Dehydrogenation Performance Research Articles

Non-Classical Deactivation Mechanism in a Supported Intermetallic Catalyst for Propane Dehydrogenation.

Platinum-based supported intermetallic alloys (IMAs) demonstrate exceptional performance in catalytic propane dehydrogenation (PDH) primarily because of their remarkable resistance to coke formation. However, these IMAs still encounter a significant hurdle in the form of catalyst deactivation. Understanding the complex deactivation mechanism of supported IMAs, which goes beyond conventional coke deposition, requires meticulous microscopic structural elucidation. In this study, we unravel a nonclassical deactivation mechanism over a PtZn/γ-Al2O3 PDH catalyst, dictated by the PtZn to Pt3Zn nanophase transformation accompanied with dezincification. The physical origin lies in the metal support interaction (MSI) that enables strong chemical bonding between hydroxyl groups on the support and Zn sites on the PtZn phase to selectively remove Zn species followed by the reconstruction towards Pt3Zn phase. Building on these insights, we have devised a solution to circumvent the deactivation by passivating the MSI through surface modification of γ-Al2O3 support. By exchanging protons of hydroxyl groups with potassium ions (K) on the γ-Al2O3 support, such a strategy significantly minimizes the dezincification of PtZn IMA via diminished metal-support bonding, which dramatically reduces the deactivation rate from 0.2044 to 0.0587 h-1. These findings decode the nonclassical PDH deactivation mechanism over supported IMA catalysts and elaborate a new logic for the design of high-performance IMA based PDH catalysts with long-term stability.

Enhanced microwave-catalytic performance for CO2 oxidative propane dehydrogenation by acidified and Bi-doped ZnO-based microwave catalysts

The oxidative dehydrogenation of propane by carbon dioxide (CO2-ODHP) has great potential in producing propylene. Resource utilization of CO2 will be the dominant trend in the future to mitigate environmental problems and cope with the growth in energy demand. However, simultaneously achieving high propane conversion, high propylene selectivity, and high CO2 conversion at low temperatures remains challenging. Herein, we report a novel efficient microwave catalyst (1.0-Zn4Bi1/Silicalite-1+SiC) by doping Bi on ZnO/Silicalite-1 and then acid treatment. The (1.0)-Zn4Bi1/Silicalite-1+SiC microwave catalyst exhibited 92 % C3H8 conversion, 84 % C3H6 selectivity, and 45 % CO2 conversion under microwave mode, significantly better than under the thermocatalysis (without microwave: 27 % C3H8 conversion, 92 % C3H6 selectivity, and 14 % CO2 conversion). The CO2 capture capacity was improved by adding Bi to ZnO/Silicalite-1. In addition, acid modification increased the propane and CO2 conversion by 1.9 and 1.3 times, respectively. Notably, acid treatment enriched the pore structure of the catalysts, altered surface acidity and alkalinity, and promoted C3H8 and CO2 activation and C3H6 desorption. In particular, the acid treatment enriches the state of the presence of Zn species in the catalyst. Microwave irradiation reduces the apparent activation energy of the catalytic system and accelerates the removal of coke from the catalyst surface. Microwave catalysis can activate CO2 and propane at lower temperatures than thermocatalysis.

Cr-MIL-101 derived nano Cr2O3 for highly efficient dehydrogenation of n-hexane

Nano Cr2O3 (n-Cr2O3) was prepared by the thermolysis of the mesoporous Cr-MIL-101, and its catalytic performance for n-hexane dehydrogenation was investigated and compared with Cr2O3 obtained by traditional method. It is found that dehydrogenation of n-hexane on n-Cr2O3 catalyst can produce n-hexenes and benzene efficiently, and the catalytic performance is related to the calcination temperature. The optimal n-hexane conversion can be obtained on n-Cr2O3 calcinated under 600 °C, is 40.6%, and the selectivities to n-hexenes and benzene are 20.1% and 69.3%, respectively. The conversion of n-hexane for n-Cr2O3 catalyst is decreased with calcination temperature increase, while the catalyst stability in dehydrogenation reaction is enhanced. n-Hexane conversion of p-Cr2O3-1 (obtained by precipitation method) and p-Cr2O3-2 (calcinating Cr(NO3)·9H2O directly) catalysts are very low (<7.5%), and their specific activity for n-hexane dehydrogenation are 1.5 and 1.7 g/(m2·h) respectively, lower than that of n-Cr2O3-600 (2.0 g/(m2·h)). The results of BET, XRD, TEM and FT-IR reveal that n-Cr2O3 is the nanoparticles with large specific surface area that more dehydrogenation active sites are exposed, while p-Cr2O3 is the large particles with extremely low surface area that few dehydrogenation active sites are presented. By contrast, industrial Cr2O3/Al2O3 catalyst possesses the highest specific activity of 2.4 g/(m2·h) due to the dispersion effect of Al2O3. Therefore, highly catalytic activity of n-Cr2O3 for n-hexane dehydrogenation is attributed to the unique properties of small particle, large specific surface area and more exposed active sites. This work not only explains the high dehydrogenation activity of nano-Cr2O3 derived by Cr-MIL-101, but also provides guidance for the precise design and synthesis of high-performance CrOx-based catalyst for the dehydrogenation of alkanes.

Comparative Study of PtM (M=Cu, Zn, Ga, Mn, Fe, In, Ce) Bimetals on Zincosilicate for Propane Dehydrogenation Reaction.

Silicoaluminate zeolites have relatively strong Brönsted (B) acid properties that can easily lead to deep cracking reactions, making them less favourable as carriers for propane dehydrogenation. Here, we utilise zincosilicate zeolite with less B-acid produced by the introduction of the heteroatom Zn into the framework as a carrier, followed by simultaneous ion exchange (IE) of M monometallic or PtM bimetallic (M = Cu, Zn and Ga, etc.). The optimized PtZn/Zn-4 exhibits a superior propane dehydrogenation performance over PtCu/Zn-4 and PtGa/Zn-4, which can achieve a propane conversion of about 30% in a pure propane atmosphere at 550 °C and can be operated for at least 168 h without significant deactivation. Characterization techniques such as spherical aberration corrected transmission electron microscopy, in situ X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared fourier transform spectroscopy with different gas adsorptions are used to investigate these PtM@zeolite catalysts in order to deepen the understanding of acid site identification, promoter effect and catalysis.

Optimized Dehydrogenation of Magnesium Hydride with Fe and Cu Additives

Solid state hydrogen storage with the use of MgH2 has gained widespread attention because of its good reversible storage capacity. This metal hydride however slowly releases hydrogen at high temperatures ranging between 325 – 375 oC. An important feature required of MgH2 is its ability to commence hydrogen release at a fast rate and reduced temperature. Transition metal-containing alloys/compounds having either Fe or Cu as the principal element have been used to improve the dissociation of hydrogen from MgH2. Studies involving the use of each metal in its elemental form as an additive are minimal. This study investigated the catalytic effects of elemental Fe and Cu on the hydrogen release performance of MgH2 for potential applications in transportation and power generation. It was observed that MgH2/Fe had a better dehydrogenation performance; the temperature of onset of MgH2/Fe and MgH2/Cu dehydrogenation were 205, and 215 oC which were 98 and 88 oC lower than that for as-received MgH2. The highest amount, 1.9 wt. % H2 was released by MgH2/Fe while 1.44 wt. % H2 was released by MgH2/Cu. The activation energy for dehydrogenation was reduced from 150.5 kJ/mol for as-received MgH2 to 89.8 and 79.8 kJ/mol in MgH2/Cu and MgH2/Fe respectively. It took 18.8 min for as-received MgH2 to commence dehydrogenation while that for MgH2/Fe and MgH2/Cu composites started from 12.2 and 13.4 min respectively. The in-situ formed Fe and Cu in MgH2 after milling acted as active catalytic sites for its improved dehydrogenation with MgH2/Fe behaving better.

Ultrafast Charge Transfer in a Core-shell CdS@Cu-TCPP-Pt Heterojunction for Photocatalytic Hydrogen Production Coupled with Selective Benzylamine Oxidation.

Photocatalytic selective oxidation of organic substances coupled with hydrogen production is believed to be one of the most favorable pathways to make full use of photogenerated charge carriers. However, this catalytic reaction is often discouraged due to the rapid recombination of photogenerated carriers in practical applications. In this work, a core-shell CdS@Cu-TCPP-Pt nanorod heterojunction was dexterously designed for boosting the photocatalytic dehydrogenation performance of benzylamine. The transient absorption results revealed that the photogenerated electron-holes could be effectively separated by properly matching the energy levels in CdS@Cu-TCPP. Surprisingly, Pt embedded in Cu-TCPP not only provided abundant hydrogen production active sites but also facilitated ultrafast charge transfer, which endowed CdS@Cu-TCPP-Pt with remarkable photocatalytic performances for the coproductions of N-benzylidenebenzylamine (1 mL) with a conversion of 23.48% and H2 (20.75 mmol g-1 h-1) under visible irradiation, far surpassing those of CdS and Cu-TCPP. Obviously, the present work verifies that designing and fabricating a hybrid photocatalyst with high separation efficiency of electron-hole pairs is also a significant avenue for other high-performance cooperative dual-functional photocatalytic reactions.

Ga-doped spinel-typed Co-Al catalysts for CO2-assisted ethane dehydrogenation

A series of Ga-doped spinel-typed Co-Al catalysts were prepared via one-step evaporation-induced self-assembly (EISA) method. These catalysts present promising catalytic performance for CO2-assisted ethane dehydrogenation, which can be ascribed to the conjunction effect of cobalt and gallium species. The incorporation of Ga into the structure of Co-Al spinel has been recognized for enhancing CO2 conversion via reverse water-gas shift reaction, leading to a favorable equilibrium shift towards ethylene, along with an improved catalyst stability as a result of coexisting Boudouard reaction. Through X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), NH3 and CO2 temperature-programmed desorption (TPD) characterizations, coordinatively unsaturated Co2+ and Ga3+ cations were identified as collaborative catalytic active sites, with gallium species taking the prominent role. These sites were closely associated with the formation of acid-base pairs on the catalyst surface, which were crucial for the adsorption and activation of the reactants.

Highly Dispersed Pd‐CeOx Nanoparticles in Zeolite Nanosheets for Efficient CO2‐Mediated Hydrogen Storage and Release

AbstractFormic acid (FA) dehydrogenation and CO2 hydrogenation to FA/formate represent promising methodologies for the efficient and clean storage and release of hydrogen, forming a CO2‐neutral energy cycle. Here, we report the synthesis of highly dispersed and stable bimetallic Pd‐based nanoparticles, immobilized on self‐pillared silicalite‐1 (SP‐S‐1) zeolite nanosheets using an incipient wetness co‐impregnation technique. Owing to the highly accessible active sites, effective mass transfer, exceptional hydrophilicity, and the synergistic effect of the bimetallic species, the optimized PdCe0.2/SP‐S‐1 catalyst demonstrated unparalleled catalytic performance in both FA dehydrogenation and CO2 hydrogenation to formate. Remarkably, it achieved a hydrogen generation rate of 5974 molH2 molPd−1 h−1 and a formate production rate of 536 molformate molPd−1 h−1 at 50 °C, surpassing most previously reported heterogeneous catalysts under similar conditions. Density functional theory calculations reveal that the interfacial effect between Pd and cerium oxide clusters substantially reduces the activation barriers for both reactions, thereby increasing the catalytic performance. Our research not only showcases a compelling application of zeolite nanosheet‐supported bimetallic nanocatalysts in CO2‐mediated hydrogen storage and release but also contributes valuable insights towards the development of safe, efficient, and sustainable hydrogen technologies.

Highly Dispersed Pd-CeOx Nanoparticles in Zeolite Nanosheets for Efficient CO2-Mediated Hydrogen Storage and Release.

Formic acid (FA) dehydrogenation and CO2 hydrogenation to FA/formate represent promising methodologies for the efficient and clean storage and release of hydrogen, forming a CO2-neutral energy cycle. Here, we report the synthesis of highly dispersed and stable bimetallic Pd-based nanoparticles, immobilized on self-pillared silicalite-1 (SP-S-1) zeolite nanosheets using an incipient wetness co-impregnation technique. Owing to the highly accessible active sites, effective mass transfer, exceptional hydrophilicity, and the synergistic effect of the bimetallic species, the optimized PdCe0.2/SP-S-1 catalyst demonstrated unparalleled catalytic performance in both FA dehydrogenation and CO2 hydrogenation to formate. Remarkably, it achieved a hydrogen generation rate of 5974 molH2 molPd -1 h-1 and a formate production rate of 536 molformate molPd -1 h-1 at 50 °C, surpassing most previously reported heterogeneous catalysts under similar conditions. Density functional theory calculations reveal that the interfacial effect between Pd and cerium oxide clusters substantially reduces the activation barriers for both reactions, thereby increasing the catalytic performance. Our research not only showcases a compelling application of zeolite nanosheet-supported bimetallic nanocatalysts in CO2-mediated hydrogen storage and release but also contributes valuable insights towards the development of safe, efficient, and sustainable hydrogen technologies.

CO2-mediated oxidative dehydrogenation of propane to propylene and syngas: Reaction and energy performance matrices

The performance of CO2-assisted oxidative dehydrogenation of propane to propylene is investigated. The energy performance matrices are defined as energy efficiency and exergy efficiency at both the reactor level and the overall system level. Oxidants are the main factor that dictates the performance of the dehydrogenation of propane. Oxygen is a strong oxidant which helps in promoting the endothermic dehydrogenation of propane. CO2 is considered a mild oxidant that hinders the over-oxidation of propane. The addition of CO2 promotes propane conversion but sacrifices the other performance matrices including propylene selectivity and the H2/CO ratio of the syngas. Consequently, the energy and exergy efficiencies of the reactor as well as the DHP system decrease with increasing CO2 supply. The addition of O2 has positive impacts on the energy performance matrices at a certain temperature range (from 863 K to 1273 K). However, the addition of O2 leads to an adverse impact on the propylene selectivity and H2/CO ratio of the syngas. Under the absence of O2, the DHP exhibits a propane conversion of 91% with the propylene selectivity and system exergy efficiency of 90% and 86%, respectively when the CO2/C3H8 ratio of 0.25 at 973.15 K. This work provides strong evidence that the reaction performance matrices have a strong relation to the energy performance matrices and offers a baseline for future research and optimization in the presence of O2 and CO2.

Stabilizing ultra-small bimetallic PtSn clusters within S-1 crystals for effective propane dehydrogenation with low Pt loading

It’s a great challenge for enhancing the stability over Pt-based catalysts with low Pt loading during propane dehydrogenation based upon the manipulation of ultra-small PtSn clusters and their compositions. Here, we developed a novel strategy to produce and stabilize sub-nanometer PtSn clusters even atomical dispersion within Silicalite-1 crystals via tailoring calcination atmosphere from air to argon, which could achieve a stable performance of propane dehydrogenation with only 0.15 wt% Pt loading. Argon calcination atmosphere of PtSn@Silicalite-1 significantly decreased the size of PtSn clusters, which further presented a strikingly catalytic performance with the high formation of propylene over 8.0 mol[C3H6]·g[Pt]−1·h−1 even after 3840 min at 600 °C (WHSV=760 g[C3H8]·g[Pt]−1·h−1). Hardly any deactivation was obtained over PtSn8@S-1-Ar-50 after long-term runs for 3840 min with an extremely low deactivation constant of 0.0001 h−1 so far, which was mainly derived from the outstanding stability of PtSn sub-nanometers within S-1 crystals through appropriate flow rate of argon calcination atmosphere.

Fine-tuning Pt nanoparticle and coordination for enhanced catalytic efficiency in microwave-assisted methylcyclohexane dehydrogenation over Pt/Al2O3 catalysts

The advancement of microwave-assisted catalysis technology will play a crucial role in the realms of energy conversion and catalysis. In this study, we developed a series of Pt/Al2O3-H catalysts by varying the reduction temperature and duration to control the Pt particle size, aiming to optimize the catalytic performance for microwave-assisted methylcyclohexane (MCH) dehydrogenation. Among the synthesized catalysts, Pt/Al2O3-H-400–15 emerged as the most effective, characterized by Pt particles of 1.5 nm and a Pt-Pt coordination number of 2.8. This particular catalyst demonstrated a high metal-support interaction, which significantly enhanced its activity and stability during the dehydrogenation process. Notably, it showed superior performance in MCH dehydrogenation under microwave irradiation, maintaining high stability and minimal methane formation over 626 h. The enhanced catalytic behavior under microwave irradiation is attributed to the elimination of low-temperature dead zones, which are commonly observed in traditional thermal catalysis, resulting in higher efficiency, greater activity, and reduced by-product and coke formation. This study underscores the potential of microwave-assisted catalysis as a more effective alternative to conventional thermal methods for the dehydrogenation of MCH.

Impact of various metal promoters on the propane dehydrogenation performance of cobalt-based catalysts

Large-scale exploitation of natural gas and shale gas has spurred the development of the propane dehydrogenation technology. While cobalt-based catalysts, known for their low cost and low toxicity, effectively activate C–H bonds, they are often deactivated because of coke formation. In this study, we prepared SBA-15 molecular sieves using a hydrothermal synthesis method and developed a series of Co-based catalysts supported on SBA-15 with various metal promoters (denoted Co-X/SBA-15, where X = Mn, Fe, Mg, Zn, or La) via an incipient wetness impregnation method. Characterization techniques and activity evaluation results revealed that the Co–O–Mg structure in the Co-Mg/SBA-15 catalyst stabilizes the primary Co2+ active site and hinders the reduction of the CoOx species. The incorporation of Mg enhances the total alkalinity of the catalyst, facilitating propane adsorption and propylene desorption, leading to superior activity and stability. Although the addition of La improved propylene selectivity, it did not significantly enhance propane conversion. Conversely, the introduction of Mn, Fe, and Zn into the catalyst inhibited the reaction.

Morphological regulation of Pt/CeO2 and its catalytic dehydrogenation of methylcyclohexane in fixed bed reactor

A series of Pt/CeO2 compounds with hollow spheres (Pt/CeO2–S), wires (Pt/CeO2–W), and particle (Pt/CeO2–P) morphologies were prepared and further used for catalytic liquid organic hydrogen carrier (LOHC) dehydrogenation. The exposure and distribution of different crystal faces affected the nucleation process of crystals and then formed different microscopic morphologies. Compared with Pt/CeO2–W and Pt/CeO2–P, Pt/CeO2–S showed hollow spherical structures with significantly higher oxygen vacancy concentrations and specific surface areas. These structural differences not only affected platinum (Pt) dispersion, but also affected the activity and stability of the catalyst, thus promoting methylcyclohexane (MCH) conversion. The fixed bed reaction showed that Pt/CeO2–S had excellent catalytic activity, with the MCH conversion rate at 97.7 % and hydrogen release rate of 350.50 mmol/g(Pt)/min, and it still maintained stable activity after 72 h. Under the same conditions, the MCH conversion rates for Pt/CeO2–W and Pt/CeO2–P were only 77.23 % and 32.02 %, respectively. Therefore, through the growth pattern and morphology controls of catalyst supports, this was an effective means for improving the dehydrogenation performance of LOHC.

Enhanced catalytic performance for aerobic dehydrogenation of N-heterocycles over bimetallic CoOX-CeO2 catalysts derived from Ce-based MOFs

N-heteroaromatics as one of cornerstones in chemical processes are in the limelight, so the synthesis of N-heteroaromatics have been attracted a great deal of attention. Among the elegant methods for the preparation of N-heteroaromatics, the direct oxidative dehydrogenation of saturated compounds affording N-heteroaromatics is a simple and efficient tactic. In this work, CoOX-CeO2 composites synthesized by the pyrolysis of Co/Ce-BTC MOFs as the precursor were employed as a heterogeneous catalyst for the dehydrogenation of N-heterocycles under aerobic conditions. CoOX-CeO2 composites were analyzed by diversified characterization techniques of SEM, TEM, BET, XRD, XPS, and ICP-OES. The characterization results demonstrate that abundant oxygen vacancies on the surface and the synergistic effect of CoOX-CeO2 composites remarkably enhance the catalytic performance of CoOX-CeO2 catalysts. Furthermore, the catalytic performance of CoOX-CeO2 composites remained excellent after six recycles. This catalytic system provides an alternative tool for the effective synthesis of aromatic compounds.

Green, mild, and rapid plasma synthesis of nitrogen/amino-cofunctionalized MWCNTs-supported Pd catalyst in solution for boosting formic acid dehydrogenation

Developing Pd catalysts with high catalytic activity and stability for formic acid dehydrogenation still remains a great challenge. Herein, a nitrogen/amino-cofunctionalized MWCNTs-supported Pd catalyst (Pd/MWCNTs-AP) was prepared in solution by a green, mild, and fast plasma technology. At 333 K reaction temperature, the turnover frequency (8415 h−1) over Pd/MWCNTs-AP for formic acid dehydrogenation was 1.26 and 5.16 times of those using Sigma-Aldrich Pd/C and thermal reduction prepared Pd/MWCNTs-AH, respectively. Impressively, the activity of Pd/MWCNTs-AP was not reduced during the six reaction cycles. In contrast, after the sixth cycle, the volume of gas produced using Sigma-Aldrich Pd/C decreased to 48 % of the initial volume. The results of structural characterization showed that Pd/MWCNTs-AP possessed ultrasmall-sized Pd, high Pd/C and N/C atomic ratios, and abundant –OH, facilitating the breakage of C–H and O–H bonds in formic acid to produce H and thus H2. Therefore, Pd/MWCNTs-AP exhibited excellent catalytic performance for formic acid dehydrogenation.

Y and Ni microalloying on Mg/MgH2 for enhancing the hydrogenation and dehydrogenation performance

Magnesium microalloying is an effective approach to reduce MgH2 stability and further improve the hydrogen storage performance. Here, we fabricated Mg-10Y and Mg-10Y-5Ni via mechanical alloying, and investigated the effect of Y and Ni microalloying on the hydrogenation and dehydrogenation performances. It was shown that the synergistic of Mg2NiH4/MgH2 can effectively reduce the hydrogen release energy barrier, playing an important role in thermodynamics. Besides, compared with pure Mg, a significant kinetics improvement of Mg-10Y was observed with 90% of the theoretical hydrogen storage capacity at only 5 min, which can be assigned to the "hydrogen pumping" effect of the dispersed YH2/YH3 phase. Furthermore, the introduction of Ni can effectively improve the hydrogen absorption/release of Mg-10Y, and the activation energy jumps from 117.76 to 59.97 kJ/mol H2. Note that the hydrogenation/dehydrogenation kinetics remained unchanged after 20 cycles, with a hydrogen uptake of 6.05 wt.% and release of 5.9 wt.%, suggesting that these alloys can be industrialized at a certain industrial level.

The effect of hydrothermal pretreatment on the catalytic performance of Zn/HZSM-5 catalysts for ethylene aromatization reaction

To address the issue of coking and deactivation of Zn/HZSM-5 catalysts used for lightolefins aromatization, a high-temperature hydrothermalmethod was employed for catalyst pretreatment. The catalysts were characterized using XRD, N2 physical adsorption-desorption, NH3-TPD, Py-FTIR, XPS, and TG techniques. The effect of high-temperaturehydrothermal pretreatment on the catalytic performance and stability of the catalyst was investigated using ethylene aromatization as a probe reaction. The results showed that the Zn/HZSM-5 catalyst exhibited excellent catalytic performance after48 h of high-temperature hydrothermal pretreatment. Although the conversion of ethylene slightly decreased, the catalyst lifetime was significantly extended, increasing from 72to 216 h, while the aromatics selectivity remained above 60%. It was suggested that the hydrothermal treatment enhanced the interaction between ZnO species and Brønsted acid sites, promoting the generation of ZnOH+ species. This not only suppressed the hydrogen transfer reaction but also significantly enhanced the dehydrogenation performance of the catalyst, improving the selectivity towards hydrogen. Additionally, the catalyst exhibited increased carbon capacity and reduced carbon deposition rate after hydrothermal treatment, demonstrating excellent anti-coking properties.

Suppressed Active Site Loss by Y-Doped ZnO/Silicalite-1 for Superior CO2 Oxidative Propane Dehydrogenation Performance by Microwave Catalysis

Suppressed Active Site Loss by Y-Doped ZnO/Silicalite-1 for Superior CO₂ Oxidative Propane Dehydrogenation Performance by Microwave Catalysis

Tunable Ptδ+/Pt0 sites by highly dispersed defected TiO2 for efficient catalytic methylcyclohexane dehydrogenation

Dehydrogenation reaction occurs for the hydrogen release process of liquid organic hydrogen carriers (LOHCs), the regenerative cooling of advanced aircraft, etc. But the synergistic effects of Pt active sites are still ambiguous. Herein, a series of Pt-based catalysts with tunable Pt0-Ptδ+ sites were fabricated by changing the ratio of highly dispersed defected TiO2 on MCM-41 (M41) for efficient dehydrogenation of methylcyclohexane (MCH). The characterizations indicate TiO2 nanoparticles (NPs) are highly dispersed on M41 support, and possess abundant Ti3+/oxygen vacancies. The increase of TiO2 loading amount can enhance the interaction between Pt NPs and TiO2, which increases Ptδ+/Pt0 ratio gradually. The dehydrogenation test and theoretical results confirm that the synergistic effect of Pt0 and Ptδ+ sites contributes the optimal dehydrogenation performance, in which Pt0 promotes the consecutive C–H bond cleavage and Ptδ+ significantly decreases the desorption energy barrier for H2 and toluene (TOL). Specifically, the MCH conversion (when applied for LOHCs) is ca. 88 % and the selectivity of TOL is over 99.5 % under 1.0Pt/0.5TiO2/M41, while the high MCH conversion of 90 % and TOL selectivity of more than 86 % are achieved under 1.0Pt/1.0TiO2/M41 (as regenerative cooling for hypersonic vehicle). This work provides the approach of modulating the synergistic active sites to obtain high-performance dehydrogenation catalyst.