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1.
The NECZ/12H-NECZ (N-ethylcarbazole/dodecahydro-N-ethylcarbazole) system is regarded as the most potential liquid organic hydrogen carrier. However, the low activity, selectivity of NECZ and high cost of catalysts for the dehydrogenation reaction restrict its efficiency and commercial applications. In this work, a series of bimetallic Pd-M(M = Cu, Ni)/SiO2 catalysts were prepared and employed to enhance catalytic activity and selectivity of NECZ for the 12H-NECZ dehydrogenation reaction. Pd3Ni1/SiO2 exhibited high catalytic performance with 100% conversion, 91.1% selectivity of NECZ and 5.63 wt% hydrogen release amount at 453 K, 101.325 kPa for 8 h. The TOF (turnover frequency) of Pd3Ni1/SiO2 is enhanced by 42.4% compared with Pd/SiO2. Combined with the characterization analysis, it was found that adjusting the alloying degree or the alloy phase in the PdCu and PdNi bimetallic catalysts could significantly enhance the dehydrogenation activity and selectivity, which were dependent on the component of bimetallic catalysts. This work may provide theoretical guidance for designing the efficient and low-cost bimetallic catalysts for the dehydrogenation of 12H-NECZ, which could boost the commercial applications of liquid organic hydrogen carriers.  相似文献   

2.
As the candidates for large-scale hydrogen storage, liquid organic hydrogen carriers (LOHCs) exhibit evident advantages in hydrogen storage density and convenience of storage and transportation. Among them, NECZ (N-ethylcarbazole)/12H-NECZ (dodecahydro-N-ethylcarbazole) is considered as a typical system with the lower hydrogenation/dehydrogenation temperature. However, the low dehydrogenation efficiency restrict its commercial applications. In this work, the single-layer Ti3C2Tx MXene was employed as the support to load the Pt nanoparticles for the 12H-NECZ dehydrogenation reaction. The effect of transition metals, loading amounts and morphologies of catalysts were analyzed. It was found that the 3 wt% Pt/S–Ti3C2Tx catalyst exhibited the best catalytic performance with 100% conversion, 91.55% selectivity of NECZ and 5.62 wt% hydrogen release amount at 453 K, 101.325 kPa for 7 h. The product distributions and kinetics analysis suggested that the elementary reaction from 4H-NECZ to NECZ was the rate-limiting step. The selectivity of NECZ is sensitive to the dehydrogenation temperature. Combined with the XRD, SEM, HRTEM, XPS, BET and FT-IR results, it could be indicated that the special two-dimension structure of S–Ti3C2Tx and electronic effect between Pt and S–Ti3C2Tx enhanced the dehydrogenation efficiency of 12H-NECZ. The measurements of cyclic dehydrogenation indicated that the Pt/S–Ti3C2Tx catalyst exhibited good stability after 42 h. This work brought a new strategy for the design of efficient catalysts using two-dimensional materials in the applications of the liquid organic storage hydrogen technology.  相似文献   

3.
Liquid organic hydrogen carrier (LOHC) is considered as a promising candidate for large-scale hydrogen storage. In this work, we found that Pt/TiO2 catalysts exhibited better catalytic activity and selectivity compared to Pd/TiO2 and commercial Pd/Al2O3 catalysts in the dehydrogenation of dodecahydro-N-ethylcarbazole (12H-NECZ) at 453 K. The catalytic activity of the noble metal catalysts followed the trend of Pt/TiO2 > Pd/TiO2 > Rh/TiO2 > Au/TiO2 > Ru/TiO2. Compared with the commercial Pd/Al2O3, Pt/TiO2 greatly improved the selectivity and conversion rate, the reaction time was also shortened. In addition, kinetics calculation was carried out to obtain fundamental reaction parameters. It was found that the third step of 4H-NECZ dehydrogenation to NECZ was the rate-limiting step of the entire dehydrogenation reaction for all catalysts.  相似文献   

4.
Hydrogen is a promising candidate to substitute the fossil fuels. However, the efficient hydrogen storage technologies restrict the commercial applications. Developing new catalysts with high activity and selectivity is important for the dehydrogenation reaction in N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) hydrogen storage system. In this work, a series of Pd-M/Al2O3 (M = Co, Ni and Cu) bimetallic catalysts are synthesized successfully and show good performance in the dehydrogenation reaction of 12H-NECZ than the commercial Pd/Al2O3 catalyst. The Pd1Co1/Al2O3 catalyst (Practical Pd content = 2.4136 wt%) showed the highest catalytic performance with 95.34% H2 release amount, TOF of 230.5 min−1 and 85.4% selectivity of NECZ. Combined with the characterization analysis, it can be proposed that the dehydrogenation performance of 12H-NECZ is dependent on the alloy phases, reasonable electronic structures and nanoparticle size of catalysts. The fine-tuned alloy degree and appropriate nanoparticle size of Pd1Co1/Al2O3 bring the 17.7% increase of H2 release amount and 99.5% increase of NECZ selectivity than those of Pd/Al2O3. For the bimetallic catalysts, the enhancement of selectivity of NECZ is mainly from the increase of the kinetic constant of rate-limiting step.  相似文献   

5.
Dehydrogenation of methylcyclohexane (MCH) for hydrogen transportation and delivery application was carried out over 3 wt% Pt/V2O5 and 3 wt% Pt/Y2O3 catalyst. The catalytic activity was tested using a spray-pulse mode of reactor. Effective dehydrogenation of MCH under spray-pulse mode of reactant injection was observed. In terms of hydrogen evolution rate at 60 min from start of reaction the activity of 958 mmol/g/min was obtained at temperature of 350 °C. Nearly 100% selectivity toward hydrogen was obtained. A relatively high conversion of 98% was observed with 3 wt% Pt/Y2O3 at 60 min using an advanced spray-pulse reactor system. The catalysts were characterized using x-ray diffraction pattern (XRD), CO-chemisorption metal analysis, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis.  相似文献   

6.
To improve the catalytic activity of Pt catalysts for methylcyclohexane (MCH) dehydrogenation, which is utilized for hydrogen transportation, the effects of the addition of Se on the performance of Pt/TiO2 catalysts were investigated. In Se/Pt/TiO2 catalysts, even a small amount of Se addition (Se/Pt = 0.01) improved the catalyst stability. Se was highly dispersed on the Pt/TiO2 surface, without volatilizing in a reducing atmosphere at temperatures below 450 °C, and did not form an alloy with Pt. The analysis of adsorption-desorption characteristics revealed that the addition of Se promoted the desorption of products, including the main product, toluene. Moreover, an electron donation effect from Se to Pt was observed by FT-IR measurement after the reduction. The desorption characteristic caused by the electron donation effect suppressed the deterioration of the catalyst and allowed stable catalytic activity toward the MCH dehydrogenation reaction.  相似文献   

7.
This paper describes the results of experiments on dehydrogenation of methylcyclohexane over Pt supported on metal oxides (Pt/MO) and Pt supported on perovskite (Pt/Per) catalysts. The reaction is being considered as a means for delivery of hydrogen to fueling stations in the form of more easily transportable methylcyclohexane. Among Pt/MO catalysts, the best activity as determined by the hydrogen evolution rate was observed over Pt/La2O3 catalyst at 21.1 mmol/gmet/min. Perovskite-supported catalysts exhibited relatively higher activity and selectivity, with Pt/La0.7Y0.3NiO3 giving the best performance. This Pt/Per catalyst had an activity of ca 45 mmol/gmet/min with nearly 100% selectivity towards dehydrogenation. The catalysts were characterized using XRD, CO-chemisorption and SEM-EDXA techniques. The present study reports catalysts that minimize the use of Pt and explores tailoring the properties of the perovskite structure.  相似文献   

8.
The problem of hydrogen storage in liquid organic hydrogen carriers is not only the choice of an appropriate organic substrate, but the development of a selective and active catalyst containing as low as possible noble metals. A synergistic effect of increasing conversion and selectivity in bicyclohexyl dehydrogenation to biphenyl on trimetallic Pt-Ni-Cr/C catalysts with an extremely low Pt loading (0.1 wt %), compared with bimetallic Ni-Cr/C and Pt/Ni/C systems, due to the supporting of platinum on nickel-chromium nanoparticles was established for the first time. The TOF values (mmol (H2)/gPt min) for hydrogen evolution under conditions of the reaction of bicyclohexyl dehydrogenation (320 °C, 0.1 MPa) on Pt supported onto a Ni-Cr/С composite exceed by two orders of magnitude the values found for the two-component catalysts. The maximum amount of the evolved hydrogen correlates to the selectivity of the complete dehydrogenation of bicyclohexyl into biphenyl on the Pt-Ni-Cr/C catalyst. The formation of a Ni-Cr solid substitution solution in a Ni-Cr composite deposited on a carbon carrier is shown by magnetometry, XRD, and TEM methods.  相似文献   

9.
The dehydrogenation of bicyclohexyl as a liquid organic hydrogen carrier on supported Pt/Sibunit catalysts based on the neutral and partially oxidized supports at a temperature of 320 °C and a space velocity of up to 1.5 h?1 was studied. The oxidized Sibunit is a more effective support for Pt catalyst in terms of TOF, conversion and selectivity than the neutral carrier. The 3 wt% Pt catalyst shows a higher conversion and selectivity to biphenyl than the 0.5 wt% Pt catalyst on both carriers, but TOF of 0.5 wt% Pt catalyst reaches 238 and 182 mol(H2)/(gPt * min) for 4 h of the reaction on oxidized Sibunit and neutral Sibunit, respectively. The TOF are 47 and 42 mol(H2)/(gPt * min) for the corresponding catalysts with a 3 wt% Pt loading.  相似文献   

10.
The behavior of selective hydrogen combustion (SHC) in the presence of propylene and propane changing with reaction temperature in a range of 100–600 °C has been investigated over the Pt catalysts supported on A-zeolites. The effect of Pt loading varying from 0.01 to 2 wt% on the catalytic SHC performance has been studied in the conditions with a feed gas molar composition of C3H8/C3H6/H2/O2 = 4/4/4/2 balanced with N2 and gas hourly space velocity of 15,000 h−1. The results show that for each Pt/3A catalyst having a different Pt loading there is a maximum of H2 conversion by combustion appearing between 300 and 400 °C, while the selectivity to comprehensive H2 conversion can maintain 100% when the temperature lower than 300 °C. Moreover, the Pt/3A catalyst with a Pt loading of 0.5 wt % performs better than the others at the temperatures higher than 300 °C. The maximal H2 combustion achieved over the 0.5 wt% Pt/3A catalyst is as high as 96.6% along with a selectivity of 100% at 300 °C, and a 92.4% H2 combustion with 98.5% selectivity can be obtained even if at 500 °C. The characterization of the catalysts reveals that the distribution of Pt atoms and the number of atoms in Pt clusters may be the key factors for giving rise to the good SHC performance. The influence of three types of A-zeolite supports on the Pt catalyzed SHC process has also been investigated. 3A zeolite is superior to 4A and 5A for supporting 0.5 wt% Pt catalyst in terms of both activity and selectivity. The lower C3H6 conversion on the 0.5 wt% Pt/3A catalyst compared to the 0.5 wt% Pt/5A may be ascribed to the insufficient sites for the C3H6 activation on the surface of Pt/3A due to the limitation of 3A channels inaccessible to C3H6. This contrarily brings about the better SHC performance on the 0.5 wt% Pt/3A catalyst.  相似文献   

11.
Herein, catalytic aqueous phase photoreforming of cellulose was carried out over Pt/m-TiO2 (i.e., mixed phase of anatase and rutile) and Pt/anatase catalysts to investigate the effect of the TiO2 support structure and Pt loading on the production of H2. The effect of the TiO2 support on the properties of the resulting Pt/TiO2 catalysts (such as actual Pt loading and BET surface area) was not significant. At low Pt loading of 0.16 wt.%, the TiO2 supports affected the sub-nanometre Pt structures which was confirmed by the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterisation (using CO as the probe). Conversely, the effect of TiO2 supports on larger Pt particles (on 1 wt.% catalysts) was insignificant possibly due to the reduced effect of restructuration of bigger Pt particles on the TiO2 supports. With an increase in Pt loading from 0.16 wt% to 1.00 wt.%, the normalised H2 production rate (with respect to the actual supported Pt amount and specific surface area of the catalysts) showed a decreasing trend over the two types of the catalysts, i.e., from 10.6 to 1.4 μmol h−1 m−2 mgPt−1 for Pt/m-TiO2, and from 8.5 to 1.2 μmol h−1 m−2 mgPt−1 for Pt/anatase. Specifically, large Pt particle sizes reduced the CO2/H2 production from cellulose photoreforming over both Pt/m-TiO2 and Pt/anatase catalysts, indicting an important role played by Pt particle size in photoreforming. Interestingly, in this study, the m-TiO2 supported catalysts only showed the benefits of enhanced charge separation across the phase junction in producing H2 with small Pt particles (at sub-nanometre), whilst, when large Pt particles (at around 1–2 nm) were supported, such a benefit was not significant in cellulose photoreforming. The promoting effect of small, sub-nm particles is attributed to the better capture of photoelectrons from bulk TiO2 and better activity of H+ coupling on small Pt particle. Further fundamental study on such guest-host interactions is devised to optimise Pt/TiO2 catalysts for improving H2 production from photoreforming reactions.  相似文献   

12.
Highly dispersed Pd nanoparticles immobilized in MIL-101 (Pd@MIL-101) were prepared and used for the catalytic dehydrogenation of Liquid organic hydrogen carriers (LOHC). The as-synthesized catalysts were characterized and it was found that 3 wt% of Pd@MIL-101 embodied smaller and highly dispersed Pd NPs. The catalytic activities of as-synthesized catalysts were investigated by the dehydrogenation of a representative LOHC compound, perhydro-N-propylcarbazole (12H-NPCZ). The results indicated that 3 wt% Pd@MIL-101 catalyst exhibited good catalytic activity and good reusability for the dehydrogenation of 12H-NPCZ, which is superior to that of commercial 5 wt% Pd/Al2O3 catalyst. This study demonstrates that Pd@MIL-101 is a promising dehydrogenation catalyst for the application of LOHC technology.  相似文献   

13.
The effect of the Pt loadings and particles sizes on the stability of Pt(x wt%)/Al2O3 catalysts were investigated in the partial oxidation of methane (POM) reaction. The Al2O3 support was prepared by sol-gel method and different Pt loadings, varying from 0.5 to 2.0 wt% were incorporated to alumina through the incipient wetness impregnation method. The physicochemical features of the catalysts were determined by XRD, ICP-OES, Nitrogen-sorption, UV–Visible, H2-TPR, CO-DRIFTS, SEM-EDS, XPS and HRTEM techniques. The metal dispersion was evaluated in the cyclohexane dehydrogenation reaction. Lower Pt loadings resulted in well dispersed Pto nanoparticles with an enhanced activity in cyclohexane dehydrogenation and POM reactions. With increasing Pt loading to 2.0 wt%, the Pt nanoparticles of the Pt(2.0 wt%)/Al2O3 showed a methane conversion of 63% in 24 h of time on stream, and the catalyst was very selective to H2 and CO. Based on the HRTEM, XPS and Raman spectroscopy techniques, an increment in the Pt loadings evidenced an enrichment of Pto clusters on the surface, however, no heavy carbon deposits formation was observed.  相似文献   

14.
Nitrogen/titanium dioxide (N/TiO2) visible light photocatalysts were prepared using the sol–gel method. The catalysts were characterized using transmission electron microscopy, reflective UV–visible spectroscopy, specific surface area measurements, and X-ray diffraction. The prepared catalysts were used to generate hydrogen gas through the water-splitting reaction under visible light (wavelengths greater than 400 nm). Various N/Ti addition ratios were tested, and the hydrogen generation rates were compared to determine the optimal ratio. The maximal hydrogen production rate (approximately 55 μmol h−1 g−1) was attained when the N/Ti ratio of N–TiO2 was 10. When PdO and Pt were loaded onto the N–TiO2 catalyst, the hydrogen generation rates increased to 544 and 772 μmol h−1 g−1, respectively. The highest hydrogen production rate (2460 μmol h−1 g−1) was obtained when bimetallic 0.05 wt% PdO-0.10 wt% Pt/N–TiO2 was used. After three times use the hydrogen yield of the catalyst was maintained as 83%. A possible mechanism of water splitting catalyzed by this visible light photocatalyst is proposed.  相似文献   

15.
Dehydrogenation of cyclohexane to benzene has been carried out over Ag supported on activated carbon cloth (Ag/ACC) catalysts using a spray- pulse reactor. Hydrogen evolution was studied for hydrogen storage and supply system applications. The maximum rate of hydrogen evolution rate using monometallic Ag/ACC catalysts was 6.9 mmol/gmet/min for Ag loading of 10 wt%. An enhanced hydrogen evolution was observed by adding a small amount of noble metal (1 wt% Pt, Pd, Rh) to the Ag based catalysts. A synergistic effect was observed in the case of the Pt promoted catalysts on the hydrogen production were twice as compared to 10 wt% Ag catalyst only.  相似文献   

16.
Xwt% Pt/Al2O3 (X = 1, 3, 5, 8, 10) and 5 wt% Pt-1wt% M/AlO3 (M = Pd, Rh, Re, Ru, Ir, Cr) catalysts were prepared, characterized and tested for aqueous phase reforming of pure and crude glycerol. Results show drastic dependence of catalytic performance of catalysts on both the active metal loading and the type of applied promoters. 5 wt% was the best Pt loading and PtRh/Al₂O₃ shows the best catalytic activity which has the highest hydrogen production rate (mmol/gcat h−1) and selectivity (89%) in continuous aqueous phase reforming of 10 wt% pure glycerol solution.  相似文献   

17.
This contribution investigate the effect of parameters for production of hydrogen by catalytic dehydrogenation of perhydrodibenzyltoluene (H18-DBT). The sensitivity of the dehydrogenation reaction to temperature (290–320 °C) is justified by an increase in degree of dehydrogenation (DoD) from 40 to 90% when using 1 wt % Pt/Al2O3 catalyst. However, the increase in temperature increases the hydrogen production rate and decreases the hydrogen purity by increasing the formation of by-products. In addition, the DoD of 96% is obtained when 2 wt % Pt/Al2O3 is used at 320 °C. The DoD obtained for Pd, Pt, and Pt–Pd catalysts is 11, 82 and 6%, respectively. Therefore, Pd is not a metal of choice for dehydrogenation of H18-DBT, in both monometallic and bimetallic system. The ab-initio density functional theory (DFT) calculations are consistent with this observation. Furthermore, dehydrogenation of H18-DBT followed 1st order reaction kinetics and the activation energies for 1 wt % Pt/Al2O3, 1 wt % Pd/Al2O3 and 1:1 wt % Pt–Pd/Al2O3 catalysts are: 205, 84 and 66 kJ/mol, respectively.  相似文献   

18.
A series of catalysts with different acid strengths were obtained by constructing unsaturated pentacoordinate (Al3+penta) sites in Al2O3 and loading with boron. The effects of support properties and the addition of boron on the strength and type of catalyst acid were investigated, and their influence on the dehydrogenation performance of methylcyclohexane (MCH) was discussed. In Pt-B/Al2O3-600 catalysts containing Al3+penta sites, the strongly acidic L acid sites gradually decreased and the weakly acidic [L + B] acid sites gradually increased with increasing boron loading, indicating coverage of the Al3+penta site by boron. In Pt-B/Al2O3-750 catalysts without Al3+penta sites, strongly acidic L acid sites gradually decrease with increasing boron loading and weakly acidic [L + B] acid sites remains essentially unchanged. For Pt-B/Al2O3-600 catalysts, the effect of boron on the interaction of Pt with Al2O3 is minimized when the loading of boron is between 0 and 1 wt% and the MCH dehydrogenation performance increases with the number of weak acid sites. At a boron loading of 1 wt%, the abundance of weak acid sites maintains the dispersion of Pt and allows a suitable interaction between Pt and Al2O3, thus enhancing the dehydrogenation performance of MCH.  相似文献   

19.
Mesoporous TiO2/AC, Pt/TiO2 and Pt/TiO2/AC (AC = activated carbon) nanocomposites were synthesized by functionalizing the activated carbon using acid treatment and sol–gel method. Photochemical deposition method was used for Pt loading. The nano-photocatalysts were characterized using XRD, SEM, DRS, BET, FTIR, XPS, CHN and ICP methods. The hydrogen production, under UV light irradiation in an aqueous suspension containing methanol has been studied. The effect of Pt, methanol and activated carbon were investigated. The results show that the activated carbon and Pt together improve the hydrogen production via water splitting. Also methanol acts as a good hole scavenger. Mesoporous Pt/TiO2/AC nanocomposite is the most efficient photocatalyst for hydrogen production compared to TiO2/AC, Pt/TiO2 and the commercial photocatalyst P25 under the same photoreaction conditions. Using Pt/TiO2/AC, the rate of hydrogen production is 7490 μmol (h g catal.)−1 that is about 75 times higher than that of the P25 photocatalyst.  相似文献   

20.
A new straightforward protocol for the deposition of the platinum oxide (PtO–PtO2) particles onto the TiO2 semiconductor via controllable hydrolysis of the sulfuric acid solution of Pt(IV) hydroxide was developed. The developed approach represents a simple and “green” way to prepare the supported Adams-type catalysts. In the constructed composites (PtO2·xH2O/TiO2) the Pt ionic species (hydrated PtO and PtO2 nanoparticles) weakly interact with the titania surface, but under heating the Pt–O–Ti bonds are established, resulting in the stabilization of the Pt(II) ionic state. This state dominates in the obtained catalysts PtOx/TiO2 with a low platinum loading, while at a higher Pt content the metallic Pt particles also appear. The prepared PtOx/TiO2 photocatalysts have been successfully tested in the production of hydrogen under UV light from aqueous solutions of ethanol and glucose, the products of starch biomass processing. Appreciable activity in the production of hydrogen from water/ethanol mixtures was achieved, even at a Pt content of up to 0.05%. PtOx/TiO2 photocatalysts with Pt content of 0.2–0.4 wt% have been successfully used to produce hydrogen from aqueous glucose solutions, and PtOx(0.29)/TiO2 photocatalyst has demonstrated an exceptionally high rate of H2 production per gram of platinum introduced and the quantum efficiency comparable to the highest published values.  相似文献   

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