Liquid-film-type catalytic decalin dehydrogeno-aromatization for long-term storage and long-distance transportation of hydrogen

A new approach for mobile storage of hydrogen has been proposed with the use of a catalytic reaction pair of decalin dehydrogenation/naphthalene hydrogenation. With the complement of the industrialized naphthalene-hydrogenation catalysis, the other endothermic catalysis for decalin dehydrogenation was now performed at around 200°C with carbon-supported platinum-based catalysts. Under liquid-film conditions, hydrogen was evolved from decalin much more efficiently than the suspended ones due to the superheated states of dehydrogenation catalysts. It was confirmed that the catalytic conversions of decalin dehydrogeno-aromatization in the liquid-film states could surpass easily the equilibrium limit, because the conditions of suppressed reactant evaporation and reactive distillation were operative here. Exergy loss in the hydrogen storage system would be reduced tremendously by adopting this catalyst-assisted decalin/naphthalene pair as the medium of hydrogen carrier.     

Microwave effect in the dehydrogenation of tetralin and decalin with a fixed-bed reactor

This study investigates the effect of microwaves on the dehydrogenation of decalin and tetralin. The reactions were studied in a fixed-bed reactor under microwave heating (MWH), and the results were compared with those under conventional heating (electrical heating) (CH). The result of this investigation showed that under the same operating conditions, increase in the conversion of tetralin in the microwave-heated system was more than that in the conventional heated system. This demonstrated the microwave effect appeared in the dehydrogenation of tetralin. In addition, the activity and stability of the catalyst also improved under MWH. The microwave effect resulted in increase in the conversion reaction of tetralin dehydrogenation by generation of a large temperature gradient from the catalyst surface to surrounding species and the subsequent mass transfer in which both vectors have direction inverted from that of CH. Such a phenomenon induced faster molecule desorption (product species) or enhancement of species transport in the system. In addition, the contiguous strong adsorption of hydrocarbon can be reduced, leading to decrease in coke deposition. Conditionally, this benefit issue particularly resulted in increase in the reaction rate in which species transport or mass diffusion is the rate-limiting step.     

Theoretical evaluation of N-alkylcarbazoles potential in hydrogen release

Alkyl chain effect (ethyl, propyl and butyl) on the dehydrogenation mechanism of H₁₂-N-alkylcarbazoles has been investigated theoretically under various different conditions. Gibbs energies of activation of about 107.88 kcal mol^?1 have been determined as the least energy barriers among the studied dehydrogenation processes for dehydrogenation of H₁₂-N-ethylcarbazole to H₄-N-ethylcarbazole in decalin and 57.44 kcal mol^?1 for dehydrogenation of H₁₂-N-propylcarbazole to H₈-N-propylcarbazole under the experimental conditions. Kinetic and thermodynamic studies have shown that the route of H₄-N-alkylcarbazoles formation passes through a higher barrier than that of the H₈-N-alkylcarbazoles. Natural bond orbital (NBO) analysis showed a decrease in electron transfer between π_C–C and σ*_C–H at the center of the reaction. The electron density of the C–H bonds of the transition states was evaluated as evidence of hydrogen release via quantum theory of atoms in the molecules (QTAIM) procedure. Based on this analysis, a change in the nature of C–H bonds was confirmed from covalence to electrostatic interactions during the reaction.     

Hydrogen as an energy carrier: A comparative study between decalin and cyclohexane in thermally coupled membrane reactors in gas-to-liquid technology

Due to proposing hydrogen as the main energy carrier, technologies including production, storage and utilization of hydrogen have attracted increasing attention recently. Regarding this, the feasibility of decalin as a promising hydrogen carrier is investigated in this study. The performance of decalin thermally coupled membrane reactor (DCTCMR) is compared with cyclohexane thermally coupled membrane reactor (CTCMR) for Fischer-Tropsch synthesis (FTS) in gas-to-liquid (GTL) technology. Some important parameters such as hydrogen production rate, H₂ recovery yield, exothermic and endothermic temperature profiles and etc. are considered as criteria to recognize the most appropriate configuration. A comparison between the modeling results of two coupled configurations shows that DCTCMR is superior to CTCMR owing to achieving remarkably higher hydrogen production (seventeen times) compared with CTCMR. Furthermore, considerably higher H₂ recovery yield (about twelve times) and faster dehydrogenation reaction rate in DCTCMR than CTCMR proposes decalin as one of the best hydrogen carriers. This study demonstrates the superiority of DCTCMR to CTCMR owing to achieving remarkably higher hydrogen production rate, H₂ recovery yield and recognizing decalin as an appropriate hydrogen carrier.     

Carbon nanotubes-supported Pt catalysts for decalin dehydrogenation to release hydrogen: A comparison between nitrogen- and oxygen-surface modification

The effect of carbon nanotubes (CNT) surface chemistry on supported Pt catalytic performance in decalin dehydrogenation to release hydrogen was investigated through modifying CNT surface with nitrogen and oxygen functional groups. The results indicate that the mechanism of improving Pt dispersion is different for nitrogen and oxygen groups. Although oxygen groups can improve Pt dispersion, their electron donating feature inhibits the electron transfer from Pt to carbon support. DFT calculations have clarified the negative effect of oxygen group on decalin dehydrogenation in aspect of adsorption energy. Moreover, the abundant oxygen species on catalyst surface lead to a bad wettability of catalyst in non-polar reaction liquid, which significantly weaken the approaching of reactant onto catalyst. Therefore, the introduction of oxygen groups is unfavorable to the catalyst activity. In contrast, the highly dispersed Pt nanoparticles anchored by nitrogen groups may be one reason for the high activity of Pt supported on CNT modified with nitrogen groups. Furthermore, nitrogen groups promote the electron transfer from Pt to CNT, leading to lower Pt d-band and weaker naphthalene adsorption. Meanwhile little change happened on the non-polar characteristics of CNT during nitrogen doping treatment. Therefore, the introduction of nitrogen functional groups is conducive to the catalytic dehydrogenation.     

On H2 supply through liquid organic hydrides – Effect of functional groups

Liquid organic hydride (LOH) based H₂ supply systems possess an excellent potential to overcome the obstacles of upcoming ‘hydrogen economy’. However, their efficiency mainly relies on the choice of organic hydride and the dehydrogenation catalyst. In the present study, we focused on the former to strengthen the understanding of H₂ supply through LOH dehydrogenation. We investigated the role of various functionalities viz., methyl group, N heteroatom, cyclic ring and their combinations in LOH dehydrogenation. Several simple representative LOH's such as methylcyclohexane, piperidine, 4-methylpiperidine and decalin were considered and their dehydrogenation was studied over a 5 wt% Pt/ACC catalyst in a spray pulse reactor at 350 °C. The H₂ evolution rates were found to follow the trend: cyclohexane < methylcyclohexane < piperidine < 4-methylpiperidine < decalin. The inductive effects caused by these functional groups and their impact on H₂ evolution were comprehensively described. Finally, the results were compared with the benchmark reaction, cyclohexane dehydrogenation to benzene.     

Oxidation chemistry of cyclic hydrocarbons in a motored engine: Methylcyclopentane,tetralin, and decalin

This work, which parallels a recent study of cyclohexane and methylcyclohexane by the authors, concerns the oxidation chemistry of methylcyclopentane (MCP), 1,2,3,4-tetrahydronaphthalene (tetralin), and decahydronaphthalene (decalin) in a motored engine at low to intermediate temperatures. The experiment is conducted with variable compression ratio from 4 to 15 at equivalence ratio of 0.25 and fixed intake temperature. Results show dramatically different reactivity in low temperature oxidation for the three compounds. MCP and tetralin show little low temperature reaction prior to autoignition, while decalin shows significant low temperature reactivity. Detailed product analysis showed that conjugate olefins, the olefin having the identical structure with the reactant except the only CC bond, account for over 70% of the products from MCP and an even higher percentage of the products from tetralin. Tetralin oxidation under the present conditions is essentially oxidative dehydrogenation with little oxygenated cyclic compound being formed. Hydronaphthalenes with various degrees of unsaturation are detected in the products from decalin, but are not as prevalent as in the case of MCP and tetralin, because of the high selectivity toward low temperature chain branching. The ring-opening paths in decalin oxidation are discussed, suggesting that breaking the common CC bond of the two rings is more likely than opening the two rings one after the other. Methyl substitution on the ring was found to significantly promote the formation of propene relative to ethene. Reaction mechanisms are proposed to explain the major products formed from each compound.     

Differential evolution (DE) strategy for optimization of hydrogen production and utilization in a thermally coupled membrane reactor for decalin dehydrogenation and Fischer-Tropsch synthesis in GTL technology

In this study, the operating conditions of a thermally coupled membrane reactor (TCMR) in gas-to-liquid (GTL) technology are optimized via differential evolution (DE) method to maximize the hydrogen mole fraction in the endothermic side as well as the gasoline yield in the exothermic side. TCMR is designed as a double pipe reactor where highly exothermic Fischer-Tropsch synthesis (FTS) reactions in the exothermic side are coupled with decalin dehydrogenation reaction in the endothermic side. The minimum required hydrogen molar flow rate in the recycled stream is optimized to compensate a hydrogen lack at the end of the reactor in the exothermic side. The optimization results show 14.28% increase in the gasoline yield in optimized TCMR compared with conventional tubular reactor (CR). Moreover, 81.49% hydrogen is produced in the endothermic side and about 1% hydrogen is recycled to the exothermic side for utilization in FTS reactions in optimized TCMR.     

Hydrogen delivery through liquid organic hydrides: Considerations for a potential technology

Carrying hydrogen in chemically bounded form as cycloalkanes and recovery of hydrogen via a subsequent dehydrogenation reaction is a potential option for hydrogen transport and delivery. We have earlier reported a novel method for transportation and delivery of hydrogen through liquid organic hydrides (LOH) such as cycloalkanes. The candidate cycloalkanes including cyclohexane, methylcyclohexane, decalin etc. contains 6 to 8 wt% hydrogen with volume basis capacity of hydrogen storage of 60–62 kg/m³. In view of several advantages of the system such as transportation by present infrastructure of lorries, no specific temperature pressure requirement and recyclable reactants/products, the LOH definitely pose for a potential technology for hydrogen delivery. A considerable development is reported in this field regarding various aspects of the catalytic dehydrogenation of the cycloalkanes for activity, selectivity and stability. We have earlier reported an account of development in chemical hydrides. This article reports a state-of-art in LOH as hydrogen carrier related to dehydrogenation catalysts, supports, reactors, kinetics, thermodynamic aspects, potential demand of technology in field, patent literature etc.     

Simultaneous hydrogen production and utilization via coupling of Fischer-Tropsch synthesis and decalin dehydrogenation reactions in GTL technology

A thermally coupled membrane dual-type reactor (TCMDR) has been proposed for simultaneous hydrogen production and utilization in gas-to-liquid technology (GTL). Decalin dehydrogenation reaction is coupled with Fischer-Tropsch synthesis (FTS) reaction to improve the heat transfer between endothermic and exothermic sides. Furthermore, Pd-Ag and Hydroxy Sodalite membrane layers are assisted in TCMDR to improve the mass transfer between exothermic/endothermic side and permeation side. Some of the produced hydrogen via decalin dehydrogenation reaction is utilized in FTS reaction and the other is extracted and stored. The modeling results show 95% hydrogen production and 5% hydrogen utilization in FTS reactions in the exothermic reaction side of TCMDR configuration. The performance of TCMDR is compared with the one of conventional reactor (CR) and fluidized-bed membrane dual-type reactor (FMDR). Moreover, the gasoline yield in TCMDR increases about 17% and 29% in comparison with the one in FMDR and CR, respectively. The enhancement in gasoline and hydrogen yields demonstrates the superiority of TCMDR to the previous reactors.     

Synergistic effect of metal components of the low-loaded Pt-Ni-Cr/C catalyst in the bicyclohexyl dehydrogenation reaction

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)/g_Pt 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.     

Graphene–CNT composite as catalyst support for microwave-assisted hydrogen releasing from liquid organic hydride

A series of composites comprised of graphene (rGO) and carbon nanotube (CNT) with various weight ratios of them have been synthesized. The catalytic performance of the Pt catalysts supported on the rGO–CNT composites has been evaluated in the dehydrogenation of liquid organic hydride (decalin) for hydrogen releasing and compared with that of Pt/rGO and Pt/CNT catalysts. Both microwave irradiation and conventional heating methods have been adopted for the reaction. The structural and surficial features of the composites and rGO as well as CNT have been characterized by means of several techniques. The thermal behaviour of different carbon materials under microwave irradiation has been measured. The results show that there is an optimal CNT weight content in the composites leading the Pt/rGO–CNT0.17 catalyst to the best performance that cannot be achieved by the other catalysts including Pt/rGO and Pt/CNT as well. This has been ascribed to the most plentiful interface formed between rGO and CNT of a proper content, which is beneficial to the deposition of the Pt nanoparticles having the highest catalytic activity. Additionally, the strong coupling effect of carbon materials with microwave irradiation gives rise to better catalytic performance in comparison to conventional heating due to its capability to induce higher reaction temperatures. Nevertheless, the intrinsic catalytic properties of the Pt catalysts supported on different carbon materials are independent on the heating modes.     

Experimental determination of the hydrogenation/dehydrogenation - Equilibrium of the LOHC system H0/H18-dibenzyltoluene

Liquid organic hydrogen carrier (LOHC) systems store hydrogen through a catalyst-promoted exothermal hydrogenation reaction and release hydrogen through an endothermal catalytic dehydrogenation reaction. At a given pressure and temperature the amount of releasable hydrogen depends on the reaction equilibrium of the hydrogenation/dehydrogenation reaction. Thus, the equilibrium composition of a given LOHC system is one of the key parameters for the reactor and process design of hydrogen storage and release units. Currently, LOHC equilibrium data are calculated on the basis of calorimetric data of selected, pure hydrogen-lean and hydrogen-rich LOHC compounds. Yet, real reaction systems comprise a variety of isomers, their respective partially hydrogenated species as well as by-products formed during multiple hydrogenation/dehydrogenation cycles. Therefore, our study focuses on an empirical approach to describe the temperature and pressure dependency of the hydrogenation equilibrium of the LOHC system H0/H18-DBT under real life experimental conditions. Because reliable measurements of the degree of hydrogenation (DoH) play a vital role in this context, we describe in this contribution two novel methods of DoH determination for LOHC systems based on ¹³C NMR and GC-FID measurements.     

High capacity multicomponent hydrogen storage materials: Investigation of the effect of stoichiometry and decomposition conditions on the cycling behaviour of LiBH4–MgH2

LiBH₄–MgH₂ is an attractive reversible hydrogen storage system, it combines two high capacity hydrides (18.3 and 7.6 wt.%, respectively) and the concerted dehydrogenation reaction has a smaller enthalpy change than either species on its own. The latter effect leads to a destabilisation of the hydrided products and results in a lowering of the dehydrogenation temperature. In situ neutron diffraction experiments have been undertaken to characterise the mechanism of decomposition of the LiBD₄–MgD₂ system, with an emphasis on investigating the synergistic effects of the components during cycling under various conditions. This study compares the effect of stoichiometry of the multicomponent system on the cycling mechanism. Results show that LiBD₄–MgD₂ in a 2:1 molar ratio can be reversibly dehydrogenated under low pressures of hydrogen or under vacuum, contrary to earlier reports in the literature, although the reaction was only partially reversed for the 2:1 mixture decomposed under vacuum. This work shows that the reaction pathway was affected by dehydrogenation conditions, but the stoichiometry of the multicomponent system played a minor role.     

Bimetallic catalysts performance during ethanol steam reforming: Influence of support materials

Ni–Cu catalysts supported on different materials were tested in ethanol steam reforming reaction for hydrogen production. These catalysts were evaluated at reaction temperature of 400 °C under atmospheric pressure. The reagents, with a water/ethanol molar ratio equal to 10, were fed at 70 dm³/(h g_cat) (after vaporization). Analysis of the ethanol conversion, as well as evaluation and quantification of the reaction products, indicated the catalyst 10% Ni–1% Cu/Ce_0.6Zr_0.4O₂ as the most appropriate for the ethanol steam reforming under investigated reaction conditions, among the studied catalysts. During 8 h of reaction this catalyst presented an average ethanol conversion of 43%, producing a high amount of H₂ by steam reforming and by ethanol decomposition and dehydrogenation parallel reactions. Steam reforming, among the observed reactions, was quantified by the presence of carbon dioxide. About 60% of the hydrogen was produced from ethanol steam reforming and 40% from parallel reactions.     

Synthesis and characterization of sodium borohydride and a novel catalyst for its dehydrogenation

Because of the growing world population and development of technology, the growing population's desire to achieve better life standarts is rising day by day. Correspondingly, there is more consumption and the amount of energy to meet the needs of production is increasing. Increasing energy demand causes the exhaustion of fossil fuels and also enforces to investigate for new and renewable energy sources' development. Although hydrogen energy is a clean energy there are some problems such as: storage, transportation and safely usage problems. Sodium borohydride is synthesized to overcome these problems. At the same time, controlled hydrogen release during dehydrogenation and its safe usage is become more important. Studies have been continued under the different reaction conditions to reach the best hydrogen yield in optimum conditions using various catalysts in this subject.In this study sodium borohydride which can store high amount of hydrogen is synthesized from sodium amide, magnesium hydride and boron oxide by mechanochemical reaction in spex type miller. Up to the authors knowledge there is no study reported in the literature that uses sodium amide as the sodium source. Ethylene diamine was used to purify the raw product. FT-IR, XRD, TGA/DTA, particle size analysis and iodimetric analysis are performed to characterize the synthesized product. As a result of experimental studies, the highest efficiency is obtained by using 30% excess MgH₂ in the spex type miller with a 500 min mechanochemical reaction time. Purification of product by using ethylene diamine results the removal of excess MgH₂ and side product MgO to give pure NaBH₄ and consequently provides 84% yield.Hydrogen is produced from the catalytic dehydrogenation of sodium borohydride to get energy. Also a novel catalyst is synthesized for the dehydrogenation of sodium borohydride in this study. Catalyst used in dehydrogenation reaction were synthesized in economical ways. Kinetic properties of dehydrogenation reactions are developed from the datum of experiments. SEM + EDS and BET analysis are carried out to investigate the surface properties and elemental compositions of catalysts.Various reaction orders were investigated and it as found that the experimental results confirm very well with the zeroth order reaction kinetics at low temperatures (R² = 0.9921) where as they confirm with the first order reaction kinetics at high temperatures. These observations were also supported by the behavior of lnk vs 1/T line. Change in the slope of lnk vs 1/T line and consequently activation energy of the reaction indicates the change in reaction mechanism. Activation energy (E_a) values for the zeroth order reaction (reaction at low temperature) and first order reaction (at high temperatures) were determined as 32.43 kJ/mol, and 94.93 kJ/mol, respectively.Required integrated system conditions were determined by carrying out the performance measurements in our PEM fuel cell test station. The performance of the synthesized catalyst was determined by performing a set of dehydrogenation-regeneration cycles. Prepared catalyst could achieve hydrogen liberation for 2171 cycle, which equals 212 days uninterruptedly.     

Kinetic analysis of dehydrogenation reaction of cyclohexane catalyzed by Raney-Ni under multiphase reaction conditions

The kinetics of dehydrogenation reaction of cyclohexane catalyzed by Raney-Ni under “wet–dry” multiphase reaction conditions was studied in this paper. The influences of the heating temperature, feeding amount of cyclohexane and catalyst dosage on conversion of cyclohexane, apparent rate constant of reaction and retardation constant for aromatic product were investigated systematically. The experimental studies indicate that the control of the dynamic energy balance of reaction system is very important, there exists an optimal energy balance point in “wet–dry” multiphase reaction system, which depends on the combined action of heating temperature, feeding amount of cyclohexane and catalyst dosage. It was found that, with 0.5 ml cyclohexane feeding amount and 7 g catalyst dosage, at 320 °C the reaction system approached its optimal energy balance point, and the dehydrogenation conversion of cyclohexane reached its highest value of 72.7%.     

CFD analysis of Pd-Ag membrane reactor performance during ethylbenzene dehydrogenation process

In this study, the catalytic dehydrogenation of ethylbenzene (EB) to styrene production was investigated in a tubular Pd-Ag membrane reactor (MR) in presence of a commercial iron oxide catalyst. To this purpose, a 2D-axisymmetric, isothermal model based on computational fluid dynamic (CFD) method is presented to investigate the Pd-Ag MR performance during EB dehydrogenation process for styrene and hydrogen production. The proposed CFD model provides the local information of velocity, pressure and component concentration for the driving force analysis. After investigation of mesh independency of CFD model, the validation of model results was carried out by experimental data and a good agreement between model results and experimental data was achieved. It was found that the efficient removal of hydrogen in the Pd-Ag MR could significantly increase the EB conversion. Moreover, using CFD simulation runs, effects of operating parameters such as reaction temperature, pressure and gas hour space velocity (GHSV) values on the Pd-Ag MR performance with two various flow patterns was evaluated in terms of EB conversion and CO_x-free hydrogen recovery. It can be concluded that the EB conversion realized in Pd-Ag MR with countercurrent flow is higher than the ones achieved for Pd-Ag MR with cocurrent flow and also for traditional reactor (TR) during EB dehydrogenation reaction, in all the studied cases. In particular, under the optimal reaction conditions, 40% enhancement in EB conversion can be obtained in the Pd-Ag MR with countercurrent flow with respect to TR.     

Improved hydrogen release from magnesium borohydride by ZrCl4 additive

Thermal dehydrogenation of Mg(BH₄)₂ was investigated with ZrCl₄ as a catalyst in vacuum and argon gas flow conditions. The results have been compared with the thermal dehydrogenation of pure-Mg(BH₄)₂ under similar experimental conditions. Two endothermic peaks were observed for pure Mg(BH₄)₂ before the actual dehydrogenation reaction whereas; in the case of catalyzed Mg(BH₄)₂, an exothermic followed by endothermic peaks appeared. Marginal hydrogen was evolved during these low-temperature events. The actual dehydrogenations of pure-Mg(BH₄)₂ were started at 235 °C and ended at 450 °C with three clear dehydrogenation steps. However; in the case of catalyzed Mg(BH₄)₂ dehydrogenation started very early (onset 197 °C) and completed before 400 °C with merely two visible dehydrogenation steps. The lower dehydrogenation temperature of catalyzed Mg(BH₄)₂ was attributed to the reduced apparent activation energy as compared to the pure Mg(BH₄)₂.     

Synthesis of highly active and stable Pd/C catalysts toward HCOOH dehydrogenation by a simple NH3 adsorption method

Pd catalysts supported on activated carbon (Pd/C–NH₃) toward HCOOH dehydrogenation were prepared by a simple adsorption method using ammonia (NH₃) and Ar as the working gas. The results show that the TOF_initial of Pd/C–NH₃ was 459.8 h⁻¹ at 50 °C. When the reaction was carried out for 4 h, the HCOOH dehydrogenation ratio over Pd/C–NH₃ was about 81.2%, which was 1.15 and 1.13 times, respectively, as that of the as-prepared Pd/C catalyst without any treatment (Pd/C–As) and the Pd/C catalyst purchased from Sigma-Aldrich (Pd/C-CM). The total amount of H₂ and CO₂ produced by using Pd/C–NH₃ to decompose HCOOH in the third cycle was 99.4% of the gas produced by the first reaction cycle, and 1.80 and 12.60 times, respectively, as that of Pd/C–As and Pd/C-CM. The characterization results indicated that the Pd active species in Pd/C–NH₃ migrated to the outer surface of the carbon support during the reaction, and the pore volume of the carbon support became larger, which were beneficial to the reaction. These factors made Pd/C–NH₃ exhibit excellent HCOOH dehydrogenation activity and stability. NH₃ adsorption is a simple and effective method for preparing high-performance Pd/C HCOOH dehydrogenation catalysts, and has important guiding significance for the preparation of other carbon supported noble metal catalysts.