaCl substrates was prepared by ion beam sputtering of a pure graphite target with discharge gas of pure N2. X-ray photoelectron spectroscopy indicated that nitrogen atoms combined with sp2- and sp3- coordinated C atoms in the film, respectively. X-ray diffraction, selected area electron diffraction and high-resolution electron microscopy were used to identify the cubic C3N4 phase. The results reconfirm the ab initio calculations on metastable structure in C-N compounds

Prediction of Henry Constants and Adsorption Mechanism of Volatile Organic Compounds on Multi-Walled Carbon Nanotubes by Using Support Vector Regression

Support vector regression （SVR） combined with particle swarm optimization for its parameter optimization is employed to establish a model for predicting the Henry constants of multi-walled carbon nanotubes （MWNTs） for adsorption of volatile organic compounds （VOCs）. The prediction performance of SVR is compared with those of the model of theoretical linear salvation energy relationship （TLSER）. By using leave-one-out cross validation of SVR test Henry constants for adsorption of 35 VOCs on MWNTs, the root mean square error is 0.080, the mean absolute percentage error is only 1.19~, and the correlation coefficient （R2） is as high as 0.997. Compared with the results of the TLSER model, it is shown that the estimated errors by SVR are ali smaller than those achieved by TLSER. It reveals that the generalization ability of SVR is superior to that of the TLSER model Meanwhile, multifactor analysis is adopted for investigation of the influences of each molecular structure descriptor on the Henry constants. According to the TLSER model, the adsorption mechanism of adsorption of carbon nanotubes of VOCs is mainly a result of van der Waals and interactions of hydrogen bonds. These can provide the theoretical support for the application of carbon nanotube adsorption of VOCs and can make up for the lack of experimental data.

Synthesis of ZnGaNO solid solution–carbon nitride intercalation compound composite for improved visible light photocatalytic activity

Visible-light-driven ZnGaNO solid solution–carbon nitride intercalation compound(CNIC) composite photocatalyst was synthesized via a mixing and heating method. The composite photocatalyst was characterized by X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM), high-resolution transmission electron microscopy(HRTEM), Fourier transform infrared(FT-IR) spectroscopy, UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy(XPS), photoluminescence(PL) spectroscopy and BET surface area measurements. The activity of ZnGaNO–CNIC composite photocatalyst for photodegradation of methyl orange(MO) is higher than that of either single-phase CNIC or ZnGaNO solid solution. The as-prepared composite photocatalysts exhibit an improved photocatalytic activity due to enhancement for the separation and transport of photo-generated electron–hole pairs.

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYTZED BY METALLOPORPHYRINS(Ⅳ)——EFFECT OF VARIOUS FACTORS ON ELECTROCARBOXYLATION

The effects of various factors on the electrocarboxylation of organic compounds with carbon dioxide catalyzed by metalloporphyrin are studied.The optimal potential of electrocar- boxylation is -1.6 V(vs.SCE).A weak protic solvent methanol can enhance catalytic activity. Tetrabutylammonium iodide is the best one of five electrolytes.The yields and current efficiencies of electrocarboxylation are increased slowly as the concentration of catalyst increases.

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅲ)——EFFECTS OF AXIAL LIGANDS ON CATALYTIC ACTIVITY OF CoTPP

The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac- tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported. The imidazole organic base,peptide containing —SH and amino acid containing imidazolyl en- hance the catalytic activity.The effect of imidazole amounts on the catalytic activity of CoTPP is studied.

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅱ)——ELECTROSYNTHESIS OF SOME ORGANIC COMPOUNDS WITH CO_2 CATALYZED BY CoTPP

The catalyzation of CoTPP for electrocarboxylation of alkyl halides, alkenes and ketones with CO_2 are studied. The electrocarboxylation of these organic compounds with CO_2 in the presenec of catalyst can occur at more positive potential than that of no catalyst. The products of electrocarboxylation were identified by UV, IR and GC-MS. The electrocarboxylation mechanisms of different organic compounds are discussed.

Mechanical Property and Microstructure of Cement Mortar with Carbonated Recycled Powder

Carbonated recycled powder as cementitious auxiliary material can reduce carbon emissions and realize high-quality recycling of recycled concrete.In this paper,microscopic property of recycled powder with three carbonation methods was tested through XRD and SEM,the mechanical property and microstructure of recycled powder mortar with three replacement rates were studied by ISO method and SEM,and the strengthening mechanism was analyzed.The results showed that the mechanical property of recycled powder mortar decreased with the increasing of replacement rate.It is suggested that the replacement rate of recycled powder should not exceed 20%.The strength index and activity index of carbonated recycled powder mortar were improved,in which the flexural strength was increased by 27.85%and compressive strength was increased by 20%at the maximum.Recycled powder can be quickly and completely carbonated,and the improvement effect of CH pre-soaking carbonation was the best.The activity index of carbonated recycled powder can meet the requirements of Grade II technical standard for recycled powder.Microscopic results revealed the activation mechanism of carbonated recycled powder such as surplus calcium source effect,alkaline polycondensation effect and carbonation enhancement effect.

Structures and Properties of High-Carbon High Speed Steel by RE-Mg-Ti Compound Modification

The effects of rare earths(RE)-Mg-Ti compound modification on the structures and properties of high-carbon high speed steel(HSS) were researched.The impact toughness(α_k),the fracture toughness(K_(1c))and threshold of fatigue crack growth(ΔK_(th))are tested.The thermal fatigue test is done on a self-straining thermal fatigue tester,the wear test is done on a high temperature wear test machine.The results show that the matrix can be refined by the RE-Mg-Ti compound modification,the eutectic carbides are inclined to spheroidicize and are distributed evenly,the morphology and distribution of eutectic carbides are improved by appropriate RE-Mg-Ti complex modification.After RE-Mg-Ti compound modification,a little effects can be found on the strength,hardness and red hardness,but the fracture toughness(K_(1c)) and threshold of fatigue crack growth(△K_(th)) are improved in the meantime,the impact toughness (α_k) is increased by over one time,and the resistance to thermal fatigue and wear resistance at an elevated temperature are remarkably improved.

Pt nanoparticles entrapped in ordered mesoporous carbons:An efficient catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives

Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.

Artificial bioconversion of carbon dioxide

CO2 is not only the most important greenhouse gas but also an important resource of elemental carbon and oxygen.From the perspective of resource and energy strategy,the conversion of CO2 to chemicals driven by renewable energy is of significance,since it can not only reduce carbon emission by the utilization of CO2 as feedstock but also store low-grade renewable energy as high energy density chemical energy.Although studies on photoelectrocatalytic reduction of CO2 using renewable energy are increasing,artificial bioconversion of CO2 as an important novel pathway to synthesize chemicals has attracted more and more attention.By simulating the natural photosynthesis process of plants and microorganisms,the artificial bioconversion of CO2 can efficiently synthesize chemicals via a designed and constructed artificial photosynthesis system.This review focuses on the recent advancements in artificial bioreduction of CO2,including the key techniques,and artificial biosynthesis of compounds with different carbon numbers.On the basis of the aforementioned discussions,we present the prospects for further development of artificial bioconversion of CO2 to chemicals.

In-situ route for the graphitized carbon/TiO composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants

TiO2 is the most photoactive material because of its superstrong photooxidizing ability,and TiO2 photocatalysis has been widely applied in sustainable water treatment and environmental remediation.However,poor sunlight or visible-light harvesting efficiency and fast recombination rate of the photogenerated charge carriers severely limit the practical applications of TiO2.To overcome these problems,the present work demonstrates a facile in-situ co-condensation method combined with hydrothermal treatment to prepare a series of graphitized carbon/TiO2 composite photocatalysts,and anatase TiO2 phase andp-p-conjugated polycyclic aromatic carbon structure are created simultaneously.As-prepared TiO2/C composites exhibit remarkably high visible-light photocatalytic activity in the degradation of aqueous emerging phenolic pollutants,acetaminophen(APAP)and methylparaben(MPB),and apparent rate constant of the TiO2/C composite with carbon doping level of 10.3%for APAP and MPB removal is 7.6 and 2.8 times higher than that of bare TiO2,and 6.2 and 2.6 times higher than that of Degussa P25 TiO2.Based on the results of photoelectrochemical experiments,indirect chemical probe measurements,and ESR spectroscopy,it is verified that doping TiO2 with graphitized carbon is responsible for this enhanced photocatalytic activity,which renders the improved visible-light harvesting ability,the accelerated separation of the photogenerated charge carriers,and enlarged BET surface areas.Through analyzing the intermediates yielded in the photodegradation process,the pathway of visible-light photocatalytic degradation of APAP and MPB over the TiO2/C composite is proposed.

Intercalation of multiply solvated hexafluorophospate anion into graphite electrode from mixtures of methyl acetate,ethyl methyl and ethylene carbonates

Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.