Enhancing photo-generated carriers transfer of K-C_(3)N_(4)/UiO-66-NH_(2) with Er doping for efficient photocatalytic oxidation of furfural to furoic acid

Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.

Preparation of PrFe_(x)Co_(1-x)O_(3)/Mt catalyst and study on degradation of 2-hydroxybenzoic acid wastewater by catalytic wet peroxide oxidation

In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.

Progress in research on catalysts for catalytic oxidation of formaldehyde

Formaldehyde（HCHO）is carcinogenic and teratogenic,and is therefore a serious danger to human health.It also adversely affects air quality.Catalytic oxidation is an efficient technique for removing HCHO.The development of highly efficient and stable catalysts that can completely convert HCHO at low temperatures,even room temperature,is important.Supported Pt and Pd catalysts can completely convert HCHO at room temperature,but their industrial applications are limited because they are expensive.The catalytic activities in HCHO oxidation of transition-metal oxide catalysts such as manganese and cobalt oxides with unusual morphologies are better than those of traditional MnO2,Co3O4,or other metal oxides.This is attributed to their specific structures,high specific surface areas,and other factors such as active phase,reducibility,and amount of surface active oxygens.Such catalysts with various morphologies have great potential and can also be used as catalyst supports.The loading of relatively cheap Ag or Au on transition-metal oxides with special morphologies potentially improves the catalytic activity in HCHO removal at room temperature.The preparation and development of new nanocatalysts with various morphologies and structures is important for HCHO removal.In this paper,research progress on precious-metal and transition-metal oxide catalyst systems for HCHO oxidation is reviewed; topics such as oxidation properties,structure–activity relationships,and factors influencing the catalytic activity and reaction mechanism are discussed.Future prospects and directions for the development of such catalysts are also covered.

Synthesis of three-dimensional ordered mesoporous MnO_2 and its catalytic performance in formaldehyde oxidation

Three-dimensional（3D）ordered mesoporous MnO2 was prepared using KIT-6 mesoporous molecular sieves as a hard template.The material was used for catalytic oxidation of HCHO.The material has high surface areas and the mesoporous characteristics of the template,with cubic symmetry（ia3d）.It consists of a β-MnO2 crystalline phase corresponding to pyrolusite,with a rutile structure.Transmission electron microscopy and X-ray photoelectron spectroscopy showed that the 3D-MnO2 catalyst has a large number of exposed Mn4＋ ions on the（110）crystal plane surfaces,with a lattice spacing of 0.311 nm; this enhances oxidation of HCHO.Complete conversion of HCHO to CO2 and H2O was achieved at 130 °C on 3D-MnO2; the same conversions on α-MnO2 and β-MnO2 nanorods were obtained at 140 and 180 °C,respectively,under the same conditions.The specific mesoporous structure,high specific surface area,and large number of surface Mn4＋ ions are responsible for the catalytic activity of 3D-MnO2 in HCHO oxidation.

Catalytic performance of cobalt oxide-supported gold-palladium nanocatalysts for the removal of toluene and o-xylene

Using the molten salt and polyvinyl alcohol-protected reduction method,we fabricated Co3O4 octahedron-supported Au-Pd（x（AuPdy）/Co3O4;x =（0.18,0.47,and 0.96） wt%;y（Pd/Au molar ratio） =1.85-1.97） nanocatalysts.The molten salt-derived Co3O4 sample possessed well-defined octahedral morphology,with an edge length of 300 nm.The Au-Pd nanoparticles,with sizes of 2.7-3.2 nm,were uniformly dispersed on the surface of Co3O4.The 0.96（AuPd1.92）/Co3O4 sample showed the highest catalytic activity for toluene and o-xylene oxidation,and the temperature required for achieving 90%conversion of toluene and o-xylene was 180 and 187 ℃,respectively,at a space velocity of 40000 mL/（g·h）.The high catalytic performance of Co3O4 octahedron-supported Au-Pd nanocatalysts was associated with the interaction between Au-Pd nanoparticles and Co3O4 and high concentration of adsorbed oxygen species.

Gas-solid catalytic reactions over ruthenium-based catalysts

Ruthenium （Ru）‐based catalysts are widely employed in several types of gas‐solid reactions because of their high catalytic activities. This review provides theoretical research on Ru‐based catalysts and an analysis of their basic properties and oxidation behavior. There is particular emphasis on Ru‐catalyzed gas‐solid catalytic reactions, including the catalytic oxidation of VOCs, preferential oxidation of CO, synthesis of ammonia, oxidation of HCl and partial oxidation of CH4. Recent litera‐ture on catalysis is summarized and compared. Finally, we describe current challenges in the field and propose approaches for future development of Ru‐based catalysts.

Pd micro-nanoparticles electrodeposited on graphene/polyimide membrane for electrocatalytic oxidation of formic acid

A novel Pd electrocatalyst with flowerlike micro-nanostructures was synthesized by electrochemical deposition on a flexible graphene/polyimide（Gr/PI） composite membrane and characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD）.The Pd micro-nanoparticles were prepared on a COOH-CNTs/PI membrane as a comparative sample.The XRD and SEM investigations for Pd electrodeposition demonstrate that the particle size of Gr/PI composite membrane is smaller than that of COOH-CNTs/PI membrane,while the uniform and dense distribution of Pd micro-nanoparticles on the Gr/PI composite membrane is greater than that on the COOH-CNTs/PI membrane.The electrocatalytic properties of Pd/Gr/PI and Pd/COOH-CNTs/PI catalysts for the oxidation of formic acid were investigated by cyclic voltammetry（CV） and chronoamperometry（CA）.It is found that the electrocatalytic activity and stability of Pd/Gr/PI are superior to those of Pd/COOH-CNTs/PI catalyst.This is because smaller metal particles and higher dense distribution desirably provide abundant catalytic sites and mean higher catalytic activity.Therefore,the Pd/Gr/PI catalyst has better catalytic performance for formic acid oxidation than the Pd/COOH-CNTs/PI catalyst.

Low-temperature catalytic oxidation of NO over Mn-Ce-O_x catalyst

A series of manganese-cerium oxide catalysts were prepared by different methods and used for low-temperature catalytic oxidation of NO in the presence of excess O2.Their surface properties were evaluated by means of BET and were characterized by using scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The activity test of Mn-Ce-Ox catalysts showed that addition of Ce enhanced the activities of NO oxidation.The most active catalysts with a molar Ce/(Mn+Ce) ratio of 0.3 were prepared by co-precip...

Structural effect and reaction mechanism of MnO_2 catalysts in the catalytic oxidation of chlorinated aromatics

Various MnO2 structures have been extensively applied in catalysis. In this study,γ-MnO2,α-MnO2, and δ-MnO2 with corresponding rod, tube, and hierarchical architecture morphologies were prepared and applied for the catalytic oxidation of chlorobenzene (CB). The redox ability, H2O activation behavior, and acidity of MnO2 were analyzed using a range of techniques, including TPR, H2O-TPD, XPS, and pyridine-IR. The catalytic activities in CB oxidation were assessed;this revealed that γ-MnO2 exhibited the highest activity and best stability, owing to its enriched surface oxygen vacancies that functioned to activate O2 and H2O, and capture labile chlorine, which reacted with dissociated H2O to form HCl. All the MnO2 phases generated toxic polychlorinated by-products, including CHCl3, CCl4, C2HCl3, and C2Cl4, indicating the occurrence of electrophilic chlorination during CB oxidation. In particular, the dichlorobenzene detected in the effluents of α-MnO2 might generate unintended dioxins via a nucleophilic substitution reaction.

2,5-Furandicarboxylic acid production via catalytic oxidation of 5-hydroxymethylfurfural:Catalysts,processes and reaction mechanism

Biomass conversion to value-added chemicals has received tremendous attention for solving global warming issues and fossil fuel depletion.5-Hydroxymethylfurfural(HMF)is a key bio-based platform molecule to produce many useful organic chemicals by oxidation,hydrogenation,polymerization,and ring-opening reactions.Among all derivatives,the oxidation product 2,5-furandicarboxylic acid(FDCA)is a promising alternative to petroleum-based terephthalic acid for the synthesis of biodegradable plastics.This review analytically discusses the recent progress in the thermocatalytic,electrocatalytic,and photocatalytic oxidation of HMF into FDCA,including catalyst screening,synthesis processes,and reaction mechanism.Rapid fundamental advances may be possible in non-precious metal and metal-free catalysts that are highly efficient under the base-free conditions,and external field-assisted processes like electrochemical or photoelectrochemical cells.

Hierarchical Ni-Al hydrotalcite supported Pt catalyst for efficient catalytic oxidation of formaldehyde at room temperature

Catalytic oxidation at room temperature is recognized as the most promising method for formaldehyde(HCHO)removal.Pt‐based catalysts are the optimal catalyst for HCHO decomposition at room temperature.Herein,flower‐like hierarchical Pt/NiAl‐LDHs catalysts with different[Ni2+]/[Al3+]molar ratios were synthesized via hydrothermal method followed by NaBH4 reduction of Pt precursor at room temperature.The flower‐like hierarchical Pt/NiAl‐LDHs were composed of interlaced nanoplates and metallic Pt nanoparticles(NPs)approximately 3–4 nm in diameter were loaded on the surface of the Pt/NiAl‐LDHs with high dispersion.The as‐prepared Pt/NiAl21 nanocomposite was highly efficient in catalyzing oxidation of HCHO into CO2 at room temperature.The high activity of the hierarchical Pt/NiAl21 nanocomposite was maintained after seven recycle tests,suggesting the high stability of the catalyst.Based on in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies,a reaction mechanism was put forward about HCHO decomposition at room temperature.This work provides new insights into designing and fabricating high‐performance catalysts for efficient indoor air purification.

Selective catalytic oxidation of NO with O_2 over Ce-doped MnO_x/TiO_2 catalysts

A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.

Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

The selective catalytic oxidation （SCO） of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica （MPS） with different Mn/Fe ratios. Effects of the amount of manganese and iron, oxygen, and calcination temperature on NO conversion were also investigated. It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of 1 showed the highest activity at the calcination temperature of 400 °C. The results showed that over this catalyst, NO conversion reached 70% under the condition of 280 °C and a space velocity of 5000 h-1. SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240 °C. In addition, the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240 °C, and such an effect was reversible after heating treatment.

Revealing the unexpected promotion effect of EuO_x on Pt/CeO_2 catalysts for catalytic combustion of toluene

Pt/Eu2O3-CeO2 materials with different Eu concentrations were prepared and applied to toluene destruction,and the remarkable promotion impact of EuOx on Pt/CeO2 can be observed.The characterization results reveal that the presence of EuOx significantly enhances the redox property,lattice O concentration,and Ce3+ ratio of the Pt/CeO2 material,which facilitates the dispersion and activity of Pt active sites and thus accelerates the decomposition process of toluene.Among all catalysts,a sample with an Eu content of 2.5 at.%(Pt/EC-2.5)possesses the best catalytic activity with 0.09 vol% of toluene completely destructed at 200 ℃ under a relatively high GHSV of 50000 h^-1.The possible reaction pathway and mechanism of toluene combustion over Pt/Eu2O3-CeO2 samples are presented according to in-situ DRIFTS,which confirms that the toluene oxidation process obeys the Mars-van Krevelen mechanism with aldehydes and ketones as primary organic intermediates.

Influence of the structure of TiO_2 , CeO_2 , and CeO_2-TiO_2 supports on the activity of Ru catalysts in the catalytic wet air oxidation of acetic acid

Ru catalysts, supported on TiO 2 , CeO 2 , and CeO 2 -TiO 2 , were prepared by the impregnation method. The effect of the structure of the supports on the activity of Ru catalysts was investigated in the catalytic wet air oxidation （CWAO） of acetic acid under 230℃ and 5 MPa in a batch reactor. Physical properties including the surface area, crystalline phase, and surface components of the Ru catalysts were characterized by N 2 adsorption, X-ray powder diffraction （XRD）, and X-ray photoelectron spectroscopy （XPS）. The CeO 2 -based Ru catalysts had good activity, and the prepared RuO 2 /CeO 2 catalyst showed markedly higher activity than the RuO 2 /CeO 2 -TiO 2 catalyst. The surface structure, the high amount of chemisorbed oxygen on the catalyst surface, and the suitable pH pzc value of the supports played an important role in the activity of the Ru catalysts in CWAO of acetic acid.

Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane

Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.

Simulation and Optimization in the Process of Toluene Liquid-phase Catalytic Oxidation

Liquid-phase oxidation of toluene with air has become the main technology for producing benzoic acid in a reactor at present. Based on the kinetic model of the toluene oxidation process obtained from laboratory and mass balance of key component, a novel model is established to simulate the industrial toluene oxidation process, in which the effects of benzaldehyde and benzyl alcohol are considered and the kinetic parameters are revised by industrial data. The simulation results show that the error of benzoic acid yield is within 3.5%. Based on the simulation model, to maximize the benzoic acid yield, an optimization model is proposed to optimize the operating parameters, including toluene feed-in mass flux and temperature. The optimization result indicates that on the allowable operating conditions the maximum benzoic acid yield obtained with the reaction temperature at 167.2 C an the mass flux at 104.1 t·h^- 1 is greater than the current one, which can be used to guide industrial reactor s operation.

Modified-EISA synthesis of mesoporous high surface area CeO_2 and catalytic property for CO oxidation

Mesoporous CeO2 particles with high surface area were synthesized using a modified evaporation-induced self assembly(EISA) method which combined citric acid as complexing agent.As-prepared powder and further thermal treatment samples were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),selected area electron diffraction(SAED),Fourier transform infrared spectrometer(FTIR),thermogravimetry and differential thermal analysis(TG-DTA),Brunauer-Emmett-Teller(BET) and Barrett-Joyner-Ha...

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO_2/MgO and SnO_2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether （DME） in the temperature range of 275 to 300 ℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate （MF） and dimethoxyethane （DMET） of 19.1% and 59.0% respectively were obtained at 275 ℃.

In-plasma catalytic degradation of toluene over different MnO_2 polymorphs and study of reaction mechanism

α‐,β‐,γ‐andδ‐MnO2catalysts were synthesized by a one‐step hydrothermal method,and were utilized for the catalytic oxidation of toluene in a combined plasma‐catalytic process.The relationship between catalytic performance and MnO2crystal structures was investigated.It was noted that the toluene removal efficiency was32.5%at the specific input energy of160J/L when non‐thermal plasma was used alone.Theα‐MnO2catalyst showed the best activity among the investigated catalysts,yielding a toluene conversion of78.1%at the specific input energy of160J/L.Forβ‐MnO2,γ‐MnO2andδ‐MnO2,removal efficiencies of47.4%,66.1%and50.0%,respectively,were achieved.By powder X‐ray diffraction,Raman spectroscopy,transmission electron microscopy,scanning electron microscopy,Brunauer‐Emmett‐Teller,H2temperature‐programmed reduction and X‐ray photoelectron spectroscopy analyses,it was concluded that the tunnel structure,the stability of the crystal in plasma,the Mn-O bond strength of MnO2and the surface‐chemisorbed oxygen species played important roles in the plasma‐catalytic degradation of toluene.Additionally,the degradation routes of toluene in non‐thermal plasma and in the plasma‐catalytic process were also studied.It was concluded that the introduction of MnO2catalysts enabled O3,O2,electrons and radical species in the gas to be adsorbed on the MnO2surface via a facile interconversion among the Mn4+,Mn3+and Mn2+states.These four species could then be transported to the toluene or intermediate organic by‐products,which greatly improved the toluene removal efficiency and decreased the final output of by‐products.