In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH_(2) by adding porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres

MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).

Electro-Deposition Pt Catalysts Supported on Carbon-Nanotubes for Methanol Oxidation

In order to study the properties of supporting Pt catalysts for methanol oxidation,carbon-nanotubes are used by electrochemical deposition method. Different deposition turns,different cyclic voltammetry scanning speeds and processing time with ascorbic acid are investigated in this paper. The micrographs of Pt / CNTs catalysts are characterized by scanning electron microscopy,the electro-catalytic properties of Pt / CNTs catalysts for methanol oxidation are investigated by cycle voltammetry and chronoamperometry. The results show that the size of platinum will be greater with the faster scanning speed. After dissolution in ascorbic acid,Pt nanoparticles disperse uniformly. The obtained Pt / CNTs catalysts show a high electro-catalytic activity and stability.

Doping effects of manganese on the catalytic performance and structure of NiMgO catalysts for controllabe synthesis of multi-walled carbon nanotubes

Doping effects of manganese （Mn） on catalytic performance and structure evolution of NiMgO catalysts for synthesis of multi-walled carbon nanotubes （MWCNTs） from methane were investigated for the first time. Addition of Mn in NiMgO catalyst can greatly improve the MWCNTs yield. Mno.2NiMgO catalyst among the tested ones gives the highest MWCNTs yield as 2244%, which is two times higher than that of the catalyst without Mn. The structure evolution, reduction behaviors and surface chemical properties of MnNiMgO catalysts with various Mn contents were studied in detail. It was found that the stable solid solution of NiMgO2 formed in NiMgO catalyst was disturbed by the addition of Mn. Instead, another solid solution of MnMg608 is formed. More amount of Ni can be reduced and dispersed on the catalyst surface to be acted as active sites. Importantly, the changes of Ni content on the surface are correlated with the Ni particle size and the outer diameter of MWCNTs, suggesting the controllable synthesis of MWCNTs over MnNiMgO catalysts.

Study on Diameter Controlled Growth of Carbon Nanotubes by LaAl_(1-x)Fe_xO_3 Catalysts

A series of LaAl 1-xFe xO 3 catalysts prepared with lanthanum nitrate, aluminium nitrate and iron nitrate was investigated in catalytical syntheses of carbon nanotubes with high yields and purity. The properties of carbon nanotubes prepared by the method of CVD(chemical vapor deposition) with n-hexane as the carbon resource were studied and it was shown that the diameter of carbon nanotubes can be controlled by the molar ratio of iron to aluminum in the catalysts and that the diameter of carbon nanotubes changes a little with the decrease of the iron content in the catalysts. From the TEM pictures of carbon nanotubes, it can be found that the LaAl 1-xFe xO 3 catalysts have a significant influence on the wall thickness of the carbon nanotubes, whereas they have little influence on the inner diameter of the carbon nanotubes.

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

Purified oxygenand nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen and nitrogen-functionalized carbon nanotubes （OCNTs and NCNTs） were applied as metal-free catalysts in selective olefin hydro- genation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 ℃ led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.

Synthesis and characterization of niobium-promoted cobalt/iron catalysts supported on carbon nanotubes for the hydrogenation of carbon monoxide

Bimetallic Co /Fe catalysts supported on carbon nanotubes( CNTs) were prepared,and niobium( Nb) was added as promoter to the 70 Co ∶30Fe /CNT catalyst. The physicochemical properties of the catalysts were characterized,and the catalytic performances were analyzed at the same operation conditions( H_2 ∶CO( volume ratio) = 2 ∶1,p = 1 MPa,and t = 260 ℃) in a tubular fixed-bed microreactor system. The addition of Nb to the bimetallic catalyst decreases the average size of the oxide nanoparticles and improves the reducibility of the bimetallic catalyst. Evaluation of the catalyst performance in a Fischer-Tropsch reaction shows that the catalyst results in high selectivity to methane,and the selectivity to C_(5+) increased slightly in the bimetallic catalyst unlike that in the monometallic catalysts. The addition of 1% Nb to the bimetallic catalyst increases CO conversion and selectivity to C_(5+). Meanwhile,a decrease in methane selectivity is observed.

Fabrication of K-promoted iron/carbon nanotubes composite catalysts for the Fischer–Tropsch synthesis of lower olefins

K-promoted iron/carbon nanotubes composite（i.e., Fe K-OX） was prepared by a redox reaction between carbon nanotubes and K2FeO4followed by thermal treatments on a purpose as the Fischer–Tropsch catalyst for the direct conversion of syngas to lower olefins. Its catalytic behaviors were compared with those of the other two Fe-IM and Fe K-IM catalysts prepared by impregnation method followed by thermal treatments. The novel Fe K-OX composite catalyst is found to exhibit higher hydrocarbon selectivity,lower olefins selectivity and chain growth probability as well as better stability. The catalyst structureperformance relationship has been established using multiple techniques including XRD, Raman, TEM and EDS elemental mapping. In addition, effects of additional potassium into the Fe K-OX composite catalyst on the FTO performance were also investigated and discussed. Additional potassium promoters further endow the catalysts with higher yield of lower olefins. These results demonstrated that the introduction method of promoters and iron species plays a crucial role in the design and fabrication of highly active,selective and stable iron-based composite catalysts for the FTO reaction.

Carbon nanotubes-Nafion composites as Pt-Ru catalyst support for methanol electro-oxidation in acid media

Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by microwave-assisted polyol process. The physical and electrochemical properties of the catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, CO stripping voltammetry, cyclic voltammetry （CV） and chronoamperometry （CA）. The results showed that the Nation incorporation in CNTs-Nation composites did not significantly alter the oxygen-containing groups on the CNTs surface. The Pt-Ru catalyst supported on CNTs-Nafion composites with 2 wt% Naton showed good dispersion and the best CO oxidation and methanol electro-oxidation activities.

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.

Production of Carbon Nanotubes and Hydrogen Catalyzed with Ni/MCM-41 Catalysts

Methane catalytic decomposition (MCD) over Ni/MCM-41 catalysts was tested in a microreactor to simultaneously produce hydrogen and carbon nanotubes (CNTs). The methane conversion reached 30% to 47% at a moderate temperature range from 400°C to 600°C and the catalytic activity of the catalysts remains stable during 500 min steam on time. CNTs were chiefly formed through tip-growth mode, due to the weak interaction between the metallic Ni and the support. Most of the Ni particles are located on the tip of the produced CNTs, which avoids rapid deactivation of the catalyst resulted from carbon encapsulation. Large Ni particles usually lead to the formation of CNTs with big diameter. During the reaction, the shape of Ni particles changed from pseudo-sphere to diamond-like. All the CNTs consist of multiple layer walls and are curved in certain degree.

Carbon Nanotubes Supported Pt-Ru-Ni as Methanol Electro-Oxidation Catalyst for Direct Methanol Fuel Cells

Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction （XRD） and energy dispersive X-ray （EDX） analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy （EIS）, linear sweep voltammetries （LSV）, and chronoamperometry （CA）. The results show that the catalysts exhibit face-centered cubic （fcc） structure. The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.

Preparation and Characterization of Carbon Nanotubes-Coated Cordierite for Catalyst Supports

The carbon nanotubes-coated cordierite （CNTs-cordierite） was fabricated by pyrolysis of ethine on cordierite with iron catalyst, which was penetrated into the cordierite substrate by vacuum impregnation. The cordierite substrate, carbon naontubes, and CNTs-cordierite were characterized by SEM, TEM/HREM, BET, and TGA. The results show that the carbon nanotubes were distributed uniformly on the surface of cordierite. A significant increase in BET surface area and pore volume was observed, and a suitable pore-size distribution was obtained. On the CNTs-cordierite, carbon nanotubes penetrated into the cordierite substrate, which led to a remarkable stability of the CNTs against ultrasound maltreatment. Growth time is an important factor for thermostability and texture of the sample. The mass increased but the purity decreased with the growth time, which caused the exothermic peak shift to low temperature, and the corresponding full width half maximum （FWHM） of the peak in DTG increased.

In-situ emb e dding zeolitic imidazolate framework derived Co–N–C bifunctional catalysts in carbon nanotube networks for flexible Zn–air batteries

Recently, the development of high-performance bifunctional oxygen catalysts integrated with flexible conductive scaffolds f or rechargeable metal-air batteries has attracted considerable interest, driving by fastgrowing wearable electronics. Herein, we report a flexible bifunctional oxygen catalyst thin film consisting of Co–N–C bifunctional catalysts embedding in carbon nanotube(CNT) networks. The catalyst is readily prepared by pyrolysis of cobalt-based zeolitic imidazolate frameworks(ZIF-67) that are in-situ synthesized in CNT networks. Such catalyst film demonstrates very high catalytic activities for oxygen reduction(onset potential: 0.91 V, and half-wave potential: 0.87 V vs. RHE) and oxygen evolution(10 m Acm^-2 at 1.58 V) reactions, high methanol tolerance property, and long-term stability(97% current retention). Moreover, our integrated catalyst film shows very good structure flexibility and robustness. Based on the obtained film air electrodes, flexible Zn–air batteries demonstrate low charging and discharging overpotentials(0.82 V at 1 m A cm^-1) and excellent structure stability in the bending tests. These results indicate that presently reported catalyst films are potential air electrodes for flexible metal–air batteries.

One step NaBH_4 reduction of Pt-Ru-Ni catalysts on different types of carbon supports for direct ethanol fuel cells : Synthe sis and characte rization

The ternary catalyst Pt75Ru5Ni20 was conducted on various types of carbon supports including functionalized Vulcan XC-72R(f-CB),functionalized multi-walled carbon nanotubes(f-MWCNT),and mesoporous carbon(PC-Zn-succinic)by sodium borohydride chemical reduction method to improve the ethanol electrooxidation reaction(EOR)for direct ethanol fuel cell(DEFC).It was found that the particle size of the metals on f-MWCNT was 5.20 nm with good particle dispersion.The alloy formation of ternary catalyst was confirmed by XRD and more clearly described by SEM element mapping,which was relevant to the efficiency of the catalysts.Moreover,the mechanism of ethanol electrooxidation reaction based on the surface reaction was more understanding.The activity and stability for ethanol electrooxidation reaction(EOR)were investigated using cyclic voltammetry and chronoamperometry,respectively.The highest activity and stability for EOR were observed from Pt75Ru5Ni20/f-MWCNT due to a good metal-carbon interaction.Ru and Ni presented in Pt-Ru-Ni alloy improved the activity and stability of ternary catalysts for EOR.Moreover,the reduction of Pt content in ternary catalyst led to the catalyst cost deduction in DEFC.

Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst for ammonia synthesis

Carbon nanotubes(CNTs) with abundant surface defects are prepared by a liquid oxidation and thermal annealing method. The defective CNTs-D supported Ba–Ru/CNTs-D catalysts exhibit superior catalytic performance in ammonia synthesis with a TOF be increased up to 0.30 s-1, which is 2.5 times of oxidized CNTs-O supported Ba–Ru/CNTs-O catalysts and 5 times of the Ba–Ru/CNTs. The characterizations by CO chemisorption, transmission electron microscope, Raman, and X-ray photoelectron spectroscopy revealed that the uniformly well dispersed Ru NPs can be stabilized on the defective sites of CNTs-D. The great improvement of the catalytic performance and stability of the Ba–Ru/CNTs-D is contributed to the strong interaction between Ru NPs and surface defect of the CNTs.

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO_2 Hydrogenation

Nitrogen-doped carbon nanotubes （NCNTs） were used as a support for iron （Fe） nanoparticles applied in car- bon dioxide （CO_2） hydrogenation at 633 K and 25 bar （1 bar = 10-5 Pa）. The Fe/NCNT catalyst promoted with both potassium （K） and manganese （Mn） showed high performance in CO_2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity （GHSV） of 3.1 L-（g·h）-1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promot- ed with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction （XRD）, temperature-programmed reduction （TPR） with molecular hydrogen （H2）, and in situ X-ray absorption near-edge structure （XANES） analysis. The Mn pro- moter stabilized wtistite （FeO） as an intermediate and lowered the TPR onset temperature. Catalytic ammo- nia （NH_3） decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

Growth of carbon nanotubes on the novel FeCo-Al_2O_3 catalyst prepared by ultrasonic coprecipitation

FeCo-Al2O3 catalyst was prepared by an ultrasonic coprecipitation （UC） method for the growth of carbon nanotubes （CNTs） from catalytic decomposition of methane.Its catalytic performance was compared with that of the FeCo-Al2O3 catalyst counterparts prepared by stepwise impregnation （I） and conventional coprecipitation （C） methods,respectively.The structure and properties of the catalysts and the CNTs as produced thereon were investigated by means of XRD,XPS,TEM and N2 adsorption techniques.It was found that the catalyst prepared by the ultrasonic coprecipitation method was more active,and the yield and purity of the synthesized CNTs were promoted evidently.The XPS results revealed that there were more active components on the surface of the catalyst prepared by the ultrasonic coprecipitation method.On the other hand,N2 adsorption demonstrated that the catalyst prepared by the ultrasonic coprecipitation method conferred larger specific surface area,which was beneficial to dispersion of active components.TEM images further confirmed its higher dispersion.These factors could be responsible for its higher activity for the growth of CNTs from catalytic decomposition of methane.

New strategy of S,N co‐doping of conductive‐copolymer‐derived carbon nanotubes to effectively improve the dispersion of PtCu nanocrystals for boosting the electrocatalytic oxidation of methanol

Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.

Synthesis and characterization of multiwall carbon nanotubes/alumina nanohybrid-supported cobalt catalyst in Fischer-Tropsch synthesis

Multiwall carbon nanotubes （MWNTs） and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis （FTS） catalyst support. Alumina nano-particles （10 wt%） were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N2-adsorption, H2 chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate （gHc/（gcat.min））, CO conversion （%）, and water gas shift rate （WGS）（gcoz/（gcat.h）） of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.