Propene Formation Research Articles

Sulfur-doped Pt/C catalyst for propane dehydrogenation with improved atomic utilization and stability

Atomically well-dispersed platinum catalysts play a vital role in various chemical processes such as direct dehydrogenation of propane (PDH), due to their high performance originated from high atom utilization. However, these catalysts suffer from complex preparation methods, and preparing atomically dispersed Pt-based catalysts with feasible methods remains challenging. Herein, we report a convenient method to prepare efficient atomically dispersed Pt/C catalysts for PDH by sulfur doping into the carbon support by simple cyclohexane impregnation method. The prepared atomically well-dispersed catalysts possess strong interactions between Pt and carbon support, which led to improved exposure of active sites and higher propylene formation rate compared to that without sulfur doping. Sintering of the Pt species was also inhibited and stability was improved by 47%. Propylene selectivity also showed a positive correlation with the amount of sulfur doping. The propane conversion first increased and then decreased, which was due to the loss of sulfur during the reaction that caused the agglomeration of Pt and the evolution of structure. It was found that the maximum catalytic activity appeared with Pt clusters of ∼ 0.71 nm with an average Pt-Pt coordination number of 3.1 and Pt-Pt bond distance of 3.09 Å.

Tricoordinated Single-Atom Cobalt in Zeolite Boosting Propane Dehydrogenation.

Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.

The enhancing effect of Co2+ on propane non-oxidative dehydrogenation over supported Co/ZrO2 catalysts

Due to the increased production of shale gas containing propane, the share of non-oxidative propane dehydrogenation (PDH) in the large-scale production of propene is expected to continue to grow. There are, however, some ecofriendly and cost shortcomings associated with the currently applied Cr- or Pt-containing catalysts. Against this background, we present here Co/ZrO2 alternatives and reveal the fundamentals affecting their activity, which can be used for purposeful catalyst design. Co2+ species homogeneously distributed within the lattice of ZrO2 significantly increase the activity of coordinatively unsaturated Zr4+ for the PDH reaction. The increase is caused by accelerating both the cleavage of CH bonds in propane and the recombination of surface H species, with the latter reaction being the rate-limiting step. The best-performing catalyst outperformed an analogue of commercial K-CrOx/Al2O3 in terms of the rate of propene formation and demonstrated durable performance over a series of 10 PDH/regeneration cycles under industrially relevant conditions. It also outperformed most previously developed Co-containing catalysts in terms of propene productivity. The space–time yield of propene formation achieved at 57 % equilibrium propane conversion at 550 °C was 0.71 kg·h−1·kgcat-1.

Rational design of structured Co3O4@silicalite-1/SiC foam catalyst for microwave-assisted highly efficient conversion of bio-isopropanol to green propylene

Globally, there is an increasing demand for propylene. Propylene can be produced through the dehydration of bio-isopropanol, which is derived from the fermentation of renewable feedstock. In this study, to enhance the efficiency of the bio-isopropanol-to-propylene (BITP) process, a microwave-sensitive Co3O4@S1/SiC foam catalyst was designed. The performance of the foam catalyst was evaluated across a range of temperatures (50–250 °C) and different heating modes. Investigations revealed that microwave irradiation resulted in a selective formation of propylene of 98.8 %, markedly surpassing the 72.7 % yield achieved with Co3O4@S1/SiC pellets. The exceptional efficiency of the Co3O4@S1/SiC foam in the bio-isopropanol-to-propylene process is predominantly attributable to the enhanced mass and heat transfer facilitated by the well-structured, microwave-sensitive foam SiC. Under microwave irradiation at lower temperatures, this foam catalyst exhibits significantly enhanced efficiency, achieving a 90 % conversion rate at 121 °C, in contrast to the 184 °C required by conventional heating methods to attain a similar rate. Moreover, the synergistic effect between Co3O4 and the second support S1 is crucial, enhancing not only the microwave absorption capacity but also the efficiency of the bio-isopropanol dehydration process.

Pyrolysis experiments of model compounds to explore carbon isotope fractionation in propane from natural gas

Investigating the mechanisms that determine the bulk and position-specific carbon isotopic distributions of propane in natural gas will help elucidate its formation and evolution. We used octadecane and squalane as model compounds that give simple precursors for gas production in gold-tube isothermal pyrolysis experiments to study the variations in intermolecular and intramolecular distributions of isotopes in the generated gaseous hydrocarbons. The δ13C values of the products and inverses of their carbon numbers (1/n where n = C1–C5) showed a negative linear relationship versus maturity, indicating that they formed by homolytic cleavage of C–C bonds and that the precursors showed homogeneous distributions of carbon isotopes. However, the significant difference in the kinetic isotopic effects (KIEs) of the gas generated by cracking of two model compounds under the same experimental conditions is not readily explained by single homolytic bond cleavage. The results indicate that besides the KIE of C–C bond cleavage, the bulk and position-specific carbon isotopic compositions of propane are related to the chemical and isotopic structures of the precursors and the propane transformation ratio. Based on the sites of C–C bond cleavage, two isotopic fractionation patterns (i.e., normal propyl and isopropyl models) may explain the bulk and position-specific carbon isotopic distributions of the generated propane. According to the propyl model, propane originates from (normal) propyl structures (CH3CH2CH2*) in the precursor via C–C bond cleavage at a terminal site of a propyl group, while the isopropyl model involves propane derived from isopropyl structures (CH3CH*CH3) in the precursor, with C–C bond cleavage at the central site. Simulations show that these distributions for propane cracked from octadecane closely follow the propyl model, whereas propane generated from squalane showed mixed contributions from both models, and its bulk and position-specific carbon isotopic distributions depend on the proportions of propyl and isopropyl structures in the precursors. Variations of propane’s position-specific carbon isotopic distributions during the main stage of propane generation indicate that free radical reactions are the main pathway for thermogenic propane formation, resulting in similar KIEs for propane terminal and central carbons. Therefore, the position-specific carbon isotopic distribution of propane can provide evidence of its formation mechanism and shows potential for revealing the origin and evolution of natural gas.

Vapor-phase deoxydehydration of 1,2-propanediol to form propylene over Cu-loaded H3PO4/SiO2-Al2O3 catalyst

Vapor-phase catalytic deoxydehydration of 1,2-propanediol (1,2-PDO) to form propylene was performed over various metal-loaded catalysts in an H2 flow at an ambient pressure. Cu-based catalysts exhibited a relatively high activity for the formation of propylene, while other metal-based catalysts, such as Pt-, Ru-, Rh-, Ni-, and Co-loaded SiO2-Al2O3, primarily produced C-C bond cleavage products. Cu-loaded H3PO4/SiO2-Al2O3 catalysts showed the best catalytic performance, and the catalyst with a Cu and H3PO4 loading of 8 and 10 wt%, respectively, could provide a propylene selectivity of 95.0% with a complete conversion of 1,2-PDO at 280 °C. The Cu-loaded H3PO4/SiO2-Al2O3 catalysts primarily contained Lewis acid sites, and the Cu particles were well dispersed on the catalyst surface with an averaged particle size of 3.1 nm. It is proposed that the vapor-phase deoxydehydration of 1,2-PDO to propylene undergoes multi-step reactions with propanal and 1-propanol as the reaction intermediates.

Theoretical insights into formation of ethylene, propylene and butylene in Co2C (020) catalyzed FTO process

Fischer–Tropsch Synthesis to lower olefins (FTO) is an important non-petroleum route to produce lower olefins. Nanoprisms Co2C has been discovered as a promising FTO catalyst possessing high selectivity to olefins and low CH4 selectivity for its exposing (020) facet. Density Functional Theory (DFT) was used to understand the reason for inhibiting methane formation, the chain growth mechanism and dominant formation pathway of three main low olefins. The results show that the activation energy for CH2* to couple with CH* (0.51 eV) was much lower than that for further hydrogenation to form CH3* (0.66 eV), which was the key species to produce methane. Therefore, the mechanism inhibiting methane formation was Co2C(020) promoting CH2*-CH*coupling rather CH2* hydrogen. Moreover, it can be predict that the carbon chain would not grow too long, because the coupling activation energy for the C1-C1 coupling, C1-C2 coupling, C1-C3 coupling were 0.51 eV, 0.54 eV and 0.69 eV, respectively. At last, it can be predicted that propylene was the easiest to produce, followed by ethylene and butylene, because their barrier energy were 1.58 eV, 1.64 eV and 2.12 eV, respectively.

Steric Perturbation of the Grob-like Final Step of Ethylene-Forming Enzyme Enables 3-Hydroxypropionate and Propylene Production.

Ethylene-forming enzyme (EFE) is an iron(II)-dependent dioxygenase that fragments 2-oxoglutarate (2OG) to ethylene (from C3 and C4) and 3 equivs of carbon dioxide (from C1, C2, and C5). This major ethylene-forming pathway requires l-arginine as the effector and competes with a minor pathway that merely decarboxylates 2OG to succinate as it oxidatively fragments l-arginine. We previously proposed that ethylene forms in a polar-concerted (Grob-like) fragmentation of a (2-carboxyethyl)carbonatoiron(II) intermediate, formed by the coupling of a C3-C5-derived propion-3-yl radical to a C1-derived carbonate coordinated to the Fe(III) cofactor. Replacement of one or both C4 hydrogens of 2OG by fluorine, methyl, or hydroxyl favored the elimination products 2-(F1-2/Me/OH)-3-hydroxypropionate and CO2 over the expected olefin or carbonyl products, implying strict stereoelectronic requirements in the final step, as is known for Grob fragmentations. Here, we substituted active-site residues expected to interact sterically with the proposed Grob intermediate, aiming to disrupt or enable the antiperiplanar disposition of the carboxylate electrofuge and carbonate nucleofuge required for concerted fragmentation. The bulk-increasing A198L substitution barely affects the first partition between the major and minor pathways but then, as intended, markedly diminishes ethylene production in favor of 3-hydroxypropionate. Conversely, the bulk-diminishing L206V substitution enables propylene formation from (4R)-methyl-2OG, presumably by allowing the otherwise sterically disfavored antiperiplanar conformation of the Grob intermediate bearing the extra methyl group. The results provide additional evidence for a polar-concerted ethylene-yielding step and thus for the proposed radical-polar crossover via substrate-radical coupling to the Fe(III)-coordinated carbonate.

Structure evolution of porous alumina during aging process and its support effect on PtSn/Al2O3 catalyzed propane dehydrogenation

Precise control of porous alumina microstructures is always challenging due to the diversity and complexity of the growth process-related alumina crystalline phase and surface properties. In this work, we established a bottom-up synthesis route with a combination of rapid precipitation at high supersaturation and high-temperature aging in terms of enhancing particle aggregation kinetics. Surprisingly, we discovered that there were two distinct growth stages of alumina precursor (ammonium aluminum carbonate hydroxide) during the aging procedure, that is, oriented attachment at the early stage of crystallization and subsequent Oswald ripening. High-temperature aging can effectively strengthen the aggregation kinetics between the particles and produce large mesoporous (∼16 nm) and a remarkable number of defect sites with the exposure of up to 14 % unsaturated pentacoordinate aluminum ions. Owing to the presence of strong metal-support interactions, the alumina-supported PtSn catalyst exhibited excellent catalytic activity in the propane dehydrogenation reaction with propylene formation with 99 % selectivity and superior stability with a low deactivation rate of 0.007 h−1 over 24 h. These results suggested that it was feasible and instructive to achieve precise control of the structure and surface properties of alumina by manipulating the aggregation process of the initial particles during the aging stage.

Identifying the active site and structure–activity relationship in propane dehydrogenation over Ga2O3/ZrO2 catalysts

ZrO2-based catalysts have attracted extensive attention in propane dehydrogenation (PDH) owing to their environmental compatibility, low costs, and superior catalytic performance. However, the structure–activity relationship and mechanistic analysis of Ga2O3/ZrO2 in PDH are rarely studied where GaOx either acts as an active site or a promoter. Here, Ga2O3/ZrO2 catalysts with different Ga/Zr ratios were synthesized by the impregnation technique, and the structure–activity relationship was revealed by combining complementary in/ex-situ characterization methods with catalytic tests. It is found the rate of propene formation first increases linearly and then reaches a plateau with the increase of Ga2O3 loading, such activity-loading dependence is related to the evolution of Ga2O3 species varying from monodisperse to single-layer and then multilayer states. Activation energy and C3H8-TPSR results suggest the formation of a new active site with high intrinsic activity over Ga2O3/ZrO2. Furthermore, the molecular level reaction mechanism of Ga2O3/ZrO2 in PDH was studied by DFT calculations, which pointed out the active site structure was GaⅡ–O3cⅡ site exhibiting enhanced activation ability toward C–H bond and lower reaction barrier compared with bare ZrO2. This work is expected to offer new insights into understanding the structure–activity relationships over ZrO2-based catalysts for PDH reaction.

Effect of supports on the kind of in-situ formed ZnOx species and its consequence for non-oxidative propane dehydrogenation

Non-oxidative propane dehydrogenation (PDH) to propene is the basis of various large-scale processes suffering however from high costs or environmental incompatibility of currently applied Pt- or Cr-containing catalysts. Herein, we demonstrate that active and selective catalysts can be obtained from cheap and commercially available Zr- or Ti-based supports and ZnO without producing any liquid or solid waste. Catalytically active species formed in situ under PDH conditions are composed of isolated ZnOx as concluded from X-ray absorption spectroscopic analysis. The kind of support affects the geometry of such species that is probably decisive for catalyst activity. ZnOx on the surface of LaZrOx revealed the highest Zn-related TOF of propene formation. However, the following activity order in terms of space time yield of propene formation (STYC3H6) at 550 °C and about 50% equilibrium propane conversion using a feed with 40 vol% propane was obtained: ZnO//TiZrOx > ZnO//SiZrOx > ZnO//LaZrOx > ZnO//TiO2. The best-performing catalyst showed STYC3H6 of 2 kg kgcat−1 h−1 and was durable in 8 PDH/regeneration cycles. Temporal analysis of products with submillisecond resolution suggests that H2 formation should be the rate-determining step in the course of the PDH reaction.

2-Propanol Dehydration on the Nodes of the Metal–Organic Framework UiO-66: Distinguishing Catalytic Sites for Formation of Propene and Di-isopropyl Ether

2-Propanol Dehydration on the Nodes of the Metal–Organic Framework UiO-66: Distinguishing Catalytic Sites for Formation of Propene and Di-isopropyl Ether

Highly dispersed and stable NiSn subnanoclusters encapsulated within Silicalite-1 zeolite for efficient propane dehydrogenation

Propane dehydrogenation (PDH) is one of the most effective methods for intentional (“on-purpose”) propylene production. Isolated Sn sites on open supports exhibit considerable PDH performance comparable to that of industrial Pt- and Cr-based catalysts, but the loss of Sn is inevitable. Herein, highly dispersed and stable NiSn subnanoclusters encapsulated within the channels of silicalite-1 zeolite are fabricated through a one-step hydrothermal synthesis in this work. The as-prepared Ni1Sn1@S-1 zeolite catalyst exhibits outstanding PDH performance with considerable propylene formation rate (ca. 12.3 mmol∙gcat-1∙h−1) and high propylene selectivity (>88 %). Most significantly, no Sn loss is detected after three regeneration cycles. Structural elucidation of NiSn sites on catalysts, by HRTEM, H2-TPR, FTIR and XPS characterizations confirms that the Ni sites embedded in the geminal silanols of zeolitic framework play a vital role in anchoring Sn species and preventing the active sites from losing and sintering. The cooperative action of robust NiSn subnanoclusters is conducive to the selective C–H activation and the propylene desorption. A plausible dehydrogenation mechanism is revealed by in situ infrared spectroscopy. This study on siliceous zeolite confined NiSn catalysts delivers an insight into the nature of selective and stable NiSn sites involved in the PDH reaction.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper‐Containing Mordenite: Insights into Reaction Mechanism and Product Protection

AbstractCopper(II)‐containing mordenite (CuMOR) is capable of activation of C−H bonds in C1‐C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time‐resolved Cu K‐edge X‐ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π‐complexes of olefins with CuI sites, formed upon reduction of CuII‐oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection.

Copper(II)-containing mordenite (CuMOR) is capable of activation of C-H bonds in C1 -C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with CuI sites, formed upon reduction of CuII -oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Rational design of vanadia-based propane ODH catalysts: A multiple operando spectroscopic investigation of VOx/TiO2/CeO2

The understanding of reaction mechanisms of supported metal oxide catalysts has significantly increased over the last years due to new methods being applied. This increased knowledge allows to develop approaches towards catalytic materials for reactions with low selectivities by rational design, such as the oxidative dehydrogenation (ODH) of propane, which is of great technical importance. Vanadia (VOx) supported on reducible oxides (TiO2, CeO2, etc.) has shown promising catalytic properties in propane ODH. In this study, we followed a rational-design approach employing atomic layer deposition (ALD) to synthesize a VOx/TiOx/CeO2 catalyst with superior selectivity, by combining favourable properties of the individual catalysts (VOx/TiO2, VOx/CeO2). By applying multiple spectroscopies, including multi-wavelength Raman, UV-Vis, DRIFT, and XP spectroscopy as well as XRD, we were able to identify the functions of each oxide and develop a mechanistic picture. The increased selectivity is the result of distinct interactions between the oxides that slow down the oxygen dynamics in the catalyst and favour reaction pathways beneficial to propylene formation. Our findings highlight the use of rational design to develop improved catalysts based on previously established mechanistic knowledge.

Исследование образования полиароматических углеводородов и углеродных наночастиц при пиролизе этилена с добавками тетрагидрофурана за ударными волнами

Currently, substances are being actively sought that could serve as the alternative fuel or fuel additive reducing formation and emission of the carbon nanoparticles. Here, processes of the polyaromatic hydrocarbons (precursors of the carbon condensed phase formation) and carbon black nanoparticles formation during the ethylene pyrolysis with addition of the tetrahydrofuran were studied by laser-induced fluorescence and laser extinction methods. Spectral dependences of laser-induced fluorescence of the polyaromatic hydrocarbons were obtained by laser-induced fluorescence at various temperatures and pyrolysis stages, and optical density of the reacting gas mixtures at wavelengths of 405 and 633 nm was obtained by laser extinction. Measurements were carried out on a shock tube behind the reflected shock waves in the temperature range of 1,695--2,500 K and pressure range of 2.7--4.1 atm. It is shown that during the ethylene pyrolysis with the tetrahydrofuran addition soot formation process is intensifying, and the temperature range of the carbon nanoparticles formation is expanding. Using the kinetic simulation, it was found that acceleration in the carbon nanoparticles formation was caused by formation of methyl radical and propylene in the tetrahydrofuran pyrolysis

Surface reactivity of VOx/CeO2 (1 1 1) and the impact of transition metal doping of CeO2 support on oxidative dehydrogenation of propane

Propane oxidative dehydrogenation (ODH) was studied over VOx/CeO2 nanoparticle catalysts for various vanadia nuclearities using Density Functional Theory simulations. On monomers and dimers, propene formation involved V=O, bridged (V–O–Ce, V–OV) and ceria surface oxygens but with low selectivity, while on trimers and possibly higher oligomers it was kinetically favourable over ceria surface oxygens, with higher selectivity than on monomers and dimers. On trimer, overoxidation via acetone formation was inhibited, but at the expense of overall catalyst reactivity. Doping of ceria support with Ni induced strong Ni–VOx interactions, stabilizing the vanadia monomer. The V–O–Ni bridged oxygen was less accessible for overoxidation, resulting in an increase in activation energy barrier for acetone formation by 0.69 eV on VO2/Ce0.89Ni0.11O2(111), while there was a minimal impact on V3O6/Ce0.89Ni0.11O2 (111). Hence, transition metal doping of ceria support is a potential strategy to improve propene selectivity over VOx/CeO2 catalysts for a wide range of V loadings.

Efficient Screening of Metal Promoters of Pt Catalysts for C-H Bond Activation in Propane Dehydrogenation from a Combined First-Principles Calculations and Machine-Learning Study.

Platinum-based materials are the most widely used catalysts in propane direct dehydrogenation, which could achieve a balanced activity between both propane conversion and propene formation. One of the core issues of Pt catalysts is how to efficiently activate the strong C-H bond. It has been suggested that adding second metal promoters could greatly solve this problem. In the current work, first-principles calculations combined with machine learning are performed in order to obtain the most promising metal promoters and identify key descriptors for control performance. The combination of three different modes of adding metal promoters and two ratios between promoters and platinum sufficiently describes the system under investigation. The activity of propane activation and the formation of propene are reflected by the increase or decrease of the adsorption energy and C-H bond activation of propane and propene after the addition of promoters. The data of adsorption energy and kinetic barriers from first-principles calculations are streamed into five machine-learning methods including gradient boosting regressor (GBR), K neighbors regressor (KNR), random forest regressor (RFR), and AdaBoost regressor (ABR) together with the sure independence screening and sparsifying operator (SISSO). The metrics (RMSE and R2) from different methods indicated that GBR and SISSO have the most optimal performance. Furthermore, it is found that some descriptors derived from the intrinsic properties of metal promoters can determine their properties. In the end, Pt3Mo is identified as the most active catalyst. The present work not only provides a solid foundation for optimizing Pt catalysts but also provides a clear roadmap to screen metal alloy catalysts.

Boosting propane dehydrogenation over Sn stabilizing dispersed Ptδ+ confined in Silicalite-1 at low temperature

Utilizing the confinement effect of zeolite pores to stabilize active sites has been developed for the improvement of catalytic stability and performance. Herein, a facile strategy is proposed to synthesize a Sn stabilizing dispersed Ptδ+ sites confined in zeolite pore catalyst via Ar calcination for propane dehydrogenation (PDH). 0.2Pt/0.5Sn-S-1-Ar shows excellent propylene formation rate of 10.0 mol C3H6·gPt−1·h−1 and propylene selectivity higher than 99.5% at 450 °C, and the superior catalyst stability in 200 h on-stream. And it has the lowest apparent activation energy barrier of 18.45 KJ/mol over Pt-based catalyst for PDH to our knowledge. According to systemic characterizations, it is demonstrated that the implantation of Sn into Silicalite-1 framework before introducing Pt is essential to generate the highly dispersed Ptδ+ species confined in zeolite pore, and the Ptδ+ species confined in zeolite pore with stronger propane adsorption and propylene desorption ability is responsible for superior PDH performance.