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1.
Herein, we report an efficient, environmentally friendly and stable catalyst development to hydrogen evolution from sodium borohydride hydrolysis. For this purpose, Ruthenium complex catalyst successfully fabricated via 5-Amino-2,4-dichlorophenol-3,5-ditertbutylsalisylaldimine ligand and RuCl3·H2O salt. Ru complex catalyst was identified with X-Ray Diffraction Analysis, Infrared Spectroscopy, Elemental Analysis, Transmission electron microscopy, Scanning Electron Microscope and Brunauer-Emmett-Teller Surface Area Analysis. According to the analysis results, it was confirmed that Ru complex catalyst was successfully synthesized. Ru complex was used as a catalyst in NaBH4 hydrolysis. The kinetic performance of Ru complex catalyst was evaluated at various reaction temperatures, various sodium borohydride concentration, catalyst concentration and sodium hydroxide concentration in hydrogen evolution. The apparent activation energy for the hydrolysis of sodium borohydride was determined as 25.8 kJ mol?1. With fully conversion, the promised well durability of Ru complex was achieved by the five consecutive cycles for hydrogen evolution in sodium borohydride hydrolysis The hydrogen evolution rates were 299,220 and 160,832 mL H2 gcat?1 min?1 in order of at 50 °C and 30 °C. Furthermore, the proposed mechanism of Ru complex catalyzed sodium borohydride hydrolysis was defined step by step. This study provides different insight into the rational design and utilization and catalytic effects of ruthenium complex in hydrogen evolution performance.  相似文献   

2.
Sodium borohydride exhibits great potential in the field of chemical hydrogen storage. A competent catalyst would accelerate its practical application for hydrogen utilization by enhance the efficiency of hydrogen generation from hydrolysis of sodium borohydride. Herein, a kind of highly efficient and durable synergistic Co–Ni bimetal inlaid carbon sphere catalyst (Co-NiΦC) was prepared by a co-pyrolysis method, of which the configuration of metal inlaid carbon sphere could effectively expose and anchor the active component by contrast with the capsule catalyst (Co–Ni@C) and supported catalyst (Co–Ni/C). Further, diverse cobalt-nickel contents of the Co-NiΦC catalysts were optimized to achieve the best hydrolysis performance of sodium borohydride. The structure-performance relationship of inlaid catalyst and the bimetallic synergistic mechanism were investigated by multiple characterization measurements and the density functional theory (DFT). As demonstrated, the inlaid Co-NiΦC-2 catalyst (Co/Ni molar ratio of 8/2) shows a promising catalytic activity of hydrogen generation rate up to 6364 mLH2·min?1·gmetal?1, a relative low reaction activation energy of 30.3 kJ/mol as well as robust durability where it still remains about 83.4% of its initial reaction rate after the fifth cycle. The outstanding performance of the optimized catalyst may ascribe to the high dispersion, remarkable Co–Ni synergy and high stabilization of the Co–Ni nanoparticles under the confinement effect of the inlaid metal-carbon sphere configuration. This work provides an alternative avenue for the application of efficient carbon-supported bimetal catalysts in the future.  相似文献   

3.
Cerium oxide supported 5-Amino-2,4-dichlorophenol-3,5-ditertbutylsalisylaldimine-Nickel complex for the first time was used to produce H2 from hydrolysis of sodium borohydride. Cerium oxide supported Nickel complex catalyzed hydrolysis system was studied depend on temperature, concentration of sodium hydroxide, amount of Cerium oxide supported Ni complex catalyst, concentration of Ni complex and concentration of sodium borohydride. Cerium oxide supported Ni(II) complex display highly effective catalytic activity in sodium borohydride hydrolysis reaction. The obtained Cerium oxide supported Ni(II) complex catalyst was characterized by using Fourier Transform Infrared Spectroscopy, Scanning Electron Microscope, Transmission Electron Microscope, Brunauer-Emmett-Teller Surface Area Analysis, X-Ray Diffraction Analysis techniques. The catalyst stability was tested, even the fifth recycle the catalytic activity was maintained at 100%. Additionally the proposed Cerium oxide supported-Ni (II) complex catalyzed sodium borohydride hydrolysis mechanism was determined carefully. The experimental results showed that Cerium oxide supported Ni (II) complex catalyst accelerate sodium borohydride hydrolysis with 43,392 and 19,630 mL H2 gcat?1 min?1 hydrogen production rates at 50 °C and 30 °C respectively and 20,587 kJ mol?1 activation energy.  相似文献   

4.
Porous Co–B nanoalloy is a low-cost and highly active catalyst towards the hydrolysis of sodium borohydride (NaBH4). In this study, a facile and room-temperature hydrogen bubble-assisted method was developed to prepare porous Co–B nanoalloy (Co-Bbubble) materials exhibiting high catalytic activity. The obtained materials are characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometer, transmission electron microscopy and surface area experiments. It is found that the hydrogen bubbles generated in-situ in the reaction system can act as template, which played an important role in determining the porous architecture of the final Co–B product. In the hydrolysis of sodium borohydride for hydrogen generation, the porous Co-Bbubble nanoalloy materials exhibit high catalytic activity with mass normalized rate constant of 5.31 Lhydrogen min?1 gcatalyst?1; a value which is much higher than those obtained for many other Co–B catalysts recently reported in the literature. The apparent activation energy (Ea) of the catalytic process is found to be ca. 30 kJ mol?1. It is proposed that the high catalytic performance and low cost of Co-Bbubble nanoalloy catalyst can be a promising material candidate in the hydrolysis of sodium borohydride for hydrogen production for commercial applications.  相似文献   

5.
Influence of using as catalysis, Ni-Schiff Base complex which we previously synthesized [1] used to support with amberzyme oxirane resin (A.O.R.) polymer for increasing the catalytic activity in NaBH4 hydrolysis reaction, to hydrogen generation was studied. The prepared catalyst was characterized by using SEM, XRD, BET, FT-IR analyze technique. Polymer supported Ni-Schiff Base complex catalyzed NaBH4 hydrolysis reaction was investigated depending on concentration of NaBH4, concentration of NaOH, temperature, percentage of Ni complex in total polymer supported Ni-Schiff Base complex and amount of catalyst factors. The maximum hydrogen production rate from hydrolysis of sodium borohydride with nickel-based complex catalyst compared to the pure nickel catalyst is increased from 772 mL H2·g?1 cat.·min?1 to 2240 mL H2 g?1 cat.·min?1 [1], and with supported amberzyme oxirane resin polymer this nickel based complex catalyst was increased to 13000 mL H2·g?1 cat.·min?1 at 30 °C. The activation energy of complex catalyzed NaBH4 hydrolysis reaction was found as 25.377 kJ/mol. This work also includes kinetic information for the hydrolysis of NaBH4.  相似文献   

6.
In this study, 5-amino-2, 4-dichlorophenol-3, 5-ditertbutylsalisylaldimine-Ni complex catalyst is synthesised and used as an alternative to previous studies to produce hydrogen from hydrolysis of sodium borohydride. The resulting complex catalyst is characterised by XRD, XPS, SEM, FT-IR and BET surface area analyses. Experimental works are carried out at 30 °C with 2% NaBH4, 7% NaOH and 5 mg of catalyst. The maximum hydrogen production rate from hydrolysis of sodium borohydride with nickel-based complex catalyst compared to the pure nickel catalyst is increased from 772 ml min?1g?1 to 2240 ml min?1g?1 by an increase of 190%. At the same time, the hydrolysis reaction with pure nickel catalyst is completed in 145 min while the hydrolysis reaction with nickel-based complex catalyst is completed in 50 min. The activation energy of this hydrolysis reaction was calculated as 18.16 kJ mol?1. This work also includes kinetic information for the hydrolysis of NaBH4.The reusability of the nickel-based complex catalyst used in this study has also been studied. The nickel-based complex catalyst is maintained the activity of 72% after the sixth use, compared to the first catalytic use.  相似文献   

7.
Herein we report for the first time the preparation and catalytic use of the ceria supported manganese(0) nanoparticles in hydrogen generation from the hydrolysis of sodium borohydride. They are in situ formed from the reduction of manganese(II) ions on the surface of ceria nanopowders during the catalytic hydrolysis of sodium borohydride in aqueous solution at room temperature. Manganese(0) nanoparticles are isolated from the reaction solution by centrifugation and characterized by a combination of analytical techniques. Nanoceria supported manganese(0) nanoparticles are highly active and long-lived catalysts providing a turnover frequency of 417 h?1 and 45,000 turnovers in hydrogen generation from the hydrolysis of sodium borohydride at 25.0 ± 0.1 °C. They also have high durability as they retain 55% of their initial catalytic activity after the fifth cycle of hydrolysis providing a release of 4 equivalent H2 gas per mol of sodium borohydride. The noticeable activity loss in successive runs of hydrolysis is attributed to the deactivation due to agglomeration. High activity and stability of ceria supported manganese(0) nanoparticles are ascribed to the unique nature of reducible cerium oxide. The formation of cerium(III) defects under catalytic conditions provides strong binding for the manganese(0) nanoparticles to oxide surface which makes the catalytic activity and stability favorable. Our report also includes the results of kinetic study of catalytic hydrolysis of sodium borohydride depending on the temperature, catalyst and substrate concentration.  相似文献   

8.
Amorphous Co-W-P catalysts, which were prepared on carbon cloth (CC) by electrodeposition, have been investigated as bifunctional non-noble catalysts for the hydrogen generation from alkaline NaBH4 solution and the reduction of 4-nitrophenol by NaBH4. Scanning electron microscopes (SEM), energy dispersive X-ray spectrometer (EDX), and X-ray diffraction (XRD) were used to characterize the Co-W-P/CC catalysts. The hydrogen generated catalytic properties of as-prepared catalysts with different content of P and the stability were investigated in the alkaline NaBH4 solution of 5 wt% NaBH4 and 2 wt% NaOH. The activation energy for hydrolysis of NaBH4 by the Co-W-P catalyst was also probed at different temperature, and the results show that the obtained Co-W-P/CC catalysts exhibit very low apparent active energy (Ea = 27.18 kJ mol?1). Finally, we detect the catalytic activity of Co-W-P/CC in the reduction of 4-nitrophenol for the first time, and it also presents outstanding catalytic capability with the apparent rate constant (kapp) of 11.91 × 10?3 s?1. These characteristics indicate that the Co-W-P/CC catalysts possess a potential application on both the sodium borohydride hydrolysis and reduction of 4-nitrophenol.  相似文献   

9.
Achieving high catalytic performance with the lowest possible amount of noble metal is critical for any catalytic applications. Herein, we report a controllable method of preparing low Ru loaded, N-doped porous carbon embedded with cobalt oxide species (Ru/CoOx@NPC) using core-shell metal-organic framework (MOF) as a template. The optimized catalyst exhibits a highly powerful yet stable performance of H2 production through sodium borohydride (NaBH4) hydrolysis. The Ru/CoOx@NPC catalyst shows a fast H2 generation rate (8019.5 mL min?1 gcat?1), high turnover frequency (1118.6 mol min?1 molRu?1), and reusability. The carbonized ZIF-8 core and the ZIF-67 outer shell supplies a porous carbon moiety that not only improves the conductivity and but also provides uniform distribution of the active sites. The XPS analysis indicates that there is a strong electronic interaction between Co species and Ru species. The superior catalytic performance can be attributable to the large specific surface area as well as the synergy between Co-oxide and Ru clusters.  相似文献   

10.
Sodium borohydride has been widely regarded as a promising hydrogen carrier owing to its greatly hydrogen storing capability (10.8 wt%), high weight density and excellent stability in alkaline solutions. Herein, we first design and synthesize a series of bimetallic M-Ru/C nanocomposites (including Fe–Ru/C, Co–Ru/C, Ni–Ru/C and Cu–Ru/C), via simply alloying of commercial Ru/C with nonprecious metal, for superior H2 evolution from the NaBH4 hydrolysis. The result exhibits that H2 generation is synergetically improved by alloying Ru/C with Co or Ni, while it is hindered by alloying Ru/C with Fe or Cu. Indeed, Co–Ru/C presents the highest efficient catalytic activity for H2 generation, with the TOF of 117.69 mol(H2)·molRu?1·min?1, whereas Ru/C is only 57.08 mol(H2)·molRu?1·min?1. In addition, the TOF of Co–Ru/C reaches to 436.51 mol(H2)·molRu?1·min?1 (96.7 L(H2)·gRu?1·min?1) in the presence of NaOH.  相似文献   

11.
Hydrogen generation from the hydrolysis of ammonia borane (AB) over heterogeneous catalysts is essential for practical applications. Herein, efficient hydrogen evolution from AB hydrolysis over the carbon-supported Rh nanoparticles synthesized with sodium citrate (Rh/C-SC) was achieved at 25 °C. The turnover frequency value of Rh/C-SC was 336 mol H2 (molRh min)?1, whereas that of Rh/C catalyst only yielded a value of 134 mol H2 (molRh min)?1. The improvement of the catalytic performance of Rh/C-SC catalyst could be attributed to the small Rh particles with highly active surface areas, which were prepared by using sodium citrate as the stabilizing agent. This result indicates that sodium citrate can be applied as a useful stabilizing agent for synthesizing active metal nanoparticles, thus highly promoting the practical application of AB system for fuel cells.  相似文献   

12.
Efficient and controllable release of hydrogen from solid hydrogen storage materials is a promising way to produce hydrogen safely and on-demand. The development of economical, highly active, easily recyclable catalysts is critical for practical applications, which remains a great challenging. Herein, the easily controllable and cost-effective corrosion strategy is ingeniously developed to simply prepare ultralow-content ruthenium coupled with nickel hydroxide on nickel foam (Ru–Ni–NF). After experiencing the spontaneous oxidation-reduction reactions between the reactive NF and Ru3+, ultrafine Ru nanoparticles decorated nickel hydroxide nanosheets are in situ intimately grown on porous NF networks. The optimal Ru–Ni–NF catalyst exhibits the excellent performance for catalytic hydrolysis of ammonia borane with a high turnover frequency (TOF) of 539.6 molH2 molRu?1 min?1 at 298 K and a low apparent activation energy of 36.4 kJ mol?1, due to the synergistic effect between Ru nanoparticles and nickel hydroxide nanosheets. Furthermore, the Ru–Ni–NF catalyst possesses easy separation and outstanding durability, which is superior to powdered catalysts. This study provides a facile and economical strategy for the preparation of ultralow-content noble metal supported metal foam-type catalysts for dehydrogenation of ammonia borane.  相似文献   

13.
Sodium borohydride (NaBH4) is one of promising hydrogen storage materials for practical application, and the development of high-efficient catalysts for NaBH4 hydrolysis to generate hydrogen is of critical importance. In this communication, Co3O4 hollow fiber composed of nanoparticles array was served as catalyst precursor and facilely prepared by combustion method with template of the absorbent cotton. For characterization, FE-SEM, HRTEM, EDS, XRD, FTIR and ICP were applied, respectively, and typical water-displacement method was performed to evaluate the catalytic activity. Using a solution composed of 10 wt% NaBH4 and 2 wt% NaOH, hydrogen generation rate was up to 11.12 L min?1 g?1 (25 °C), which is much higher than that of the commercial cobalt oxides and similar catalyst precursors reported in literature.  相似文献   

14.
The catalyst with high activity and durability plays a crucial role in the hydrogen generation systems for the portable fuel cell generators. In the present study, a ruthenium supported on graphite catalyst (Ru/G) for hydrogen generation from sodium borohydride (NaBH4) solution is prepared by a modified impregnation method. This is done by surface pretreatment with NH2 functionalization via silanization, followed by adsorption of Ru (III) ion onto the surface, and then reduced by a reducing agent. The obtained catalyst is characterized by transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). Very uniform Ru nanoparticles with sizes of about 10 nm are chemically bonded on the graphite surface. The hydrolysis kinetics measurements show that the concentrations of NaBH4 and NaOH all exert considerable influence on the catalytic activity of Ru/G catalyst towards the hydrolysis reaction of NaBH4. A hydrogen generation rate of 32.3 L min−1 g−1 (Ru) in a 10 wt.% NaBH4 + 5 wt.% NaOH solution has been achieved, which is comparable to other noble catalysts that have been reported.  相似文献   

15.
Ni-based catalysts were synthesized in water, methanol and ethanol solvents by chemical reduction with sodium borohydride (NaBH4). The obtained catalyst for the first time was used to catalyze the NaBH4 hydrolysis reaction with phosphoric acid and acetic acid including different concentrations. The maximum hydrogen production rates obtained in the hydrolysis reaction including 0.5 M phosphoric acid and 0.1 M acetic acid of the Ni-based catalyst prepared in ethanol solvent were 5214 and 3650 ml g?1 min?1, respectively.  相似文献   

16.
Ni–Co–B hollow nanospheres were synthesized by the galvanic replacement reaction using a Co–B amorphous alloy and a NiCl2 solution as the template and additional reagent, respectively. The Ni–Co–B hollow nanospheres that were synthesized in 60 min (Ni–Co–B-60) showed the best catalytic activity at 303 K, with a hydrogen production rate of 6400 mLhydrogenmin?1gcatalyst?1 and activation energy of 33.1 kJ/mol for the NaBH4 hydrolysis reaction. The high catalytic activity was attributed to the high surface area of the hollow structure and the electronic effect. The transfer of an electron from B to Co resulted in higher electron density at Co sites. It was also found that Ni was dispersed on the Co–B alloy surface as result of the galvanic replacement reaction. This, in turn, facilitated an efficient hydrolysis reaction to enhance the hydrogen production rate. The parameters that influenced the hydrolysis of NaBH4 over Ni–Co–B hollow nanospheres (e.g., NaOH concentration, reaction temperature, and catalyst loading) were investigated. The reusability test results show that the catalyst is active, even after the fifth run. Thus, the Ni–Co–B hollow nanospheres are a practical material for the generation of hydrogen from chemical hydrides.  相似文献   

17.
In this work, a series of shaped CoB/Ni-foam catalysts were directly synthesized by using a convenient and simple electroless plating method. Despite the low loading amount of CoB, the catalysts showed high catalytic performance in the hydrolysis of NaBH4 solution, and the maximum hydrogen generation rate reached 1930 mL min?1 (g CoB)?1 in 1 wt % NaBH4 + 5 wt % NaOH solution at 293 K. The catalysts demonstrated distinct stability, and the hydrogen generation rate was almost unchanged after 6 cycles. Furthermore, the catalysts could be easily recovered from the reaction system by a magnet. These characteristics make CoB/Ni-foam a high performance and cost effective catalyst for practical applications of hydrogen generation.  相似文献   

18.
Monometallic (Co) and bimetallic (Co-Ni and Co-Cu) oxides catalysts supported on the almond based activated carbon (AC) were prepared by the heterogeneous deposition-precipitation method. The activity of these catalysts was evaluated as a function of reaction temperature, NaOH, and NaBH4 concentration. Several analysis methods including XRD, XPS, FTIR, TEM, FESEM, ICP-OES, and BET were applied to characterize the structure of prepared samples. Well-dispersed supported bimetallic nano-catalysts with the size of particles below 20 nm were formed by using nickel and copper oxides as a promoter which was confirmed by XRD and TEM techniques. Surface composition of alloy and core-shell cobalt-nickel oxides catalysts was analyzed by ICP-OES which was in a good agreement with nominal content during catalyst preparation. The performance of bimetallic cobalt-nickel oxides catalysts indicated the synergic effect between cobalt and nickel in comparison with monometallic and bimetallic cobalt-copper samples for hydrogen production. Maximum hydrogen generation rate was measured for the supported core-shell catalyst as named Ni1/Co3/AC. The reaction rate increased with increasing the temperature of the alkaline solution as a significant parameter while other operating conditions were kept constant. The optimal values for NaOH and NaBH4 content were calculated to be 10 wt % for both variables at 30 °C. Hydrogen production rates were calculated to be 252.0, 310.8 and 658.8 mL min?1.g?1 by applying Co3/Ni1/AC, Co3-Ni1/AC (alloy) and Ni1/Co3/AC at 30 °C in 5 wt % NaBH4 and 5 wt % NaOH solutions, respectively. Obtained activation energy (50 kJ mol?1) illustrated that the suitable catalysts were synthesized for hydrogen generation. The experimental study showed that the hydrolysis of NaBH4 was a zero-order type reaction with the respect to the sodium borohydride concentration. A semi empirical kinetic model was derived at the various temperatures and NaOH concentrations.  相似文献   

19.
Carbon supported Ni@Pt nanoparticles are synthesized using sodium dodecyl sulphate (SDS) and sodium borohydride (NaBH4) as a structure-directing and reducing agents, respectively. The metal loading in synthesized nanocatalyst is 20 wt% and the ratio of Ni:Pt in the nanocatalyst is 1:1. The structural characterizations and morphologies of Ni@Pt/C nanocatalyst are investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD). The electrocatalytic activity of Ni@Pt/C catalyst toward borohydride (BH4?) oxidation in alkaline medium is studied by means of cyclic voltammetry (CV), chronopotentiometry (CP) and chronoamperometry (CA). The results show that Ni@Pt/C catalyst has superior catalytic activity toward borohydride oxidation (8825.38 mA mg Pt?1). The Membrane Electrode Assembly (MEA) used in fuel cell set-up is fabricated with catalyst-coated membrane (CCM) and catalyst coated gas diffusion medium (CCG) techniques. The effect of two MEA performances on current–voltage (I–V) and current–power density (I–P) curves in the direct borohydride-hydrogen peroxide fuel cell was investigated using Pt/C 0.5 mg cm?2 as cathode catalyst and Ni@Pt/C 1 mg cm?2 as anode catalyst. The influence of cell temperature, sodium borohydride and hydrogen peroxide concentration on the I–V and I–P is determined. The results show that the maximum power density in MEA prepared using CCM method (CCM-MEA) is 68.64 mW cm?2 at 60 °C, 1 M sodium borohydride and 2 M hydrogen peroxide (H2O2) that is higher than MEA prepared using CCG method (CCG-MEA). The impedance results show that with increasing temperature and discharging current, the overall anodic and cathodic charge transfer resistances reduce.  相似文献   

20.
The fast release of hydrogen from borohydride is highly desired for a fuel cell system. However, the generation of hydrogen from borohydride is limited by the low activity and low stability of the catalyst. Herein, a highly active catalyst is synthesized through a simple one-step chemical reduction using bacterial cellulose (BC) derived carbon as a support for the active Co–B alloy. The morphology and microstructure of the BC/Co–B nanocomposite are characterized by SEM, TEM, XRD, and BET adsorption analysis. The BC/Co–B possesses high surface area (125.31 m2 g?1) high stability and excellent catalytic activity for the hydrolysis of NaBH4. Compared with unsupported Co–B nanocomposite or commercial carbon supported Co–B, the BC/Co–B nanocomposite shows greatly improved catalytic activity for the hydrolysis of NaBH4 with a high hydrogen generation rate of 3887.1 mL min?1 g?1 at 30 °C. An activation energy of 56.37 kJ mol?1 was achieved for the hydrolysis reaction. Furthermore, the BC/Co–B demonstrated excellent stability. These results indicate that the BC/Co–B nanocomposite is a promising candidate for the hydrolysis of borohydrides.  相似文献   

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