An optical-thermal coupling ethane anaerobic dehydrogenation catalyst, a preparation method and application thereof
By loading Pt, Pd, Cu or Au and co-catalysts such as Ba, K, Cs, Na, Ca or Li onto a TiO2 substrate, a photothermal coupled ethane oxygen-free dehydrogenation catalyst was constructed, solving the problem of efficient catalysis of ethane catalytic conversion to ethylene under mild conditions, and realizing efficient and selective ethylene production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ANHUI NORMAL UNIV
- Filing Date
- 2026-05-06
- Publication Date
- 2026-06-02
AI Technical Summary
Existing technologies for the catalytic conversion of ethane to ethylene at high temperatures suffer from carbon buildup and high energy consumption, making it difficult to efficiently catalyze the oxygen-free dehydrogenation of ethane under mild conditions.
A photothermal coupled ethane oxygen-free dehydrogenation catalyst was used. By loading a first cocatalyst such as Pt, Pd, Cu or Au and a second cocatalyst such as Ba, K, Cs, Na, Ca or Li onto a TiO2 substrate, a dual cocatalyst metal synergistic system was constructed to optimize the active sites and electronic structure of the catalyst. The photothermal synergistic effect catalysis was carried out in a continuous fixed-bed photothermal reactor.
The method achieves highly efficient catalytic dehydrogenation of ethane to ethylene under mild conditions with an ethylene yield of up to 22.147 mmol/g/h. It exhibits high selectivity, and the catalyst is readily available and simple to prepare, making it suitable for large-scale production.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of energy catalysis technology, and in particular to a photothermal coupled ethane oxygen-free dehydrogenation catalyst, its preparation method, and its application. Background Technology
[0002] Ethylene (C2H4) is a basic chemical feedstock, traditionally produced primarily through the high-temperature steam cracking of naphtha. However, with the increasing abundance of ethane (C2H6) resources in shale gas, and the ethylene production yield from its cracking reaching 10% to 20%, the route for producing ethylene from ethane is attracting growing attention. Therefore, achieving the direct catalytic conversion of ethane to ethylene is extremely attractive.
[0003] Although significant progress has been made in thermocatalytic dehydrogenation technology using zeolite and vanadium-based catalysts, the reaction temperature still needs to exceed 500°C due to the high bond energy of the CH bond in ethane (415 kJ / mol), and it is prone to carbon deposition problems.
[0004] Therefore, it is necessary to develop a method for the continuous catalytic dehydrogenation of ethane to ethylene under relatively mild conditions. Summary of the Invention
[0005] The purpose of this invention is to provide a photothermal coupled ethane oxygen-free dehydrogenation catalyst and its preparation method. This invention optimizes the active sites and electronic structure of the catalyst by constructing a dual-co-catalyst metal synergistic system and regulating its interface structure.
[0006] The purpose of this invention is to provide an application of a photothermal coupled ethane oxygen-free dehydrogenation catalyst in the continuous production of ethylene. With the help of a designed continuous fixed-bed photothermal reactor, the catalyst can efficiently catalyze the continuous production of ethylene from ethane through oxygen-free dehydrogenation under relatively mild conditions through a photothermal synergistic effect. Moreover, the preparation method is simple, easy to operate, and can be mass-produced.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a photothermal coupled ethane oxygen-free dehydrogenation catalyst, wherein a first co-catalyst metal and a second co-catalyst metal are distributed in a single-atom dispersed form on a TiO2 substrate to constitute the photothermal coupled ethane oxygen-free dehydrogenation catalyst; the first co-catalyst metal is one or more of Pt, Pd, Cu or Au; and the second co-catalyst metal is one or more of alkali metals or alkaline earth metals.
[0008] According to a specific embodiment of the present invention, preferably, the second co-catalyst metal is one or more of Ba, K, Cs, Na, Ca or Li.
[0009] The loading of the first co-catalyst metal is 0.05~1 wt.%, and the loading of the second co-catalyst metal is 0.05~0.5 wt.%.
[0010] According to a specific embodiment of the present invention, preferably, the size of the substrate is 10 nm.
[0011] This invention provides a method for preparing the photothermal coupled ethane oxygen-free dehydrogenation catalyst, the method comprising the following steps: 1) The substrate is immersed in the second co-catalyst precursor solution for impregnation treatment; 2) Calcine the product from step 1); 3) Disperse the product from step 2) in deionized water, adjust the pH of the deionized water, and then add the first co-catalyst precursor solution dropwise to carry out the hydrolysis reaction; 4) The product from step 3) is calcined to obtain the photothermal coupled ethane oxygen-free dehydrogenation catalyst.
[0012] In step 1), the second cocatalyst precursor is one or more of the following: chloride, sulfate, nitrate, carbonate, phosphate or acetate of alkali metal or alkaline earth metal, and the concentration of the second cocatalyst precursor solution is 0.2~2mM.
[0013] In step 1), the immersion treatment is carried out at room temperature for 0.5 to 1 hour.
[0014] According to a specific embodiment of the present invention, preferably, after impregnation in step 1), drying is performed without separating the substrate and the second cocatalyst precursor solution. The drying temperature is 80 °C and the drying time is 8~12 h.
[0015] In steps 2) and 4), the calcination temperature is 350~450 ℃ and the calcination time is 2~4h.
[0016] In step 3), the first cocatalyst precursor is a chloride, carbonate, or nitrate of Pt, Pd, Cu, or Au; the concentration of the first cocatalyst precursor solution is 0.1~1.6 mM.
[0017] In step 3), the pH value of the hydrolysis reaction is 10-12, the reaction time is 1-2 hours, and the reaction temperature is room temperature.
[0018] This invention provides an application of the photothermal coupled ethane oxygen-free dehydrogenation catalyst described herein in the continuous production of ethylene.
[0019] A method for the continuous production of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: Under heating conditions, the continuous fixed-bed photothermal reactor is purged with ethane-containing gas for 20-30 minutes, followed by the introduction of ethane-containing gas and the activation of the light source to continuously produce ethylene through photothermal coupled catalytic oxygen-free dehydrogenation of ethane.
[0020] The continuous fixed-bed photothermal reactor is filled with the photothermal coupled ethane oxygen-free dehydrogenation catalyst described in this invention.
[0021] Furthermore, the filling method of the continuous fixed-bed photothermal reactor includes the following steps: The photothermal coupled ethane oxygen-free dehydrogenation catalyst was ultrasonically dispersed in deionized water, and then the product was dropped onto a microporous filter membrane, dried to form a catalyst membrane, and then placed in a continuous fixed-bed photothermal reactor.
[0022] According to a specific embodiment of the present invention, preferably, the heating condition is 80°C.
[0023] According to a specific embodiment of the present invention, preferably, the light source is a 365 nm xenon lamp.
[0024] According to a specific embodiment of the present invention, preferably, the ethane-containing gas is an ethane-argon mixture, and the volume percentage of ethane in the ethane-argon mixture is 20%.
[0025] In the aforementioned photothermal coupled catalytic method for the continuous production of ethylene from ethane through oxygen-free dehydrogenation, the photothermal coupled ethane oxygen-free dehydrogenation catalyst, under the combined action of light and heat, generates high-energy electron-hole pairs with reductive and oxidizing capabilities by photoexciting the substrate, promoting the separation of photogenerated electron-hole pairs. Thermal energy, on the other hand, facilitates mass transfer between ethane molecules and promotes timely product desorption. Simultaneously, thermal excitation extends the lifetime of the photogenerated charge, maintaining the catalyst's high efficiency and stability, thus achieving the goal of high-yield and highly selective continuous ethylene production.
[0026] Compared with the prior art, the present invention has the following advantages: 1. By using a continuous fixed-bed photothermal reactor, efficient and highly selective photocatalytic dehydrogenation of ethane to ethylene is achieved. 2. The catalyst raw materials described in this invention are readily available, have extremely low metal loading, and the preparation steps are simple and easy to implement under mild conditions, allowing for large-scale preparation in a short time; 3. The catalyst described in this invention is used for the continuous preparation of ethylene, with an ethylene yield ≥22.147 mmol / g / h. Attached Figure Description
[0027] Figure 1 Figure a shows a schematic diagram of the continuous ethylene production apparatus of Application Example 2 of the present invention, and Figure b shows a photograph of the continuous ethylene production apparatus of Application Example 2 of the present invention; Figure 2 A TEM image of the PdBa / TiO2 prepared in Example 1 is shown; Figure 3 The energy dispersive X-ray spectroscopy (EDS) mapping of PdBa / TiO2 prepared in Example 1 is shown. Figure 4 The AC-STEM image of PdBa / TiO2 prepared in Example 1 is shown; Figure 5 The XRD patterns of the catalysts prepared in Example 1 and Comparative Examples 1-3 are shown. Figure 6 The ultraviolet-visible (UV-Vis) absorption spectrum of PdBa / TiO2 prepared in Example 1 is shown. Figure 7 The PL plots of the catalysts prepared in Example 1 and Comparative Examples 1-3 are shown. Figure 8 XPS images of the PdBa / TiO2 prepared in Example 1 are shown; Figure 9 The graphs showing the ethylene yield and ethylene selectivity performance of the catalysts prepared in Example 1 and Comparative Example 3 in Application Example 2 are illustrated. Figure 10 The graphs show the ethylene yield and ethylene selectivity of PdBa / TiO2 prepared in Example 1 over a period of 0 to 165 h in Application Example 2. Figure 11 The graphs show the ethylene yield and ethylene selectivity of PdBa / TiO2 prepared in Example 1 in Application Example 2 and Application Comparative Example 1, where dark represents Application Comparative Example 1 and light represents Application Example 2. Figure 12 The graph shows a comparison of ethylene yield and ethylene selectivity data for PdBa / TiO2 prepared in Example 1 in Application Example 2 and Application Comparative Examples 2-4. Figure 13 A comparative graph showing ethylene yield and ethylene selectivity data using the catalysts of Examples 1-6 and Comparative Examples 2-3 in Application Example 2 is presented. Figure 14 A comparison graph showing the ethylene yield and ethylene selectivity data of the catalysts used in Example 1 and Comparative Examples 1-2 in Application Example 2 is shown. Detailed Implementation
[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0029] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.
[0030] Example 1
[0031] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: 1) Take 700 mg of TiO2 with a size of 10 nm as a substrate and place it in a reaction vessel. Add 510 μL of 0.01 mol / L barium chloride and 10 mL of deionized water as a second co-catalyst precursor solution. Stir for 30 min at 25 °C with the rotation speed controlled at 800 rpm. Then place it in a forced-air drying oven and dry at 80 °C for 10 h. 2) After grinding the product from step 1), place it in a muffle furnace and heat it to 400℃ at a rate of 5℃ / min, maintain the temperature for 2 hours, then cool it down and remove it. Theoretically, the Ba loading is 0.1 wt.%. 3) Add 25 ml of deionized water to a beaker, add 0.01 g of NaOH to adjust the pH to 12, then add 500 mg of the product from step 2), stir at 800 rpm for 0.5 h, add 1410 μL of 0.01 mol / L palladium chloride aqueous solution dropwise, and use the solution after the palladium chloride aqueous solution is added as the first co-catalyst precursor solution. Stir at 500 rpm for 1 h at room temperature, wash the product three times with deionized water, and dry it in a 25℃ forced-air drying oven for 3 days. 4) Grind the product from step 3) into powder, place it in a muffle furnace, heat it to 400℃ at a rate of 5℃ / min and maintain it for 4h to obtain the photothermal coupled ethane oxygen-free dehydrogenation catalyst, the product is labeled as PdBa / TiO2.
[0032] Example 2
[0033] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: The only difference between this embodiment and Example 1 is that barium chloride in step 1) is replaced with lithium nitrate, and the product is labeled as PdLi / TiO2.
[0034] Example 3
[0035] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: The only difference between this embodiment and Example 1 is that barium chloride in step 1) is replaced with calcium nitrate, and the product is labeled as PdCa / TiO2.
[0036] Example 4
[0037] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: The only difference between this embodiment and Example 1 is that barium chloride in step 1) is replaced with sodium carbonate, and the product is labeled as PdNa / TiO2.
[0038] Example 5
[0039] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: The only difference between this embodiment and Example 1 is that barium chloride in step 1) is replaced with cesium carbonate, and the product is labeled as PdCs / TiO2.
[0040] Example 6
[0041] A method for preparing a photothermal coupled ethane oxygen-free dehydrogenation catalyst specifically includes the following steps: The only difference between this embodiment and Example 1 is that barium chloride in step 1) is replaced with potassium sulfate, and the product is labeled as PdK / TiO2.
[0042] Comparative Example 1 A method for preparing a catalyst, specifically including the following steps: The difference between this comparative example and Example 1 is that step 3 is omitted, and the product is labeled as Ba / TiO2.
[0043] Comparative Example 2 A method for preparing a catalyst, specifically including the following steps: The difference between this comparative example and Example 1 is that steps 1) and 2) are omitted, and the product in step 2) of step 3) is replaced with 500 mg of TiO2 with a size of 10 nm. The product is labeled as Pd / TiO2.
[0044] Comparative Example 3 This comparative example uses a 10nm TiO2 substrate, and the product is labeled as TiO2.
[0045] Application Example 1 A method for loading a continuous fixed-bed photothermal reactor specifically includes the following steps: Ten mg of the catalysts prepared in each example and comparative example were ultrasonically dispersed in deionized water. The product was then dropped onto a microporous filter membrane, dried to form a catalyst membrane, and then placed into a continuous fixed-bed photothermal reactor to complete the loading of the continuous fixed-bed photothermal reactor.
[0046] Application Example 2 A method for the continuous production of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: At 80°C, the continuously fixed-bed photothermal reactor described in Example 1 was purged with 20% C2H6 / Ar for 0.5 h. Then, 20% C2H6 / Ar was introduced at a flow rate of 214 mL / min, and the temperature was maintained at 80°C. A 365 nm xenon lamp was started to continuously produce ethylene from ethane through photothermal coupled catalytic oxygen-free dehydrogenation.
[0047] Application Comparative Example 1 A method for the continuous preparation of ethylene from ethane via thermocatalytic oxygen-free dehydrogenation, the method comprising the following steps: The only difference between this comparative example and Example 2 is that the 365 nm xenon lamp was not activated.
[0048] Application Comparative Example 2 A method for the continuous production of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: The only difference between this comparative application and application example 2 is that maintaining 80°C is replaced with lowering the temperature to 45°C.
[0049] Application Comparative Example 3 A method for the continuous production of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: The only difference between this comparative application and application example 2 is that maintaining 80°C is replaced with lowering the temperature to 55°C.
[0050] Application Comparative Example 4 A method for the continuous production of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: The only difference between this comparative application and application example 2 is that maintaining 80°C is replaced with lowering the temperature to 65°C.
[0051] Figure 2 The TEM image of the PdBa / TiO2 prepared in Example 1 is shown below. Figure 2 As shown, no Pd or Ba particles were observed, according to Figure 2 It is determined that Pd and Ba are likely distributed on the substrate in a single-atom dispersion form.
[0052] Figure 4The image shows an aberration-corrected transmission electron microscope (AC-STEM) image of PdBa / TiO2 prepared in Example 1. Isolated bright atomic points can be observed in the image, indicating the presence of single-atom dispersed metal species in PdBa / TiO2. Figure 2 The absence of observed metal particles indicates that Pd and Ba are distributed in a single-atom dispersion on the TiO2 substrate. Figure 5 The XRD pattern of PdBa / TiO2 prepared in Example 1 is shown. Figure 5 As can be seen, loading Pd and Ba does not change the crystal structure of TiO2.
[0053] Figure 6 The UV-Vis pattern of PdBa / TiO2 prepared in Example 1 is shown. Figure 6 As can be seen, the light absorption capacity of the catalyst is improved after loading Pd and Ba.
[0054] Figure 7 The PL plot of PdBa / TiO2 prepared in Example 1 is shown. Figure 7 As can be seen, the charge separation efficiency of the catalyst is improved after the introduction of Pd and Ba.
[0055] Figure 8 The XPS plot of PdBa / TiO2 prepared in Example 1 is shown. Figure 8 As can be seen from this, the Pd in PdBa / TiO2 is Pd 2+ .
[0056] Test Example 1 Tests for yield and selectivity: The yield and selectivity of ethylene in Application Example 2 and Application Comparative Examples 1-4 were analyzed and detected by online gas chromatography. Gas chromatography equipped with flame ionization detector and thermal conductivity detector was used. The tail gas components were analyzed by autosampler, and the concentrations of ethylene, methane, carbon monoxide and carbon dioxide were quantitatively determined by external standard method.
[0057] The yield of ethylene is defined as the amount of ethylene produced per unit mass of catalyst per unit time, and its calculation formula is as follows: ; In the formula R C2H4 Ethylene yield, in mmol / g -1 h -1 F represents the total intake airflow rate, in mL / h; C C2H4 V represents the volume concentration of ethylene in the exhaust gas as determined by gas chromatography. m denoted as the molar volume of the gas under standard conditions; m represents the mass of the catalyst loaded in the continuous fixed-bed photothermal reactor, in grams.
[0058] The selectivity of ethylene is calculated based on carbon balance, which is the percentage of carbon atoms in ethylene products relative to the total number of carbon atoms in all carbon-containing products. These products include C2H4, CH4, CO, and CO2. The calculation formula is as follows:
[0059] In the formula S C2H4 n represents the selectivity for ethylene; n(C2H4) represents the molar amount of ethylene detected; n(CH4), n(CO), and n(CO2) represent the molar amounts of the corresponding byproducts detected.
[0060] Figure 9 and Figure 10 The following graph shows the reaction performance data of using the catalyst PdBa / TiO2 provided in Example 1 for a continuous 165 h in Application Example 2, as shown. Figure 9 As shown, compared to pure TiO2, the ethylene yield of the PdBa / TiO2 photothermal coupled catalytic reaction of ethane oxygen-free dehydrogenation was significantly increased to 32.275 mmol / g / h, with an ethylene selectivity of 97.87%; Figure 10 As shown, the ethylene yield remained relatively stable during the 165-h experiment, indicating that the PdBa / TiO2 provided by this invention possesses excellent photothermal coupling catalytic activity and reaction stability.
[0061] Figure 11 and Figure 12 The graphs showing the ethylene yield and ethylene selectivity of PdBa / TiO2 prepared in Example 1 in Application Example 2 and Comparative Examples 1-4 are illustrated. Figure 11 As shown, under purely thermocatalytic conditions, almost no ethylene is produced. This indicates that the PdBa / TiO2-catalyzed oxygen-free dehydrogenation of ethane to ethylene is coupled with photocatalysis and thermocatalysis, rather than a solar-driven thermocatalytic reaction. Figure 12 As shown, the ethylene yield increases with increasing temperature. Under the condition of reactor temperature of 80℃, the highest ethylene yield of PdBa / TiO2 is 32.275 mmol / g / h.
[0062] Figure 13 A comparative graph showing ethylene yield and ethylene selectivity data using the catalysts of Examples 1-6 and Comparative Examples 2-3 in Application Example 2 is shown, as follows: Figure 13 As shown, loading PdLi, PdCa, PdNa, PdCs and PdK can all enhance its reactivity, which proves that the photothermal coupled ethane oxygen-free dehydrogenation catalyst and its preparation method provided by the present invention have universality.
[0063] Figure 14The reaction performance data of the catalyst PdBa / TiO2 provided in Example 1 and Comparative Examples 1-2 in Application Example 2 are shown. PdBa / TiO2 has a significant performance improvement compared with pure TiO2, Ba / TiO2 and Pd / TiO2, indicating that there is a significant synergistic enhancement effect between Pd and Ba. The joint introduction of the two effectively optimizes the electronic structure of the active site, and maintains extremely high ethylene selectivity while greatly improving the ethane dehydrogenation activity.
[0064] It should be noted that the above embodiments are merely some preferred embodiments of the present invention, and not all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.
[0065] The above description of the embodiments is intended to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.
Claims
1. A photothermal coupled ethane oxygen-free dehydrogenation catalyst, characterized in that, The first and second cocatalyst metals are distributed in a single-atom dispersed form on the TiO2 substrate to form the photothermal coupled ethane oxygen-free dehydrogenation catalyst; the first cocatalyst metal is one or more of Pt, Pd, Cu or Au; the second cocatalyst metal is one or more of alkali metal or alkaline earth metal.
2. The photothermal coupled ethane oxygen-free dehydrogenation catalyst according to claim 1, characterized in that, The loading of the first co-catalyst metal is 0.05~1 wt.%, and the loading of the second co-catalyst metal is 0.05~0.5 wt.%.
3. A method for preparing the photothermal coupled ethane oxygen-free dehydrogenation catalyst as described in claim 1, characterized in that, The preparation method includes the following steps: 1) The substrate is immersed in the second co-catalyst precursor solution for impregnation treatment; 2) Calcine the product from step 1); 3) Disperse the product from step 2) in deionized water, adjust the pH of the deionized water, and then add the first co-catalyst precursor solution dropwise to carry out the hydrolysis reaction; 4) The product from step 3) is calcined to obtain the photothermal coupled ethane oxygen-free dehydrogenation catalyst.
4. The preparation method according to claim 3, characterized in that, In step 1), the second cocatalyst precursor is one or more of the following: chloride, sulfate, nitrate, carbonate, phosphate or acetate of alkali metal or alkaline earth metal, and the concentration of the second cocatalyst precursor solution is 0.2~2mM.
5. The preparation method according to claim 3, characterized in that, In step 1), the immersion treatment is carried out at room temperature for 0.5 to 1 hour.
6. The preparation method according to claim 3, characterized in that, In steps 2) and 4), the calcination temperature is 350~450℃ and the calcination time is 2~4h.
7. The preparation method according to claim 3, characterized in that, In step 3), the first cocatalyst precursor is a chloride, carbonate, or nitrate of Pt, Pd, Cu, or Au; the concentration of the first cocatalyst precursor solution is 0.1~1.6 mM.
8. The preparation method according to claim 3, characterized in that, In step 3), the pH value of the hydrolysis reaction is 10-12, the reaction time is 1-2 hours, and the reaction temperature is room temperature.
9. The application of the photothermal coupled ethane oxygen-free dehydrogenation catalyst as described in claim 1 in the continuous production of ethylene.
10. A method for the continuous preparation of ethylene from ethane via photothermal coupled catalytic oxygen-free dehydrogenation, the method comprising the following steps: Under heating conditions, a continuous fixed-bed photothermal reactor is purged with ethane-containing gas for 20-30 minutes, followed by the introduction of ethane-containing gas and the activation of the light source to continuously produce ethylene via photothermal coupled catalytic oxygen-free dehydrogenation of ethane. The continuous fixed-bed photothermal reactor is characterized by being filled with the photothermal coupled ethane oxygen-free dehydrogenation catalyst as described in claim 1.