首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 20 毫秒
1.
The concentration of photogenerated electrons on support surface has a significant impact on the photocatalytic performance of the corresponding catalyst. Herein, the CeO2-based homojunction support consisted of quantum dots/nanorods (QDs/NRs) was fabricated by two-step calcination with assistance of KCI and NaCl. Based on CeO2-QDs/NRs support, the Co-based catalyst exhibited excellent catalytic performance for photocatalytic hydrogen evolution from Ammonia Borane (NH3BH3). The catalysts exhibited the highest activity with TOF 96.15 min−1 under optimized conditions, which was significantly improved compared Co/CeO2 NRs (68.5 min−1). Detailed structure characterizations revealed that the QDs with size range from 2 to 5 nm grow on the surface of NRs, which had capacity to transfer more photogenerated electrons from the bulk to surface compared with pristine CeO2 NRs. Meanwhile, work function was upshifted from CeO2 NRs to CeO2-QDs/NRs. The synergy of two factors drove more electrons transfer from CeO2-QDs/NRs to active metal Co, accelerating the adsorption and activation of NH3BH3. In addition, the forming mechanization QDs by inducing the morphological evolution of CeO2 nanoparticles was also investigated. This work not only provides efficient photocatalyst for H2 evolution from NH3BH3 but also provides new insights into the design and preparation efficient QDs-based homojunction catalyst.  相似文献   

2.
Aimed at achieving the photo-enhanced dehydrogenation of ammonia borane (NH3BH3) in aqueous solutions, p-type cobalt (Co) doped n-type semiconductors (TiO2, WO3 and TiO2-WO3) based heterojunction structures were proposed for hydrogen production. In the present study, the Co doped n-type semiconductors such as titanium dioxide (TiO2) and tungsten oxide (WO3) were synthesized by hydrothermal synthesis to obtain heterojunction structure and characterized by XRD, SEM/EDS, TEM, FT-IR and UV–Vis techniques. The photo-enhanced catalytic hydrogen production from NH3BH3 dehydrogenation over Co doped n-type semiconductors were tested under light-irradiation (UV-light and day-light) in presence of organic and inorganic scavengers. The experimental results showed that Co @TiO2-WO3 heterojunction structure improved hydrogen production almost three times in terms of TOF values (821 h−1) compared to Co@TiO2 (292 h−1) due to photoelectrons and hole pairs increases activity. The pseudo first order kinetics based on Langmuir-Hinshelwood (L-H) kinetic model fitting revealed that apparent adsorption constant calculated in presence of Co@TiO2-WO3 with lowest value as 4.99 h−1 and 9.75 h−1 for both region, respectively.  相似文献   

3.
The hydrolysis of ammonia borane (NH3BH3) is recognized as an efficient way of hydrogen generation if it can be effectively catalyzed. In this work, a series of cobalt–molybdenum–boron (Co–Mo–B) nanoparticles (NPs) on copper (Cu) foil are introduced as catalysts for NH3BH3 hydrolysis by electroless deposition method. The influence of the depositing pH value on the catalytic property is investigated by adjusting the pH value ranged from 10.5 to 12.0. By optimizing the value to 11, the ultrafine Co–Mo–B NPs with the grain size around 4.3 nm show the best catalytic property for NH3BH3 hydrolysis. The hydrogen generation rate reaches 5818.0 mL·min−1·g−1 when the hydrolysis temperature is 298 K. The thermodynamic tests show that the lower activation energy (Ea) is estimated to be 59.3 kJ·mol−1. It can be found that the catalytic property in this work overtakes that of partial non-precious metal NPs, and is even better than some precious metal NPs previously reported. The hydrolysis reaction of NH3BH3 catalyzed by ultrafine Co–Mo–B NPs is a non-spontaneous process. In addition, the cycling ability of the ultrafine Co–Mo–B NPs is also studied and the results demonstrate that the catalyst is a recyclable one toward the hydrolysis of NH3BH3 under mild reaction conditions.  相似文献   

4.
Nowadays, there is still no suitable method to store large amounts of energy. Hydrogen can be stored physically in carbon nanotubes or chemically in the form of hydride. In this study, sodium borohydride (NaBH4) was used as the source of hydrogen. However, an inexpensive and useful catalyst (Co–Cr–B/CeO2) was synthesized using the NaBH4 reduction method and its property was characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), x-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) measurements. The optimized Co–Cr–B/CeO2 catalyst exhibited an excellent hydrogen generation rate (9182 mLgmetal−1min−1) and low activation energy (35.52 kJ mol−1). The strong catalytic performance of the Co–Cr–B/CeO2 catalyst is thought to be based on the synergistic effect between multimetallic nanoparticles and the effective charge transfer interactions between the metal and the support material.  相似文献   

5.
In this work, cobalt–tungsten–boron nanoparticles (Co–W–B) have been successfully deposited on foam Ni to manufacture thin-film catalysts by electroless plating technique and applied in hydrogen generation from ammonia borane (NH3BH3) hydrolysis. Physicochemical properties of Co–W–B nanoparticles are characterized by XRD (Powder X–ray diffraction), SEM (Scanning electron microscopy), and EDS (Energy dispersive X–ray spectroscopy). It is observed that Co–W–B showed irregular spherical structure on the surface of foam Ni substrate. An increase of depositional pH value in the preparation process leads to the change of particle size. When the pH value is equal to 11.5, as-synthesized Co–W–B exhibits the smaller particle size, which suggests that depositional pH value has directly impacted the nucleation and growth of catalysis particles. The optimized Co–W–B catalyst displays higher catalytic activity toward NH3BH3 hydrolysis with a specific rate of hydrogen generation of 12933.3 mL min?1·g?1 at room temperature. Moreover, the lower apparent activation energy of 47.3 kJ mol?1 is achieved. Compared with previously reported catalysts, the as-obtained catalytic performance is situated at the better rank. Moreover, the reusability has been investigated under the mild NH3BH3 hydrolysis conditions. It reveals that as-fabricated thin-film Co–W–B maintains excellent durability after five cycles. A possible mechanism for the released hydrogen from NH3BH3 hydrolysis using Co–W–B catalyst has been proposed.  相似文献   

6.
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   

7.
Increasing worldwide energy consumption has prompted considerable study into energy generation and energy storage systems in recent years. Chemical fuels may be produced efficiently via electrocatalytic water splitting, which uses electric and solar power. The development of efficient anodic electrocatalysts for efficient oxygen evolution reaction (OER) is a greater concern of present energy research. Cerium oxide (CeO2) are promising electrocatalysts that exhibit outstanding OER but their reduced stability obstructs the practical application. A novel strategy was established to construct an effective catalyst of heteroatom (N, B, P and S) doped CeO2 matrix were prepared. Moreover, the doping of heteroatoms into the CeO2 matrix processes the improved electronic conductivity, reactive sites, increases the electrochemical catalytic activity, which enhances the water oxidation reaction. Consequently, well-suited alkaline electrolysers were brought together for water oxidation to ideal OER electrocatalytic activity. The OER activity of the electrocatalysts follows the order of S–CeO2 (190 mV@10 mA cm−2), N– CeO2 (220 mV @10 mA cm−2), P– CeO2 (230 mV @10 mA cm−2), B–CeO2 (250 mV @10 mA cm−2) and CeO2 (260 mV @10 mA cm−2) in 1 M of KOH. From the kinetics analysis, Tafel slope value achieved for catalysts CeO2, B–CeO2, P–CeO2, N–CeO2 and S–CeO2 are 142 mV dec−1,121 mV dec−1, 102 mV dec−1, 98 mV dec−1 and 83 mV dec−1 respectively. These results validate that the S–CeO2 electrode is prominent for OER performance with the requirement of cell voltage of 1.42 V at 10 mA cm−2 current density. In addition, sulphur doped CeO2 relatively have excellent stability through chrono-potentiometric analysis lasting for 20 h. Although the heteroatoms doped CeO2 is acts as anode material, the preparation method is widespread, which will reduce the synthesis cost and streamline the preparation of electrode for OER. This research effort delivers a complete advantage for the development of robust, environmentally friendly and highly dynamic electrocatalysts for OER activity.  相似文献   

8.
Hydrogen production from water electrolysis with catalysts is a simple, effective, and environmentally friendly way. However, the slow kinetics of the oxygen evolution reaction (OER) directly affects the catalytic efficiency of water electrolysis during hydrogen production. While the high cost of noble metal catalysts limits their engineering applications. Therefore, there is an urgent need to develop an economical and abundant catalyst with efficient OER performance to replace noble metal catalysts to reduce costs. In this work, we propose a method for the preparation of composite catalytic electrodes by magnetically induced jet electrodeposition. Ni–Co–CeO2/Ni composite electrodes with a unique micro-nano structure and a large specific surface area were rapidly obtained through magnetically induced adsorption of nano-mixed particles. It was found that the Ni–Co–CeO2/Ni composite electrode deposited by magnetically induced electrodeposition exhibited a lower overpotential of 301 mV@10 mA/cm2 when the nano-mixed particle concentration was 2 g/L, and the corresponding Tafel slope was as low as 43.72 mV/dec. The key parameters of overpotential and Tafel slope reach or even outperform the best noble metal electrode in the industry, indicating that the Ni–Co–CeO2/Ni composite electrode had excellent OER catalytic performance. The study demonstrates that magnetically induced jet electrodeposition provides a new method for the preparation of catalytic electrodes, which has important applications in the electrolysis of water for hydrogen production.  相似文献   

9.
Electrospun Ni and Cu metal oxide catalysts are successfully synthesized through electrospinning and conventional sol-gel methods to show advantages of electrospinning on catalytic performance in ammonia borane (NH3BH3) methanolysis for hydrogen production. An experimental assessment is presented by the characterization of interior and exterior properties of all catalysts and their catalytic activity towards NH3BH3 methanolysis. The systematic studies are performed in order to figure out of kinetic interpretation. Catalytic NH3BH3 methanolysis reactions are carried out at different catalyst amounts (5–15 mg), initial NH3BH3 concentrations (0.36–6.0 M) and temperatures (20–50 °C). Thanks to the higher pore volume/SBET ratio, fiber type nanostructured Cu oxide catalyst exhibits the highest catalytic activity compared with sol-gel prepared ones. The results of kinetic studies show that the fiber type Cu oxide catalyst catalyzed methanolysis of NH3BH3 and follows the first order reaction kinetic model with 35 kJ mol−1 activation energy value.  相似文献   

10.
《Journal of power sources》2006,163(1):364-370
We have studied catalytic performance of supported non-noble metals for hydrogen generation from aqueous NH3BH3 at room temperature. Among the tested non-noble metals, supported Co, Ni and Cu are the most catalytically active, with which hydrogen is released with an almost stoichiometric amount from aqueous NH3BH3, whereas supported Fe is catalytically inactive for this reaction. Support effects on the catalytic activity have been investigated by testing the hydrogen generation reaction in the presence of Co supported on γ-Al2O3, SiO2 and C and it is found that the Co/C catalyst has higher activity. Activation energy for hydrogen generation from aqueous NH3BH3 in the presence of Co/γ-Al2O3 was measured to be 62 kJ mol−1; this may correspond to the step of BN bond breaking. Particle size, surface morphology and surface area of the supported metal catalysts were examined by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray (EDX) and BET experiments. It is found that with decreasing the particle size the activity of the supported catalyst is increased. The low-cost and high-performance supported non-noble metal catalysts may have high potential to find its application to the hydrogen generation for portable fuel cells.  相似文献   

11.
《能源学会志》2020,93(4):1511-1518
WO3/CeO2 catalysts with different support morphologies were fabricated by incipient wetness technique and applied to selective catalytic reduction of NO by NH3 (NH3-SCR). WO3/CeO2 rod (WCR) displayed higher catalytic activity and resistance to SO2 and H2O compared with WO3/CeO2 polyhedron (WCP) and WO3/CeO2 cube (WCC). N2-BET, XRD, Raman, H2-TPR, TEM, HRTEM, NH3-TPD, XPS and in situ DRIFTS were conducted to investigate the physicochemical properties of the catalysts and the adsorption of NH3 and NOx species on the catalytic surface. These characterization results demonstrated that the larger BET surface area, the smaller CeO2 particle size, the higher surface acidity, the more oxygen defects, the better redox performance, and the higher Ce3+ and Oα ratios of the catalysts played critical functions in obtaining more outstanding NH3-SCR catalytic performance. All of these characterization results were also closely related to the CeO2 morphology. The results of the in situ DRIFTS showed that the WCR had the highest intensities of the adsorbed NOx and NH3 species among these three catalysts. The reactions between adsorbed species attributed to NOx and NH3 on the catalyst surface can also be a key factor in the NH3-SCR catalytic performance enhancement.  相似文献   

12.
The development of inexpensive and high performing catalysts for ammonia borane (NH3BH3) hydrolysis is crucial for hydrogen production. In our research, a high-performance plate-like Cu2O–CoO nanocomposite catalyst for NH3BH3 hydrolysis has been developed for the first time. In the hydrolytic reaction, both Cu2O and CoO are separately inactive, while Cu2O–CoO nanoplates show a high turnover frequency of 34.1 molhydrogen min−1 molcat−1, which is attributed to the synergistic effect between Cu2O and CoO. It is interesting to discover that the induction time for the hydrolytic reaction is reduced to null when a small amount of Cu2O is introduced into CoO. The reaction kinetics of NH3BH3 hydrolysis catalyzed by Cu2O–CoO is also investigated. This work may provide other researchers some valuable insights into designing inexpensive and synergistic catalysts with enhanced catalytic activity for NH3BH3 hydrolysis for hydrogen production.  相似文献   

13.
Electrospun nanofibers are prepared through electrospinning followed by post-treatment and preferred to use in catalytic applications. The electrospinning provides advantages for active catalysts design based on activity profiles and features of catalyst. In the present study, we fabricated nano-crystalline cobalt oxide (Co3O4) catalyst by electrospinning technique followed by thermal conditioning. Polyacrylonitrile (PAN) based Co as-spun mats (Co/NMs) with homogeneous diameter were prepared by electrospinnig process under several conditions as applied voltage (15–25 kV), working distance (5–7.5 cm) with the feed rate of 1 ml min−1. The calcination process as a post-treatment was applied at different temperatures (232 °C, 289 °C and 450 °C) to obtain electrospun nano-crystalline Co3O4 catalyst. Co/NMs catalysts were characterized by XRD, SEM, TEM, XPS, FT-IR, TG/DTG, and ICP-MS techniques. The parametrically study was performed for evaluating the hydrogen production activity of catalyst from sodium borohydride (NaBH4, SBH) and its originated compounds as ammonia borane (NH3BH3, AB) and methyl-amine borane (CH3NH2BH3, MeAB). The relation between the internal-external properties and catalytic activities of catalysts for hydrogen production was investigated. The beadless Co/NMs-1 catalyst with homogeneous diameter was obtained under electrospinnig process conditions at 15 kV applied voltage and 7.5 cm working distance. All catalysts showed activity for hydrogen production, also the significant effect of post treatment process was observed on the catalytic activity as given order: Co/NMs-1450 > Co/NMs-1289 > Co/NMs-1 > Co/NMs-1232. Furthermore, mesoporous Co3O4 cubic crystals (26 nm) in fibrous architecture was prepared by 450 °C-post-treatment. Hydrogen production rates were recorded at 60 °C as 2.08, 2.20, and 6.39 l H2.gcat−1min−1 for NaBH4, CH3NH2BH3, and NH3BH3, respectively.  相似文献   

14.
15.
Epoxy-activated acrylic particulate polymer, namely Eupergit CM, supported Co–Fe–Ru–B catalyst (EP/Co–Fe–Ru–B) for the first time was used to produce H2 from hydrolysis of NH3BH3. The EP/Co–Fe–Ru–B showed very effective performance in the production of H2 from the hydrolysis of NH3BH3. Various techniques such as XRD, SEM-EDS, ICP-OES, and TEM have been used to characterize these catalysts. The parameters on the hydrolysis reaction of NH3BH3 such as the effect of metal amount, the effect of Ru percentage, the effect of NH3BH3 concentration, the effect of NaOH concentration, the amount of catalyst, temperature, and catalyst durability were investigated in detail. Eupergit CM based polymer support and Ru particles have been found to be highly effective in H2 production reactions. The hydrogen production rate (HGR) of the EP/Co–Fe–Ru–B catalyst was found to be 36,978 mL/min/gcat, which was quite good compared to the values reported in the literature. In addition, the activation energy (Ea) of the polymer-supported Co–Fe–Ru–B catalyst was determined as 24.91 kJ/mol.  相似文献   

16.
This study presents a novel and highly efficient CeO2-based type of additives to improve the performance of PEM fuel cells. Cerium(IV) oxide (CeO2) nanorods and CeO2 nanorod decorated nitrogen-doped reduced graphene oxide (NrGO) (CeO2/NrGO) were synthesized and utilized to enhance the ORR performance of PEMFCs. With a low energy transition between Ce+3 to Ce+4 and its high catalytic activity, CeO2 could promote O2 reduction. The structural properties of CeO2 nanorods and the CeO2/NrGO composite were investigated using XRD, RAMAN, SEM, TEM, TGA, BET, and XPS. The synthesized CeO2 nanorods and CeO2/NrGO composite were mixed with a low platinum loading (0.09 mgPt.cm−1), and ex-situ electrochemical characterizations were performed (CV and LSV) to evaluate their catalytic activities. Fuel cell performance tests and in-situ impedance analyses were also conducted to confirm the electrochemical results. Compared to commercial Pt/C-based MEA (269 mW.cm−2), the addition of both CeO2 nanorods (382 mW.cm−2) and CeO2/NrGO (389 mW.cm−2) to the catalyst layer showed a significant enhancement in fuel cell performance, due to the unique oxygen buffer ability of the synthesized additives.  相似文献   

17.
The catalytic dehydrogenation of ammonia borane (NH3BH3, AB) molecule is most frequently employed by metal catalysts, but a reliable dehydrogenation mechanism in molecular level has yet to be fully illuminated. Herein, adopting the density functional theory (DFT) method, the dehydrogenation mechanism and performance of NH3BH3 under the transition metal catalysts (Cu/MgO, Co/MgO, CuCo/MgO) were studied. The calculated results show that the dehydrogenation mechanism of AB refers to stepwise dehydrogenation mechanism: AB is adsorbed in the transition metal catalysts firstly, then one H(N) atom transferred to H(B) of ―BH3 and to form H2 molecule via the broken of B―H and N―H bond, finally, H2 molecule desorption from the catalyst complexes. Among the transition metal catalysts, CuCo/MgO have the perfect catalytic activity in dehydrogenation reaction of NH3BH3, its barrier energy of the feasible pathway (path A) is 22.26 kcal/mol, which is lower than the barrier energy of AB‐Cu/MgO(28.13 kcal/mol), AB‐Co/MgO(27.46 kcal/mol), and the results of thermogravimetric analysis further verified the reasonability of DFT calculational results. Besides, partial density of states calculational results show the electron orbital hybridization of Cu, Co atom may account for the excellent catalytic performance of CuCo/MgO(100) compared with the Cu/MgO(100) and Co/MgO(100) in dehydrogenation process of AB.  相似文献   

18.
《能源学会志》2020,93(4):1332-1340
The effect of Na2O and NaCl on CeO2–TiO2 catalyst for the selective catalytic reduction of NO with NH3 was investigated with BET, XRD, XPS, NH3-TPD, H2-TPR, in-situ DRIFT and catalytic activity measurements. The results showed that both Na species could deactivate the CeO2–TiO2 catalyst and Na2O had a stronger effect than NaCl. The more serious deactivation by Na2O could be ascribed to smaller surface area, fewer surface Ce3+ and chemical adsorbed oxygen, lower surface acidity, and worse reducibility. The introduction of NaCl and Na2O facilitated the formation of new surface NOx adspecies, but were inactive in NH3-SCR reaction. The adsorption of NH3 were inhibited. The NH3-SCR reaction over the CeO2–TiO2 catalyst was governed by both E-R and L-H mechanisms. The introduction of NaCl and Na2O didn't change the NH3-SCR reaction mechanisms.  相似文献   

19.
In this study, we report the results of a kinetic study on the hydrogen (H2) generation from the hydrolysis of ammonia borane (NH3BH3) catalyzed by Platinum supported on carbon nanotube-graphene hybrid material (Pt/CNT-G). Synthesized catalyst was characterized by TGA, XRD, CP-OES, TEM and SEM-EDX techniques. Characterization studies have shown that the CNT-G hybrid support material provides desired distribution of the Pt particles on the support material. The effect of various parameters such as catalyst loading, reaction temperature, effect of NaOH and the effect of NH3BH3 concentration are also determined. Experimental results showed that the Pt/CNT-G catalyst exhibited high catalytic activity on NH3BH3 hydrolysis reaction to release H2. It has been found that Pt/CNT-G catalyst shows low activation energy of 35.34 kJ mol−1 for hydrolysis reaction of NH3BH3. Pt/CNT-G catalyst also exhibited high catalytic activity with turnover frequency (TOF) of 135 (molH2/molcat.min). Therefore, the synthesized Pt/CNT-G catalyst is a potential candidate for enhanced H2 generation through NH3BH3 hydrolysis.  相似文献   

20.
In this work, many kinds of V doped Co(OH)2 electrodes were in situ synthesized on Ni foam by a one-step typical hydrothermal process. It is worth noting that the phase transition composition of the V doped Co(OH)2 material can be modulated by the difference of the amount of the V introduced. Different crystal phase compositions show different water oxidation activities. It is worth noting that the V2–Co(OH)2/NF electrode shows better oxygen evolution performance (Overpotential of 320 mV@50 mA cm−2) compared with Co(OH)2/NF (450 mV@50 mA cm−2), V1–Co(OH)2/NF (340 mV@50 mA cm−2) and V3–Co(OH)2/NF (350 mV@50 mA cm−2) electrodes. The experimental results show that not all doping can improve the electrochemistry performance of electrodes, such as the oxidation of urea. Density functional theory calculation further proves that the doping of the V is favorable to the adsorption of water and inhibits the adsorption of urea. This study provides a new idea for the development of efficient overall water splitting catalysts.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号