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1.
The poly(2-aminoethyl methacrylate) (p(AEM)) microgels were synthesized by microemulsion polymerization technique and used for in situ metal nanoparticle preparation to render as p(AEM)-M (M: Co or Ni) microgel composites and were used in p(AEM) based poly ionic liquid (PIL) microgels. Next, these p(AEM)) based microgel materials were used as catalysts for hydrogen (H2) production from both hydrolysis and methanolysis reactions of sodium borohydride (NaBH4). It was found that the catalytic hydrolysis of the NaBH4 reaction, catalyzed by p(AEM)-Co microgel composite was completed in 140 min, whereas the methanolysis of NaBH4 methanolysis catalyzed by the PIL of p(AEM)+Cl microgels was completed in 5 min both with 250 ± 2 mL H2 production. Furthermore, p(AEM)-Co microgel composite catalysts maintained 80% catalytic activity after 5 consecutive uses in NaBH4 hydrolysis. On the other hand, p(AEM)+Cl microgels were found to afford more than 50% catalytic activity even after 20 repetitive use in NaBH4 methanolysis due to superior regeneration ability. Moreover, activation energy values for p(AEM)-Co microgel composites catalyzed NaBH4 hydrolysis reaction were calculated as 38.9 kJ/mol in comparison to 37.3 kJ/mol activation energy of p(AEM)+Cl microgel catalyzed methanolysis reaction.  相似文献   

2.
The development of efficient and non-noble catalyst is of great significance to hydrogen generation techniques. Three surface-oxidized cobalt borides of Co–B–O@CoxB (x = 0.5, 1 and 2) have been synthesized that can functionalize as active catalysts in both alkaline water electrolysis and the hydrolysis of sodium borohydride (NaBH4) solution. It is discovered that oxidation layer and low boron content favor the oxygen evolution reaction (OER) activity of Co–B–O@CoxB in alkaline water electrolysis. And surface-oxidized cobalt boride with low boron content is more active toward hydrolysis of NaBH4 solution. An alkaline electrolyzer fabricated using the optimized electrodes of Co–B–O@CoB2/Ni as cathode and Co–B–O@Co2B/Ni as anode can deliver current density of 10 mA cm−2 at 1.54 V for overall water splitting with satisfactory stability. Meanwhile, Co–B–O@Co2B affords the highest hydrogen generation rate of 3.85 L min−1 g−1 for hydrolysis of NaBH4 at 25 °C.  相似文献   

3.
The introduction of magnetism into a catalyst can greatly optimize its separation performance. In the present work, a kind of magnetically separable catalysts for promoting NaBH4 hydrolysis have been fabricated by anchoring cobalt nanoparticles on magnetic dendritic KCC-1 nanospheres composed of magnetic Fe3O4 core and fibrous shell. The fabricated catalysts were characterized with various characterization methods, including absorption spectroscopy (AAS), scanning electron microscopy (SEM), high-resolution transmission electronic microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and Fourier transform infrared (FT-IR), etc. This kind of catalysts exhibit high catalytic activity for promoting the hydrolysis of NaBH4 under alkaline conditions, giving a hydrogen generation rate and activation energy of 3.83 L min−1 gCo−1 (30 °C) and 53.63 kJ mol−1, respectively. After used for 5 cycles, the catalyst showed 36.5% catalytic activity reserved. Most importantly, the magnetism of the catalyst made it easily separated and recycled from the solution after the reaction completed. The development of this kind of catalysts could provide a promising option for catalyzing NaBH4 hydrolysis for portable hydrogen production from.  相似文献   

4.
In this study, the metallurgic sludge which contained oil and was obtained as waste of grinding, sharpening and milling parts was used in the production of hydrogen (H2) from sodium borohydride (NaBH4). The hydrolysis of NaBH4 with the metallurgic sludge catalyst was investigated depending on several parameters such as sodium hydroxide (NaOH) concentration, catalyst amount, NaBH4 concentration and temperature. The obtained metallurgic sludge catalyst was characterized by the XRD, FT-IR and SEM techniques and was evaluated for its activity in the H2 generation from NaBH4 hydrolysis. The maximum H2 production rate from the hydrolysis of NaBH4 with the metallurgic sludge catalyst was calculated as 9366 ml min−1.gcat−1. The value of activation energy was found as 48.05 kJ mol−1.  相似文献   

5.
In this study, grinded apricot kernel shell (GAKS) biobased waste was used for the first time as a cost-effective, efficient, green and metal-free catalyst for hydrogen generation from the hydrolysis reaction of sodium borohydride (NaBH4). For the hydrogen production by NaBH4 hydrolysis reaction, GAKS was treated with various acids (HCl, HNO3, CH3COOH, H3PO4), salt (ZnCl2) and base (KOH). As a result, the phosphoric acid (H3PO4) demonstrated better catalytic activity than other chemical agents. The hydrolysis of NaBH4 with the GAKS-catalyst (GAKScat) was studied depending on different parameters such as acid concentration, furnace burning temperature and time, catalyst amount, NaBH4 concentration and hydrolysis reaction temperature. The obtained GAKScat was characterized by ICP-MS, elemental analysis, TGA, XRD, FT-IR, Boehm, TEM and SEM analyses and was evaluated for its catalytic activity in the hydrogen production from the hydrolysis reaction of NaBH4. According to the results, the optimal H3PO4 percentage was found as 15%. The maximum hydrogen generation rate from the hydrolysis of NaBH4 with the GAKScat was calculated as 20,199 mL min−1 gcat−1. As a result, it can be said that GAKS treated with 15% H3PO4 as a catalyst for hydrogen production is an effective alternative due to its high hydrogen production rate.  相似文献   

6.
Hydrogen production via chemical processes has gained great attention in recent years. In this study, Co-based complex catalyst obtained by adsorption of Co metal to Amberlite IRC-748 resin and Diaion CR11 were tested for hydrogen production from alkaline NaBH4 via hydrolysis process. Their catalytic activity and microstructure were investigated. Process parameters affecting the catalytic activity, such as NaOH concentration, Co percentage and catalyst amount, as well as NaBH4 concentration and temperature were investigated. Furthermore, characteristics of these catalysts were carried out via SEM, XRD and FT-IR analysis. Hydrogen production rates equal to 211 and 221 ml min−1 gcat−1 could be obtained with Amberlite IRC-748 resin and Diaion CR11 Co based complex catalysts, respectively. The activation energies of the catalytic hydrolysis reaction of NaBH4 were calculated as 46.9 and 59.42 kJ mol−1 for Amberlite IRC-748 resin and Diaion CR11 based catalysts respectively kJ mol−1 from the system consisting of 3% Co, 10 wt% NaBH4 and 7 wt% NaOH as well as 50 mg catalyst dosage. It can be concluded that Co-based resins as catalysts for hydrogen production is an effective alternative to other catalysts having higher rate.  相似文献   

7.
Well dispersed magnetically recyclable bimetallic CoxNi1−x (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using the mixture of sodium borohydride (NaBH4) and methylamine borane (MeAB) as the reducing agent under ambient condition. These NPs were composition dependent for catalytic hydrolysis of amine boranes. Among all the CoNi/graphene catalysts tested, the Co0.9Ni0.1/graphene NPs exhibit the highest catalytic activity toward hydrolysis of AB with the turnover frequency (TOF) value of 16.4 (mol H2 min−1 (mol catalyst)−1), being higher than that of most reported non-noble metal-based NPs, and even many noble metal-based NPs. Moreover, the activation energy (Ea) value is 13.49 kJ/mol, which is the second lowest value ever reported for catalytic hydrolytic dehydrogenation of ammonia borane, indicating the superior catalytic performance of the as-synthesized Co0.9Ni0.1/graphene catalysts. Additionally, Compared with other reducing agents, such as NaBH4, AB, MeAB, and the mixture of NaBH4 and AB, the as-synthesized Co0.9Ni0.1/graphene catalysts reduced by the mixture of NaBH4 and MeAB exert the highest catalytic activity. The Co0.9Ni0.1 NPs supported on graphene exhibit higher catalytic activity than catalysts with other conventional supports, such as SiO2, carbon black, and γ-Al2O3. Furthermore, the as-synthesized Co0.9Ni0.1/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of amine boranes, which make the practical reusing application of the catalysts more convenient.  相似文献   

8.
Recently, effective hydrogen (H2) evolution upon hydrolysis of different hydrogen storage materials has received much attention. Herein, graphene quantum dots-transition metal nanoparticles (GQDs-TMNPs), with high dispersibility and activity, have been successfully applied in the hydrolysis of both NH3BH3 (AB) and NaBH4 for the first time. GQDs-RhNPs, GQDs-RuNPs, and GQDs-PtNPs are very effective in the hydrolysis of AB and the turnover frequencies (TOFs) can achieve to as high as 656, 384, and 281 molH2·molcat?1 min?1, respectively. Moreover, the synergistic effect between GQDs and TMNPs is explored, and the mechanisms of catalytic hydrolysis of AB and NaBH4 by GQDs-TMNPs are proposed. This work not only paves the way for the development of GQDs-TMNPs nanocatalysts for the different hydrogen storage materials, but also further advances the understanding of the synergistic effects between GQDs and TMNPs.  相似文献   

9.
The current study provided the first example to develop the Fe-based catalyst for COx-free hydrogen production via ammonia decomposition through the unique MgFe-layered double hydroxides (MgFe-LDHs) of different stoichiometric Mg/Fe ratio. The so obtained Fe-based catalyst is low-cost, readily obtainable, and environmentally friendly. Structurally, the Fe(FeNx) species are 3D-isolated by the nano-MgO entities, improving anti-sintering potential of Fe(FeNx); and electronically, the Fe (FeNx) species are promoted by the nano-MgO matrix, showing the strongest promoting effect of MgO on Fe(FeNx). At a GHSVNH3 of 150,000 mL gcat−1 h−1, the current N–Mg5.3FeOm catalyst can give an outstanding H2 formation rate of 9.83 mol gcat−1 h−1 at 680 °C and a TOFH2 = 2.19 s−1 at 530 °C. The influence of Mg/Fe constitution on catalyst structure, surface property, and performance was systematically investigated. The in-situ ammonia treatment was superior to the usually adopted hydrogen pre-reduction for the Fe–Mg oxide precursor, leading to easy development of small sized FeNx specimen and activity enhancement.  相似文献   

10.
In this work, the photocatalysts containing oxygen-deficient molybdenum oxide and macroscopic three-dimensional porous graphitic carbon nitride phase composite (MoO3-x/PCN) were prepared by in situ self-assembly method. The crystal phase and structure were characterized by XRD, XPS, FT-IR, SEM, and TEM measurements. Hydrogen production results showed that introducing of MoO3-x resulted in a higher hydrogen production rate of MoO3-x/PCN composite catalyst than that of PCN. Among them, the highest hydrogen production rate of 2336.15 μmol g−1 h−1 was achieved for MoO3-x-10/PCN, which was 2.23 times higher than PCN (1048.00 μmol g−1 h−1). When the reaction system temperature was 100 °C, the photothermal hydrogen production rate of MoO3-x-10/PCN was 8902.00 μmol g−1 h−1, which was 3.81 times higher than that at room temperature. PL spectra, UV–vis spectra and photoelectrochemical measurements showed that the localized surface plasmon resonance (LSPR) effect of MoO3-x effectively enhanced the photo response range and increased the temperature of the reaction system. ESR measurements showed that he composites should follow the Z-scheme charge transfer mechanism, the electrons in the CB of MoO3-x further migrate to the VB of PCN, which hinders the charge complexation in MoO3-x and PCN, improving the hydrogen production activity. This study provides a new idea for constructing a plasma-based photothermal synergistic catalytic hydrogen production strategy.  相似文献   

11.
The Rh/Ce0·75Zr0·25O2–δ-ƞ-Al2O3/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h−1. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h−1), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h−1. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h−1. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H2, CO, CO2), the reaction should be carried out at GHSV = 20,000 h−1. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.  相似文献   

12.
In this research study, orange peel-based biocatalysts developed from different acid protonation were used as a metal-free catalyst for hydrogen production from sodium borohydride (NaBH4). In order to prepare the orange peel-based biocatalyst with higher catalytic activity, experiments were conducted with pure orange peel, different acid molar concentrations, and calcination temperatures. The physical morphology, surface texture, and chemical interaction were thoroughly analyzed by XRD, FTIR Raman, FESEM, BET, and TGA. As a result of the experiment, it was determined that the highly acid-treated biocatalyst (40% H3PO4, 40% H2SO4, 40% HCl) and calcinated at 450 °C for 1 h had higher catalytic activity. As a result, bio-hydrogen production at 35 °C and 70 °C methanolysis with 3% NaBH4 catalyzed by a mixture of acid-treated catalysts were found as 46,213 and 63,842 ml min−1g.cat−1, respectively. However, with the increase of molar concentration of biocatalyst with 40% individual acid prolonged samples, the HGR rates will not have a satisfactory value in comparison with the 40% mixture of the acid-treated catalyst due to less number of active sites.  相似文献   

13.
A series of Cu0.1-xNixCe0.9O2-y catalysts with different Cu/Ni molar ratios were prepared by the ball milling method. The obtained catalytic materials were characterized by XRD, H2-TPR, BET, XPS and Ramen and the effects of different Cu/Ni content on the structure, properties and CO catalytic oxidation performance of the catalysts were explored. The results evidenced the formation of Cu–Ni–Ce mixed oxide solid solution in all ternary catalysts. In addition, there is a synergistic interaction between Cu and Ni in ternary catalysts, resulting in more oxygen vacancies and improved reduction performance, and hence demonstrating better CO catalytic oxidation activity in the ternary catalysts than binary ones. Under a GHSV of 60000 mL·gcat−1·h−1, the required reaction temperature for reaching less than 10 ppm CO is lowed from 160 °C with Cu0·1Ce0·9O2-y to 130 °C with Cu0·07Ni0·03Ce0·9O2-y.  相似文献   

14.
CeOx-induced amorphization of CoPt nanoparticles (NPs) is achieved by a facile co-reduction method using sodium borohydride (NaBH4) as the reducing agent at room temperature (298 K) under ambient atmosphere. The investigation results indicate that CeOx plays a critical role in transferring the crystalline CoPt nanoalloy into the amorphous one. To our surprise, the resultant Co0.65Pt0.30(CeOx)0.05 NPs exhibit high catalytic kinetic performance with 72.1% hydrogen (H2) selectivity for the H2 generation from hydrous hydrazine (N2H4) within only a few minute at 298 K. Although complete conversion is not achieved, but the initial turnover frequency value of 194.8 h−1 for the present amorphous catalyst is much higher than that of crystalline one. Moreover, such a highly rapid catalyst may greatly encourage the practical application of hydrous N2H4 as a hydrogen storage material.  相似文献   

15.
In recent years, catalytic hydrolysis of sodium borohydride is considered to be a promising approach for hydrogen generation towards fuel cell devices, and highly efficient and noble-metal-free catalysts have attracted increasing attention. In our present work, Co3O4 nanocubes are synthesized by solvothermal method, and then vapor-phase phosphorization treatment is carried out for the preparation of novel Co−O−P composite nanocatalysts composed of multiple active centers including Co, CoO, and Co2P. For catalyst characterization, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and X-ray photoelectric spectroscopy (XPS) are conducted. Optimal conditions for catalyst preparation and application were investigated in detail. At room temperature (25 °C), maximum hydrogen generation rate (HGR) is measured to be 4.85 L min−1 g−1 using a 4 wt% NaBH4 − 8 wt% NaOH solution, which is much higher than that of conventional catalysts with single component reported in literature. It is found that HGR remarkably increases with the increasing of reaction temperature, and apparent activation energy for catalytic hydrolysis of NaBH4 is calculated to be 63 kJ mol−1. After reusing for five times, the Co−O−P composite nanocatalysts still retains 78% of the initial activity.  相似文献   

16.
NH3 decomposition over non-noble catalyst to generate COx-free H2 has attracted great attention in recent years. In this work, fumed SiO2-supported Ni, Co and Ni–Co bimetallic catalysts are synthesized by using a co-impregnation method and evaluated for NH3 decomposition, which shows that the bimetallic catalysts exhibit better catalytic activity than the monometallic ones. This enhanced activity observed on bimetallic catalyst can be largely attributed to the more appropriate catalyst metal-N binding energy resulting from the synergistic effect between Ni and Co in the formed Ni–Co alloy. Among the synthesized catalysts, Ni5Co5/SiO2 synthesized with the Ni/Co molar ratio of 5:5 achieves 76.8% NH3 conversion under a GHSV of 30,000 mL h−1 g−1cat at 550 °C and shows the best catalytic activity, which can be further improved by doping with K (78.1% NH3 conversion at 30,000 mL h−1 g−1cat), and the obtained Ni5Co5/SiO2–K also shows excellent catalytic stability.  相似文献   

17.
Herein, the CoB catalyst supported on the sepiolite clay treated with phosphoric acid was utilized to produce hydrogen from the NaBH4 hydrolysis. In order to analyse the performance of the phosphoric acid treated sepiolite clay supported-CoB catalyst, the NaBH4 concentration effect, phosphoric acid concentration effect, phosphoric acid impregnation time effect, CoB catalyst percentage effect, and temperature effect were studied. In addition, XRD, XPS, SEM, TEM, BET, and FTIR analysis were performed for characterization of Co–B catalyst supported on the acid-treated sepiolite. The completion time of this hydrolysis reaction with Co–B (20%) catalyst supported on the sepiolite treated by 5 M phosphoric acid was approximately 80 min, whereas the completion time of this hydrolysis reaction with acid-free sepiolite-supported Co–B (20%) catalyst was approximately 260 min. There is a five-fold increase in the maximum production rate. The maximum hydrogen production rates of this hydrolysis reaction at 30 and 60 °C were found as 1486 and 5025 ml min−1g−1catalyst, respectively. Activation energy was found as 21.4 kJ/mol. This result indicates that the acid treatment on sepiolite is quite successful. The re-usability of NaBH4 hydrolysis reaction by CoB catalyst supported on sepiolite treated phosphoric acid for successive five cycles of NaBH4 at 30 °C was investigated.  相似文献   

18.
Ni(10 wt%)@UiO-66 and Ni(10 wt%)@MIL-101 composites were prepared by the classical impregnation method (IMP) and the “double solvent method” (DS), followed by the rapid and simple reduction of Ni2+ to Ni0 by aqueous solution of NaBH4. Structural characterization by BET, XRD, TGA, SEM/EDX, EELS, XPS showed that Ni nanoparticles of maximum 4 nm are uniformly dispersed on the microporous UiO-66 or the mesoporous MIL-101 support, regardless of the deposition method, without any significant difference in crystallinity and morphology of the MOF support. Functional characterization through temperature programmed desorption of CO2 (CO2-TPD) reveals an important contribution of the Ni-MOF interaction in the CO2 adsorption capacity. The best catalytic performance in CO2 hydrogenation reaction was obtained in case of the Ni@MIL-101 (IMP) sample: XCO2 of 56.4%, and SCH4 of 91.6% at 320 °C, 4650 h−1 and CO2:H2 = 1:8. All catalyst samples show stable catalytic performance parameters over a 10 h time on stream.  相似文献   

19.
The hydrolysis of sodium borohydride (NaBH4) over catalysts is a promising method to produce hydrogen. Although Co-based catalysts exhibit high activity for NaBH4 hydrolysis, they are still far from satisfying practical applications, especially their poor durability in alkaline media. Herein, a carbon shell structure was designed and synthesized to improve the stability of the mixture of Co0 and CoxOy nanofilms (Co/CoxOy@C) during NaBH4 hydrolysis via a facile polymerization-pyrolysis strategy with Co/CoxOy nanofilms as the precursor. As a result, the Co/CoxOy@C catalyst can achieve a remarkable H2 generation rate of 4348.6 mL min?1 gCo?1 with a low activation energy of 43.6 kJ mol?1, which is superior to most previously reported catalysts. Moreover, the catalyst shows high stability with an H2 generation-specific rate of 79% after five cycles. The excellent performance of carbon substrate can well prevent the agglomeration of Co-based nanoparticle and improve the corrosion resistance of the active Co to BO2? and OH?. This work would widen the road for the preparation of nanoconfined catalysts, which has prospective application potentials for H2 production from NaBH4 hydrolysis.  相似文献   

20.
FeRu alloy (FRA) nanoparticles surface decorated Ruddlesden-Popper type layer perovskite PrSrFe1-xRuxO4+δ (RP-PSFeRu) was prepared by in-situ reduction of the cubic (Pr0.5Sr0.5)0.9Fe0.9Ru0.1O3-δ (P–PSFeRu) in H2 at 800 °C. When used as the SOFC anode material, it has excellent catalytic activity for H2 and hydrocarbon fuels. The La0.8Sr0.2Ga0.83Mg0.17O3-δ electrolyte supported SOFC single cell with RP-PSFeRu-FRA-GDC composite anode can deliver a maximum power density of 0.75 and 0.50 W cm−2 in wet H2 and C3H8 at 800 °C, respectively. Furthermore, the single cell shows a stability outputs at a constant current load of 0.5 A cm−2 in wet H2 and 0.15 A cm−2 in wet C3H8 fuels, indicating an exceptional stability and cooking resistance.  相似文献   

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