Selective hydrogenation of dimethyl toluene-2,4-dicarbamate over supported Rh-based catalysts:Effect of support properties

The selective hydrogenation of dimethyl toluene-2,4-dicarbamate(TDC)to methyl cyclohexyl-2,4-dicarbamate(also called hydrogenated TDC,HTDC)is an essential process for non-phosgene synthesis of methylcyclohexane-2,4-diisocyanate.Herein,we prepared a series of supported Rh-based catalysts by the excessive impregnation method and investigated their catalytic performance for the selective hydrogenation of TDC.The emphasis was put on the influence of support properties on the catalytic performance.Among the prepared catalysts,Rh/g-Al_(2)O_(3)performed the best:a HTDC yield of 88.4%was achieved with a 100%conversion of TDC under the conditions of 100℃,3 MPa and 1 h.Furthermore,Rh/γ-Al_(2)O_(3)could be repetitively used for 4 times without a significant loss of its catalytic activity.TEM,XRD,N_(2)adsorption-desorption,H_(2)-TPR,NH_(3)/CO_(2)-TPD,XPS and ICP characterizations were employed to distinguish the properties of the prepared catalysts and the results were correlated with their catalytic performance.It is indicated that the yield of HTDC shows a positive relevance with the percentage of moderate-to-strong acid sites and the content of Rh^(n+)(n≥3)in the catalysts.High values of the percentage and the content can promote a strong interaction between Rh nanoparticles and the supports,facilitating both the transfer of electrons from Rh to the support and the formation of Rh^(n+)species.This is conducive to activating the benzene ring of TDC and thereby improving the yield of HTDC.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Catalytic removal of volatile organic compounds using ordered porous transition metal oxide and supported noble metal catalysts

Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.

Pt/Co_3O_4/3DOM Al_2O_3:Highly effective catalysts for toluene combustion

Three-dimensionally ordered macro-/mesoporous alumina（3DOM Al2O3）-supported cobalt oxide and platinum nanocatalysts（xPt/yCo3O4/3DOM Al2O3,Pt mass fraction（x%）= 0-1.4%,Co3O4 mass fraction（y%） = 0-9.2%） were prepared using poly（methyl methacrylate） templating,incipient wetness impregnation and polyvinyl alcohol-protected reduction.The resulting xPt/yCo3O4/3DOM Al2O3 samples displayed a high-quality 3DOM architecture with macropores（180-200 nm in diameter） and mesopores（4-6 nm in diameter） together with surface areas in the range of 94 to 102m^2/g.Using these techniques,Co3O4 nanoparticles（NPs,18.3 nm） were loaded on the 3DOM Al2O3 surface,after which Pt NPs（2.3-2.5 nm） were uniformly dispersed on theyCo3O4/3DOM Al2O3.The1.3Pt/8.9Co3O4/3DOM Al2O3 exhibited the best performance for toluene oxidation,with a T（90%） value（the temperature required to achieve 90%toluene conversion） of 160 ℃ at a space velocity of20000 mL g^（-1） h^（-1）.It is concluded that the excellent catalytic performance of the 1.3Pt/8.9Co3O4/3DOM Al2O3 is owing to well-dispersed Pt NPs,the high concentration of adsorbed oxygen species,good low-temperature reducibility,and strong interaction between the Pt and Co3O4 NPs,as well as the unique bimodal porous structure of the support.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Selective hydrogenation of phenol to cyclohexanone in water over Pd catalysts supported on Amberlyst-45

A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.

Designing of highly selective and high-temperature endurable RWGS heterogeneous catalysts: recent advances and the future directions

Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually significance in enabling a rebuilt ecological system for unconventional fuels. This concept is appealing when the process is considered as a solution for the storage of renewable energy, which may also find a variety of potential end uses for the outer space exploration. However, a big challenge to this issue is the rational design of high temperature endurable RWGS catalysts with desirable CO product selectivity. In this work, we present a comprehensive overview of recent publications on this research topic,mainly focusing on the catalytic performance of RWGS reaction over three major kinds of heterogeneous catalysts, including supported metal catalysts, mixed oxide catalysts and transition metal carbides. The reaction thermodynamic analysis, kinetics and mechanisms are also described in detail. The present review attempts to provide a general guideline about the construction of well-performed heterogeneous catalysts for the RWGS reaction, as well as discussing the challenges and further prospects of this process.

Effects of the Supports on Activity of Supported Nickel Catalysts for Hydrogenation of m-Dinitrobenzene to m-Phenylenediamine

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.

Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts

The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundamental understanding of the nature of active sites and structure–performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection.This review surveys the effects of multiple factors,including the metal size,shape,support,alloy and ligand modifier,on the coordinated environment of active center and further their influence on the catalytic reactions,aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance.Subsequently,the key structure characterization techniques in determining the coordination structure of active metal sites,especially the dynamic coordination structure change under the reaction condition,are well summarized.A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.

Transition metal-based single-atom catalysts(TM-SACs);rising materials for electrochemical CO_(2) reduction

The continuous increase of global atmospheric CO_(2) concentrations brutally damages our environment. A series of methods have been developed to convert CO_(2) to valuable fuels and value-added chemicals to maintain the equilibrium of carbon cycles. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is one of the promising methods to produce fuels and chemicals, and it could offer sustainable paths to decrease carbon intensity and support renewable energy. Thus, significant research efforts and highly efficient catalysts are essential for converting CO_(2) into other valuable chemicals and fuels. Transition metal-based single atoms catalysts(TM-SACs) have recently received much attention and offer outstanding electrochemical applications with high activity and selectivity opportunities. By taking advantage of both heterogeneous and homogeneous catalysts, TM-SACs are the new rising star for electrochemical conversion of CO_(2) to the value-added product with high selectivity. In recent years, enormous research effort has been made to synthesize different TM-SACs with different M–Nxsites and study the electrochemical conversion of CO_(2) to CO. This review has discussed the development and characterization of different TMSACs with various catalytic sites, fundamental understanding of the electrochemical process in CO_(2) RR,intrinsic catalytic activity, and molecular strategics of SACs responsible for CO_(2)RR. Furthermore, we extensively review previous studies on 1 st-row transition metals TM-SACs(Ni, Co, Fe, Cu, Zn, Sn) and dual-atom catalysts(DACs) utilized for electrochemical CO_(2) conversions and highlight the opportunities and challenges.

Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

Effect of the support on cobalt carbide catalysts for sustainable production of olefins from syngas

Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.

Covalent organic frameworks as heterogeneous catalysts

Covalent organic frameworks （COFs）, established as an emerging class of crystalline porous polymers with high surface area, structural diversity, and esignability, attract much interest and exhibit potential applications in catalysis. In this review, we summarize the use of COFs as a versatile platform to develop heterogeneous catalysts for a variety of chemical reactions. Catalytic COFs are categorized in accordance with the types of active sites, involving single functional active sites, bifunctional active sites, and metal nanoparticles （NPs） embedded in pores. Special emphasis is placed on the deliberate or incidental synthesis strategies, the stability, the heterogeneity, and the shape/size selectivity for COF catalysis. Moreover, a description of the application of COFs as photocatalysts and electrocatalysts is presented. Finally, the prospects of COFs in catalysis and remaining issues in this field are indicated.

Support effect of the supported ceria-based catalysts during NH_3-SCR reaction

To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.

Simultaneous catalytic removal of NOx and diesel soot particulate over perovskite-type oxides and supported Ag catalysts

A series of perovskite type oxides and supported Ag catalysts were prepared, and characterized by X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.

Hydrogenation of Commercial Polystyrene over Pd/BaSO_4 Catalysts: Effect of Carrier Structure

A variety of barium sulfate(BaSO4) carriers with or without mesopore structure were synthesized via precipitation reaction in aqueous solution of barium hydroxide and sulfuric acid with ethylene glycol as a modifying agent, and then calcined at various temperatures. The obtained BaSO4 was used as catalyst carriers for polystyrene(PS) hydrogenation, and BaSO4 supported palladium(Pd) catalysts with Pd content of 5wt% were prepared by using impregnation method. N2 physisorption, transmission electron microscopy, X-ray diffraction and kinetics studies were used to investigate the effect of carrier structure on the dispersion and geometric location of active metal and their catalytic activities in PS hydrogenation. It was found that the pore structure of carrier played an important role in the dispersion and location of Pd grains. The activation energy values for all the Pd/BaSO4 catalysts were around 49.1kJ/mol, while the pre-exponential factor for Pd/BSC-6H was much higher than others. The Pd/BSC-6H without mesopores had Pd grains deposited on the external surface of the carrier, and exhibited better activity than the mesoporous catalysts. It is indicated that the utilization of Pd/BSC-6H can reduce the pore diffusion of PS coils and enabled more active sites to participate in the PS hydrogenation.

Sodium-treated sepiolite-supported transition metal(Cu,Fe,Ni,Mn,or Co)catalysts for HCHO oxidation

Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples were characterized by means of various techniques, and their catalytic activities for HCHO(0.2%) oxidation were evaluated. Among the samples, Cu/Na Sep exhibited superior performance, and complete HCHO conversion was achieved at 100 ℃(GHSV = 240000 m L/(g·h)). Additionally, the sample retained good catalytic activity during a 42 h stability test. A number of factors, including elevated acidity, the abundance of oxygen species, and favorable low-temperature reducibility, were responsible for the excellent catalytic activity of Cu/Na Sep. According to the results of the in-situ DRIFTS characterization, the HCHO oxidation mechanism was as follows:(i) HCHO was rapidly decomposed into dioxymethylene(DOM) species on the Cu/Na Sep surface;(ii) DOM was then immediately converted to formate species;(iii) the resultant formate species were further oxidized to carbonates;(iv) the carbonate species were eventually converted to CO2 and H2O.

Ultrafine Pt nanoparticles supported on double-shelled C/TiO2 hollow spheres material as highly efficient methanol oxidation catalysts

Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.

Partial oxidation of methane over SiO2 supported Ni and NiCe catalysts

Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.

Dry reforming of methane on active and coke resistant Ni/Y_2Zr_2O_7 catalysts treated by dielectric barrier discharge plasma

In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.