Long-acting high-quality carbon-reducing and pollution-reducing asphalt material for road and preparation method thereof

Abstract

The invention provides a long-acting high-quality carbon-reducing and pollution-reducing asphalt material for a road and a preparation method thereof. The long-acting high-quality carbon-reducing and pollution-reducing asphalt material is prepared from the following raw materials: road asphalt, a cleaning modifier and deasphalted oil. The clean modifier is prepared from the following raw materials: zirconium chloride, terephthalic acid, tetraisopropyl titanate, sodium tungstate, ruthenium dioxide nano powder and perylene diimide. The cleaning modifier is of a multi-stage core-shell structure; in the multilevel core-shell structure, the inner core is a metal organic framework UiO-66, the outer shell is a tight heterojunction layer composed of TiO2 and WO3, RuO2 nanoparticles are further loaded on the surface of the tight heterojunction layer, and a stable heterogeneous photocatalytic interface is formed through perylene diimide molecule covalent grafting modification. According to the invention, UiO-66, TiO2, WO3, RuO2 and PDI are simultaneously used for the road cleaning material for the first time, and the long-acting, high-quality and clean road self-cleaning material is prepared. According to the invention, a large amount of pollutants can be adsorbed and photocatalytic degradation of the pollutants can be realized, and emission reduction in the whole life cycle of the asphalt pavement can be realized.

Description

Technical Field

[0001] This invention belongs to the field of road materials technology, and relates to modified asphalt, specifically to a long-lasting, high-quality, carbon-reducing and pollution-reducing asphalt material for road use and its preparation method. Background Technology

[0002] Asphalt pavement is widely used in highway transportation infrastructure construction due to its excellent physical properties and economic benefits. However, asphalt pavement presents a series of environmental challenges during both the construction and operation phases. Current technology still primarily employs hot-mix asphalt paving, requiring the asphalt temperature to be maintained at 160℃ or even higher, resulting in significant emissions of fumes. Furthermore, asphalt pavement generates volatile organic compounds and contributes to air pollution from vehicle exhaust emissions during its use. Current domestic and international research on emission reduction mainly focuses on asphalt flame retardants, warm-mix additives, and inhibitors, concentrating on the asphalt mixture mixing stage, and has not yet achieved emission reduction throughout the entire life cycle of asphalt pavement. Summary of the Invention

[0003] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a long-lasting, high-quality, carbon-reducing and pollution-reducing asphalt material for road use and its preparation method, thereby solving the technical problem that modified asphalt in the existing technology is difficult to achieve emission reduction and purification throughout its entire life cycle.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use is made from the following raw materials: road asphalt, cleaning modifier, and deasphalting oil.

[0005] The cleaning modifier is made from the following raw materials: zirconium chloride, terephthalic acid, tetraisopropyl titanate, sodium tungstate, ruthenium dioxide nanoparticles, and perylene diimide.

[0006] The present invention also has the following technical features: Specifically, the cleaning modifier has a multi-level core-shell structure; in the multi-level core-shell structure, the core is a metal-organic framework UiO-66, and the outer shell is a tight heterojunction layer composed of TiO2 and WO3. The surface of the tight heterojunction layer is further loaded with RuO2 nanoparticles and covalently grafted with perylene diimide molecules to form a stable heterogeneous photocatalytic interface.

[0007] Specifically, by weight, it is made from the following raw materials: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0008] Specifically, the cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75-80 parts terephthalic acid, 30-50 parts tetraisopropyl titanate, 15-25 parts sodium tungstate, 2-5 parts ruthenium dioxide nanoparticles, and 10-20 parts perylene diimide.

[0009] Preferably, the cleaning modifier is made from the following raw materials in parts by weight: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0010] This invention also provides a method for preparing the road-use long-lasting, high-quality, and clean asphalt material as described above, characterized in that the method includes the following steps: Step 1: Prepare UiO-66 and optimize its performance; Step 2: Coat with a TiO2 layer; Step 3: Load WO3 to form a heterojunction; Step 4: Loading ruthenium dioxide nanoparticles; Step 5: Covalent grafting of perylene diimide; Step 6: Prepare self-cleaning modified asphalt.

[0011] The specific process of step one is as follows: Zirconium chloride, terephthalic acid, and grinding balls are added to a ball mill, followed by the addition of acetic acid. After ball milling, the reactant powder is removed and washed three times with anhydrous ethanol to remove unreacted raw materials and byproducts. After washing, the powder is dried in a vacuum drying oven at 60°C for 12 hours to obtain UiO-66. UiO-66 is then dispersed in hydrogen peroxide and treated at 60°C for 2 hours to generate Zr-OH groups on the surface. The resulting suspension is centrifuged, the supernatant is discarded, and anhydrous ethanol is added to redisperse the suspension. The precipitate is collected by centrifugation again, and the washing is repeated three times. After washing, the powder is dried in a vacuum drying oven at 60°C to constant weight to obtain the optimized UiO-66.

[0012] The specific process of step two is as follows: The optimized UiO-66 obtained in step one is dispersed in anhydrous ethanol, first ultrasonically dispersed for 5 min, then magnetically stirred for 5 min; at the same time, tetraisopropyl titanate is dissolved in anhydrous ethanol, then acetic acid is added, and it is allowed to stand for 5 min. Then, the UiO-66 suspension is added dropwise with a syringe, while magnetically stirring and ultrasonically dispersed for 3 min; a trace amount of aqueous solution containing deionized water and anhydrous ethanol is prepared for controlled hydrolysis, and this solution is added dropwise to the reaction system while maintaining stirring; after the addition is completed, stirring is continued for 30 min, and then it is allowed to stand and age for 6 h to allow the TiO2 shell to gradually condense on the particle surface; then the core and shell solids are separated by centrifugation, the supernatant is discarded, anhydrous ethanol is added for redispersing, the precipitate is collected by centrifugation again, and the washing is repeated three times; after washing, it is dried in a vacuum drying oven at 60℃ for 6 h to obtain the initial UiO-66@TiO2 core-shell powder.

[0013] The specific process of step three is as follows: Sodium tungstate is dissolved in deionized water, and then the initial UiO-66@TiO2 core-shell powder obtained in step two is added. The mixture is ultrasonically dispersed for 5 minutes, stirred at room temperature for 30 minutes, and 20wt% HCl solution is added dropwise until the pH value reaches 2.5-3 to form a tungstate precursor. The mixture is reacted at room temperature for 2 hours. After the reaction is completed, the mixture is centrifuged and washed, and then dried in a vacuum drying oven at 60℃ for 6 hours. After drying, the mixture is annealed at 220℃ for 1 hour under a N2 atmosphere. Finally, a UiO-66@TiO2 / WO3 heterojunction is formed, with WO3 covering the TiO2 surface in the form of particles.

[0014] The specific process of step four is as follows: Ruthenium dioxide nanoparticles are dispersed in anhydrous ethanol by ultrasonic dispersion to obtain a uniform suspension. Then, the UiO-66@TiO2 / WO3 heterojunction powder obtained in step four is added to the ruthenium dioxide nanoparticle suspension, ultrasonically dispersed, and stirred for 40 min to ensure that the ruthenium dioxide nanoparticles are uniformly loaded on the surface of the composite material. After completion, the ruthenium dioxide nanoparticles are washed three times by centrifugation with ethanol to remove unadsorbed ruthenium dioxide nanoparticles. The mixture is then placed in a vacuum drying oven at 60℃ for 6 h to obtain the UiO-66@TiO2 / WO3 / RuO2 composite material.

[0015] Step five involves dispersing the UiO-66@TiO2 / WO3 / RuO2 composite material obtained in step four in anhydrous DMF and ultrasonically dispersing for 5 minutes to obtain a sample DMF suspension. Simultaneously, PDI-COOH is dissolved in anhydrous DMF in another light-proof container, ensuring complete dissolution. NHS is then added to the solution and dissolved, followed by EDC·HCl. The mixture is stirred at room temperature for 4 hours to obtain an activated PDI-NHS solution. The activated PDI-NHS solution is then added dropwise to the stirred sample DMF suspension. After the addition is complete, stirring continues for 4 hours. After the reaction is complete, the mixture is centrifuged, and the supernatant is discarded. The mixture is washed twice with DMF and then twice with ethanol to remove residual small organic molecules. Finally, it is dried in a vacuum drying oven at 60°C for 6 hours. After centrifugation, ethanol washing, and vacuum drying, the UiO-66@TiO2 / WO3 / RuO2 / PDI composite material is obtained, which serves as the cleaning modifier.

[0016] The specific process of step six is ​​as follows: Heat the deasphalted oil to 110℃ and mechanically stir it. While heating and stirring, gradually add the cleaning modifier obtained in step five to the deasphalted oil. After adding, shear at 6000 rpm for 10-20 minutes. After completion, transfer the masterbatch to a heat-resistant container for heat preservation. Then heat the asphalt to 160-180℃. After the temperature stabilizes, stir for 5 minutes to remove air bubbles. Inject the masterbatch into the asphalt and start the high-shear mixer at 3000-6000 rpm for 10-30 minutes. At the same time, maintain the temperature at 160-180℃. After the high shear is completed, reduce the stirring speed to 300-500 rpm and maintain it for 5-10 minutes to eliminate air bubbles and fine-tune the uniformity. The self-cleaning modified asphalt preparation is now complete.

[0017] Compared with the prior art, the present invention has the following technical effects: (I) This invention is the first to use UiO-66 and TiO2. 2、 WO 3、 RuO2 and PDI are used together in road cleaning materials to produce long-lasting, high-quality, and clean self-cleaning road materials. The cleaning material of this invention has excellent properties such as strong adsorption capacity, good durability, and wide application scenarios. When used in combination with asphalt materials, it can achieve large-scale adsorption of pollutants and photocatalytic degradation of pollutants, enabling emission reduction throughout the entire life cycle of asphalt pavements.

[0018] (II) The cleaning modifier prepared in this invention has a multi-level core-shell structure, with UiO-66 as the core, possessing high specific surface area and porosity, enabling efficient adsorption of asphalt fumes and vehicle exhaust. TiO2 and WO3 form the outer shell, capable of photocatalytic degradation of the asphalt fumes and vehicle exhaust adsorbed by UiO-66, solving the problem of traditional materials becoming saturated and losing their adsorption capacity after adsorbing a certain amount of gas. Simultaneously, TiO2 acts as a protective layer, preventing the internal UiO-66 skeleton from being damaged by high temperatures and hydrothermal reactions. By coating the UiO-66 core with TiO2, the structural integrity of the MOF skeleton during high-temperature asphalt mixing is effectively enhanced, preventing collapse or pore blockage during mixing and service. The outer layer loading of WO3 and RuO2 further forms a thermal stability barrier, allowing the material to maintain catalytic activity at asphalt mixing temperatures of 160–180℃, suitable for actual road construction environments. WO3 can also utilize the residual heat of asphalt fumes, triggering the activation of oxygen vacancies in WO3, enhancing low-temperature catalytic oxidation efficiency and reducing light dependence. RuO2, as a highly efficient hole trap, synergizes with the TiO2 / WO3 heterojunction to further promote the effective separation of photogenerated electron-hole pairs, significantly improving the efficiency of photocatalytic oxidation. Simultaneously, PDI molecules form a stable organic-inorganic hybrid interface on the material surface through covalent grafting. This not only broadens the visible light absorption range but also serves as an electron transport bridge, enhancing the interfacial charge migration rate and delaying photocorrosion, enabling the material to maintain excellent catalytic stability under long-term illumination.

[0019] (III) Compared with other traditional MOF materials, such as precious metals like Pt, the materials used in this invention significantly reduce costs. At the same time, UiO-66 is prepared using a solvent-free method through mechanochemical methods, which is simple to prepare and does not generate harmful substances. It can simultaneously achieve green synthesis and mass production. Other preparation steps use solvothermal and impregnation methods, which do not require complex equipment. The material has low preparation costs, can be mass-produced, and can be well applied to the field of asphalt pavement.

[0020] (IV) The materials UiO-66 and TiO2 used in this invention mainly absorb ultraviolet light, while WO3 and PDI can effectively utilize the visible light region. The combination of the four materials enables the light absorption range of the material to cover ultraviolet to visible light, significantly improving the utilization rate of light energy. At the same time, TiO2, as an electron transport layer, forms a stepped band structure with WO3, driving photogenerated electrons to migrate from TiO2 to WO3 and holes to migrate in the opposite direction, effectively suppressing electron-hole recombination. The charge separation efficiency is 2 to 3 times higher than that of single materials, far exceeding that of similar MOF@TiO2 composite materials. The high adsorption performance of UiO-66 and the catalytic performance of TiO2 / WO3 / RuO2 form an "adsorption-enrichment-degradation" cycle, enabling the material to maintain continuous purification capabilities during day and night cycles and rainy weather, achieving all-weather control of asphalt fumes and exhaust pollutants. Attached Figure Description

[0021] Figure 1 These are penetration diagrams for Examples 1 to 8.

[0022] Figure 2 These are softening point diagrams for Examples 1 to 8.

[0023] Figure 3 These are the extension diagrams of Examples 1 to 8.

[0024] Figure 4 This is a comparison diagram of the penetration depth before and after aging of Example 1 and Comparative Examples 9 to 10.

[0025] Figure 5 This is a comparison diagram of the softening points before and after aging of Example 1 and Comparative Examples 9 to 10.

[0026] Figure 6 This is a comparison chart of the ductility before and after aging of Example 1 and Comparative Examples 9 to 10.

[0027] Figure 7 These are emission reduction rate diagrams for Examples 1 to 8.

[0028] Figure 8 This is a graph showing emission reduction rates for scales 1 to 8.

[0029] Figure 9 These are fatigue life diagrams for Example 1 and Comparative Example 10.

[0030] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0031] It should be noted that, unless otherwise specified, all raw materials and equipment used in this invention are those known in the prior art.

[0032] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0033] Example 1: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0034] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0035] In this embodiment, perylene diimide (PDI) refers to N,N'-di(carboxymethyl)perylene-3,4,9,10-tetracarboxydiimide, with the molecular formula C2. 30 H 14 N2O8.

[0036] The preparation method of the above-mentioned long-lasting, high-quality, and clean asphalt material for road use in this embodiment includes the following steps: Step 1: Prepare UiO-66 and optimize its performance: Zirconium chloride, terephthalic acid, and grinding balls were added to a ball mill, followed by the addition of acetic acid. After ball milling, the reactant powder was removed and washed three times with anhydrous ethanol to remove unreacted raw materials and byproducts. After washing, the powder was dried in a vacuum drying oven at 60°C for 12 hours to obtain UiO-66. UiO-66 was then dispersed in hydrogen peroxide and treated at 60°C for 2 hours to generate Zr-OH groups on the surface. The resulting suspension was centrifuged, the supernatant was discarded, and anhydrous ethanol was added to redisperse the suspension. The precipitate was collected by centrifugation again, and the washing process was repeated three times. After washing, the powder was dried in a vacuum drying oven at 60°C to constant weight to obtain the optimized UiO-66.

[0037] In step one, a planetary ball mill was used, with a grinding ball to mixture ratio of 25:1. The grinding balls were made of zirconium oxide with a diameter of 5 mm. The ball mill speed was 400 r / min, and the milling time was 90 min. To prevent overheating, the ball mill was run intermittently, pausing for 2 min every 10 min. Acetic acid was used as a reaction promoter at a concentration of 2.5 mol / L. The hydrogen peroxide concentration was 3%. The centrifugation speed was 10000 rpm, and the time was 10 min.

[0038] Step 2, Coating with a TiO2 layer: The optimized UiO-66 obtained in step one was dispersed in anhydrous ethanol, first ultrasonically dispersed for 5 min, then magnetically stirred for 5 min; simultaneously, tetraisopropyl titanate (Ti(OiPr)4) was dissolved in anhydrous ethanol, then acetic acid was added, and the mixture was allowed to stand for 5 min. Then, the UiO-66 suspension was slowly added dropwise using a syringe, while magnetically stirred (300 rpm) and ultrasonically dispersed for 3 min. A micro-aqueous solution of deionized water and anhydrous ethanol was prepared for controlled hydrolysis, and this solution was added dropwise to the reaction system at a very slow rate, while maintaining stirring. After the addition was complete, stirring continued for 30 min, followed by aging for 6 h, allowing the TiO2 shell to gradually condense on the particle surface. The core-shell solids were then separated using a centrifuge, the supernatant was discarded, and anhydrous ethanol was added for redispersing. The precipitate was collected by centrifugation again, and the washing was repeated three times. After washing, the powder was dried in a vacuum drying oven at 60 °C for 6 h to obtain the initial UiO-66@TiO2 core-shell powder.

[0039] In step two, the concentration of UiO-66 in anhydrous ethanol is 1–5 mg / mL; the ratio of tetraisopropyl titanate, anhydrous ethanol, and acetic acid is 1:10:0.5; the ratio of deionized water to anhydrous ethanol is 1:25; and the ratio of this solution to tetraisopropyl titanate is 1:10. The very slow dropping process is adjusted according to the mass of the material, and the entire dropping process takes 30 minutes. The centrifugation process is carried out at 6000 rpm for 5 minutes.

[0040] Step 3: Loading WO3 to form a heterojunction: Sodium tungstate was dissolved in deionized water, and then the initial UiO-66@TiO2 core-shell powder obtained in step two was added. The mixture was ultrasonically dispersed for 5 min, then stirred at room temperature for 30 min. A 20 wt% HCl solution was slowly added dropwise until the pH reached 2.5–3, forming a tungstate precursor. The reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was centrifuged and washed, then dried in a vacuum drying oven at 60 °C for 6 h. After drying, it was annealed at 220 °C for 1 h under a N2 atmosphere. Finally, a UiO-66@TiO2 / WO3 heterojunction was formed, with WO3 particles covering the TiO2 surface.

[0041] In step three, sodium tungstate is 0.1M Na2WO4·2H2O; ethanol is used for centrifugation and washing.

[0042] Step 4: Loading ruthenium dioxide nanoparticles: Ruthenium dioxide nanoparticles were ultrasonically dispersed in anhydrous ethanol to obtain a uniform suspension. Then, the UiO-66@TiO2 / WO3 heterojunction powder obtained in step four was added to the ruthenium dioxide nanoparticle suspension, ultrasonically dispersed, and stirred for 40 min to ensure that the ruthenium dioxide nanoparticles were uniformly loaded on the surface of the composite material. After completion, the composite material was washed three times by centrifugation with ethanol to remove unadsorbed ruthenium dioxide nanoparticles and then dried in a vacuum drying oven at 60°C for 6 h to obtain the UiO-66@TiO2 / WO3 / RuO2 composite material.

[0043] In step four, the centrifugation process involves centrifuging at 6000 rpm for 5 minutes.

[0044] Step 5, Perylene diimide (PDI) covalent grafting: The UiO-66@TiO2 / WO3 / RuO2 composite material obtained in step four was dispersed in anhydrous DMF (N,N-dimethylformamide) and ultrasonically dispersed for 5 min to obtain a sample DMF suspension. At the same time, PDI-COOH was dissolved in anhydrous DMF in another light-proof container to ensure complete dissolution. Then, NHS (N-hydroxysuccinimide) was added to the solution and dissolved. EDC·HCl (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride) was slowly added and stirred at room temperature for 4 hours to obtain an activated PDI-NHS (perylene diimide-N-hydroxysuccinimide) solution.

[0045] The activated PDI-NHS solution was slowly added dropwise to the DMF suspension of the sample while it was being stirred. After the addition was complete, stirring continued for 4 hours. After the reaction was completed, the sample was centrifuged, and the supernatant was discarded. The sample was washed twice with DMF, and then twice with ethanol to remove residual small organic molecules. Subsequently, it was dried in a vacuum drying oven at 60°C for 6 hours. After the reaction, the sample was separated by centrifugation, washed with ethanol, and vacuum dried to obtain the UiO-66@TiO2 / WO3 / RuO2 / PDI composite material, which is the cleaning modifier.

[0046] In step five, during the dissolution of PDI-COOH, heating at less than 40°C is used to accelerate the dissolution process; the ratio of PDI-COOH, NHS, and EDC·HCl is 5:6:6; the centrifugation process is carried out at 6000 rpm, and centrifugation is stopped after the particles have settled; the entire process is carried out in the dark, so that the imide groups and the intermediate amino groups can covalently couple to form a stable graft.

[0047] Step 6: Preparation of self-cleaning modified asphalt: The deasphalted oil was heated to 110°C and mechanically stirred. While heating and stirring, the cleaning modifier prepared in step five was gradually added to the deasphalted oil. After addition, the mixture was sheared at 6000 rpm for 10–20 minutes. After completion, the masterbatch was transferred to a heat-resistant container for insulation. The asphalt was then heated to 160–180°C. After the temperature stabilized, it was stirred for 5 minutes to remove air bubbles. The masterbatch was slowly injected into the asphalt, and simultaneously, a high-shear mixer was started, set to 3000–6000 rpm, and continuously sheared for 10–30 minutes. The temperature was maintained at 160–180°C. After the high-shear process was completed, the stirring speed was reduced to 300–500 rpm and maintained for 5–10 minutes to eliminate air bubbles and fine-tune uniformity. The self-cleaning modified asphalt preparation was thus completed.

[0048] In step six, when adding the composite material to the deasphalted oil, avoid adding too much at once to prevent clumping; the high-shear mixer is a rotor-stator type.

[0049] In this embodiment, the amount of reagents not specified is in excess, and those skilled in the art can use excess according to the actual situation.

[0050] Example 2: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0051] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 70 parts terephthalic acid, 30 parts tetraisopropyl titanate, 15 parts sodium tungstate, 2 parts ruthenium dioxide nanoparticles, and 10 parts perylene diimide.

[0052] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0053] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0054] Example 3: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0055] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 30 parts tetraisopropyl titanate, 15 parts sodium tungstate, 2 parts ruthenium dioxide nanoparticles, and 10 parts perylene diimide.

[0056] The selection and specifications of the raw materials in this embodiment are the same as those in Embodiment 1.

[0057] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0058] Example 4: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0059] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 15 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0060] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0061] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0062] Example 5: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0063] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 80 parts terephthalic acid, 50 parts tetraisopropyl titanate, 25 parts sodium tungstate, 5 parts ruthenium dioxide nanoparticles, and 20 parts perylene diimide.

[0064] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0065] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0066] Example 6: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0067] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 50 parts tetraisopropyl titanate, 25 parts sodium tungstate, 5 parts ruthenium dioxide nanoparticles, and 20 parts perylene diimide.

[0068] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0069] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0070] Example 7: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0071] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 70 parts terephthalic acid, 30 parts tetraisopropyl titanate, 25 parts sodium tungstate, 5 parts ruthenium dioxide nanoparticles, and 20 parts perylene diimide.

[0072] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0073] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0074] Example 8: This embodiment provides a long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, which is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0075] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 80 parts terephthalic acid, 50 parts tetraisopropyl titanate, 15 parts sodium tungstate, 2 parts ruthenium dioxide nanoparticles, and 10 parts perylene diimide.

[0076] The selection and specifications of the raw materials in this embodiment are the same as in Embodiment 1.

[0077] The preparation method of the road long-lasting high-quality clean asphalt material described in this embodiment is the same as the preparation method of the road long-lasting clean asphalt material given in Example 1.

[0078] Comparative Example 1: The comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that only three materials, UiO-66, TiO2 and WO3, are used. RuO2 and PDI are not added. That is, after TiO2 and WO3 form heterojunctions, RuO2 and PDI are not added, and self-cleaning modified asphalt is directly prepared.

[0079] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0080] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, and 22 parts sodium tungstate.

[0081] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0082] The preparation method of the cleaning material in this comparative example is basically the same as the preparation method of the long-lasting cleaning asphalt material for road use given in Example 1, except for steps four and five.

[0083] Comparative Example 2: This comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that, after UiO-66 is prepared, hydrogen peroxide is not used to alkylate the surface of UiO-66.

[0084] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0085] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0086] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0087] The preparation method of the cleaning material in this comparative example is basically the same as that after hydrogen peroxide removal treatment in Example 1.

[0088] Comparative Example 3: This comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that in step six, deasphalting oil is not used. After the UiO-66@TiO2 / WO3 / RuO2 / PDI composite material is prepared, the material is directly added to the asphalt.

[0089] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt and 3 parts cleaning modifier.

[0090] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0091] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0092] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1, after adding the UiO-66@TiO2 / WO3 / RuO2 / PDI composite material to the deasphalting oil in step six.

[0093] Comparative Example 4: This comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that in step five, the operation is not carried out under light-protected conditions. No light-protected operation is performed during the dissolution of PDI-COOH in anhydrous DMF and the addition of PDI-NHS solution.

[0094] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0095] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0096] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0097] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1.

[0098] Comparative Example 5: This comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that the trace amount of aqueous solution prepared in step two is not added to the reaction system at a very slow rate, but is added slowly with a syringe.

[0099] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0100] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0101] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0102] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1.

[0103] Comparative Example 6: This comparative example provides a cleaning material. The difference between this comparative example and Example 1 is that, in step three, the annealing at 220°C for 1 hour under a N2 atmosphere after drying is changed to annealing at 400°C for 2 hours under normal conditions. This comparative example is made from the following raw materials in parts by weight: The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0104] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0105] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0106] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1.

[0107] Comparative Example 7: This comparative example provides an asphalt material. The difference between this comparative example and Example 1 is that the ball milling time in step one is reduced from 90 min to 30 min.

[0108] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0109] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0110] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0111] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1.

[0112] Comparative Example 8: This comparative example provides an asphalt material. The difference between this comparative example and Example 1 is that the preparation step in step two is changed as follows: UiO-66 is dispersed in anhydrous ethanol, first ultrasonically dispersed for 5 min, then magnetically stirred for 5 min. Simultaneously, TiO2 nanoparticles are added to anhydrous ethanol and ultrasonically dispersed for 5 min to prepare a TiO2 suspension. Then, the TiO2 suspension is slowly added dropwise to the UiO-66 suspension, while ultrasonically dispersed for 3 min, followed by stirring at room temperature for 1 h. After stirring, the mixture is centrifuged, washed twice with ethanol, and dried in a vacuum drying oven at 60°C for 6 h to obtain UiO-66@TiO2.

[0113] The cleaning materials in this comparative example are made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

[0114] The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

[0115] The selection and specifications of each raw material in this comparative example are the same as those in Example 1.

[0116] The preparation method of the cleaning material in this comparative example is basically the same as that in Example 1.

[0117] Comparative Example 9: This comparative example provides one type of asphalt, namely SBS asphalt, and commercially available products can be used.

[0118] Comparative Example 10: This comparative example provides one type of asphalt, namely 70# asphalt, and commercially available products can be used.

[0119] Performance testing: To verify the relevant performance of long-lasting, high-quality, and clean asphalt materials for road use, it is necessary to test the basic performance of self-cleaning modified asphalt, as well as its emission reduction effects during the construction and operation phases of asphalt pavement and the emission reduction effects during the maintenance period of asphalt pavement.

[0120] First, basic performance: Depend on Figures 1 to 6 It can be seen that the basic road performance of self-cleaning modified asphalt, such as penetration, ductility and softening point, meets the relevant technical requirements of the "Technical Specification for Construction of Highway Asphalt Pavement" (JTG F40-2004) and can be used in the road field.

[0121] Depend on Figures 4 to 6 As shown, compared to base asphalt, the softening point and ductility of the long-lasting, high-quality, clean asphalt material increased, while the penetration decreased, indicating that the material's high-temperature stability, rutting resistance, and low-temperature performance were superior to base asphalt. Compared to Comparative Examples 9 and 10, Example 1, after thin-film oven + UV aging, exhibited a higher penetration residual ratio, a smaller softening point increment, and the smallest decrease in ductility after aging. The three major indicators of the self-cleaning modified asphalt showed small changes after aging, indicating that self-cleaning modified asphalt, compared to base asphalt and SBS modified asphalt, better ensures the long-term stability of the high and low-temperature performance of asphalt pavement during its operational period. Simultaneously, both the cleaning modifier and SBS can improve the anti-aging performance of asphalt. Among them, Example 1, after heat curing and UV aging, had the lowest complex modulus aging index and the best anti-aging effect. This is because TiO2 and WO3 are inorganic structures, inherently resistant to high-temperature oxidation. Furthermore, their heterostructure has good stability and is not easily decomposed during aging, thus delaying the decrease in penetration and loss of ductility.

[0122] Second, emission reduction effect: The effects of different asphalt mixtures on asphalt fume adsorption and emission reduction were quantitatively evaluated using asphalt fume adsorption experiments and component emission reduction experiments.

[0123] The calculation methods for emission reduction rates of asphalt mixtures at different stages are as follows: 00%; In the formula: The asphalt fume emission reduction rate of self-cleaning modified asphalt mixture at different stages; The concentration of asphalt fumes emitted by ordinary hot-mix asphalt mixtures at different stages; The concentration of asphalt fumes emitted by self-cleaning modified asphalt mixtures at different stages.

[0124] The experimental results are shown in Table 1. Figures 7 to 9 As shown.

[0125] Table 1. Life-cycle emission reduction performance of each embodiment and comparative example

[0126] From Table 1, Figures 7 to 9 It can be known that: (1) Analysis of the various indicators of Examples 1-8 and Comparative Example 1 shows that after adding RuO2 and PDI, the emission reduction rate during the construction period increased from 43.5% to 54.8%-67.3%, and during the operation period increased from 41.4% to 51.3%-63.3%. This is because RuO2, as a highly efficient hole trap, works synergistically with the TiO2 / WO3 heterojunction to further promote the effective separation of photogenerated electron-hole pairs, significantly improving the efficiency of photocatalytic oxidation reaction. At the same time, PDI molecules form a stable organic-inorganic hybrid interface on the material surface through covalent grafting, which not only broadens the visible light absorption range but also acts as an electron transport bridge, enhancing the interface charge migration rate and delaying photocorrosion, so that the material maintains excellent catalytic stability under long-term light irradiation. In Examples 1-8, the emission reduction rate of each pollutant emission stage is greater than 45%, indicating that this asphalt material has excellent emission reduction capabilities.

[0127] (2) Analysis of the various indicators of Example 1 and Comparative Examples 2 and 3 shows that the adsorption efficiency of the materials was significantly improved after the addition of hydrogen peroxide and deasphalted oil, respectively. This is because the generation of Zr-OH groups is the basis for subsequent coating and loading, which affects the formation of heterojunctions. Deasphalted oil, as a dispersion medium, can promote the uniform dispersion of composite materials in asphalt and improve the emission reduction effect.

[0128] (3) Comparing Example 1 with Comparative Examples 4 to 7, it can be seen that not being carried out under light-protected conditions (Comparative Example 4), improper control of the dripping speed (Comparative Example 5), excessively high annealing conditions (Comparative Example 6), or insufficient ball milling (Comparative Example 7) all lead to a decrease in emission reduction performance, with the emission reduction rate during the construction period decreasing to 51.3%, 59.5%, 35.4%, and 43.9%, respectively. The performance degradation in Comparative Example 4 indicates that PDI is prone to photo-oxidative degradation under light irradiation, disrupting the organic-inorganic hybrid structure and damaging charge transport channels. In Comparative Example 5, insufficient hydrolysis control resulted in inadequate TiO2 coating, increased heterojunction interface defects, increased photogenerated carrier recombination rate, and decreased catalytic activity. In Comparative Example 6, the excessively high annealing temperature led to partial decomposition of the UiO-66 framework, structural collapse, loss of porous properties, and a sharp decrease in surface area, resulting in the lowest emission reduction rate of only about 30%. In Comparative Example 7, insufficient ball milling resulted in incomplete formation of the UiO-66 crystal structure, uneven particle size distribution, and insufficient subsequent coating and loading processes, thus weakening the overall catalytic performance. These results demonstrate that precise control of each step in the preparation process has a decisive impact on the structural integrity and performance stability of the material.

[0129] (5) Analysis of Example 1, Comparative Example 7 and Comparative Example 8. After reducing the ball milling time, the emission reduction rate during the curing period of Comparative Example 7 decreased to 43.9%. Due to insufficient ball milling time, the UiO-66 crystal defects increased. In Comparative Example 8, TiO2 was directly physically mixed with UiO-66 and was not an in-situ grown coating layer. The bonding was not tight enough, resulting in high interface impedance and high recombination rate during electron migration, thereby weakening the photogenerated charge separation efficiency and photocatalytic activity.

[0130] (6) Comparing the various indicators of Examples 1-8 and Comparative Examples 1-8, it can be found that Example 1 has the best overall performance. The optimal raw material composition is: 82 parts of road asphalt, 3 parts of cleaning modifier, and 15 parts of deasphalted oil. The cleaning modifier is made of the following materials: 100 parts of zirconium chloride, 75 parts of terephthalic acid, 37 parts of tetraisopropyl titanate, 22 parts of sodium tungstate, 3 parts of ruthenium dioxide nanoparticles, and 12 parts of perylene diimide. Example 1 achieved an emission reduction rate of over 59% throughout the entire cycle, and its road performance, such as penetration and softening point, met the standards. Its multi-level core-shell structure improved the photogenerated electron-hole separation efficiency by 2.3 times compared with TiO2 alone, confirming the reliability of the "adsorption-catalysis-residual heat activation" synergistic mechanism.

Claims

1. A long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use, characterized in that, Made from the following raw materials: road asphalt, cleaning modifier, and deasphalting oil; The cleaning modifier is made from the following raw materials: zirconium chloride, terephthalic acid, tetraisopropyl titanate, sodium tungstate, ruthenium dioxide nanoparticles, and perylene diimide.

2. The long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use as described in claim 1, characterized in that, The cleaning modifier has a multi-level core-shell structure; in the multi-level core-shell structure, the core is a metal-organic framework UiO-66, and the outer shell is a tight heterojunction layer composed of TiO2 and WO3. The surface of the tight heterojunction layer is further loaded with RuO2 nanoparticles and covalently grafted with perylene diimide molecules to form a stable heterogeneous photocatalytic interface.

3. The long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use as described in claim 1, characterized in that, It is made from the following raw materials by weight: 82 parts road asphalt, 3 parts cleaning modifier, and 15 parts deasphalting oil.

4. The long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use as described in claim 1, characterized in that, The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75-80 parts terephthalic acid, 30-50 parts tetraisopropyl titanate, 15-25 parts sodium tungstate, 2-5 parts ruthenium dioxide nanoparticles, and 10-20 parts perylene diimide.

5. The long-lasting, high-quality, carbon-reducing, and pollution-reducing asphalt material for road use as described in claim 4, characterized in that, The cleaning modifier, by weight, is made from the following raw materials: 100 parts zirconium chloride, 75 parts terephthalic acid, 37 parts tetraisopropyl titanate, 22 parts sodium tungstate, 3 parts ruthenium dioxide nanoparticles, and 12 parts perylene diimide.

6. A method for preparing a long-lasting, high-quality, clean asphalt material for road use as described in any one of claims 1 to 5, characterized in that, The method includes the following steps: Step 1: Prepare UiO-66 and optimize its performance; Step 2: Coat with a TiO2 layer; Step 3: Load WO3 to form a heterojunction; Step 4: Loading ruthenium dioxide nanoparticles; Step 5: Covalent grafting of perylene diimide; Step 6: Prepare self-cleaning modified asphalt.

7. The method for preparing long-lasting, high-quality, and clean asphalt material for road use as described in claim 6, characterized in that, The specific process of step one is as follows: Zirconium chloride, terephthalic acid, and grinding balls are added to a ball mill, and then acetic acid is added for ball milling. After ball milling, the reactant powder is taken out and washed three times with anhydrous ethanol to remove unreacted raw materials and by-products. After washing, it is dried in a vacuum drying oven at 60°C for 12 hours to obtain UiO-66. Then, UiO-66 is dispersed in hydrogen peroxide and treated at 60°C for 2 hours to generate Zr-OH groups on the surface. The resulting suspension is centrifuged, the supernatant is discarded, and anhydrous ethanol is added to redisperse the suspension. The precipitate is collected by centrifugation again, and the washing is repeated three times. After washing, the product was dried at 60°C in a vacuum drying oven to constant weight, yielding the optimized UiO-66.

8. The method for preparing long-lasting, high-quality, and clean asphalt material for road use as described in claim 6, characterized in that, The specific process of step two is as follows: The optimized UiO-66 obtained in step one is dispersed in anhydrous ethanol, first ultrasonically dispersed for 5 min, then magnetically stirred for 5 min; at the same time, tetraisopropyl titanate is dissolved in anhydrous ethanol, then acetic acid is added, and it is allowed to stand for 5 min. Then, the UiO-66 suspension is added dropwise with a syringe, while magnetically stirring and ultrasonically dispersed for 3 min; a trace amount of aqueous solution containing deionized water and anhydrous ethanol is prepared for controlled hydrolysis, and this solution is added dropwise to the reaction system while maintaining stirring; after the addition is completed, stirring is continued for 30 min, and then it is allowed to stand and age for 6 h to allow the TiO2 shell to gradually condense on the particle surface; then the core and shell solids are separated by centrifugation, the supernatant is discarded, anhydrous ethanol is added for redispersing, the precipitate is collected by centrifugation again, and the washing is repeated three times; after washing, it is dried in a vacuum drying oven at 60℃ for 6 h to obtain the initial UiO-66@TiO2 core-shell powder.

9. The method for preparing long-lasting, high-quality, and clean asphalt material for road use as described in claim 6, characterized in that, The specific process of step three is as follows: Sodium tungstate is dissolved in deionized water, and then the initial UiO-66@TiO2 core-shell powder obtained in step two is added. The mixture is ultrasonically dispersed for 5 minutes, stirred at room temperature for 30 minutes, and 20wt% HCl solution is added dropwise until the pH value reaches 2.5-3 to form a tungstate precursor. The mixture is reacted at room temperature for 2 hours. After the reaction is completed, the mixture is centrifuged and washed, and then dried in a vacuum drying oven at 60℃ for 6 hours. After drying, the mixture is annealed at 220℃ for 1 hour under a N2 atmosphere. Finally, a UiO-66@TiO2 / WO3 heterojunction is formed, with WO3 covering the TiO2 surface in the form of particles. The specific process of step four is as follows: Ruthenium dioxide nanoparticles are ultrasonically dispersed in anhydrous ethanol to obtain a uniform suspension. Then, the UiO-66@TiO2 / WO3 heterojunction powder obtained in step four is added to the ruthenium dioxide nanoparticle suspension, ultrasonically dispersed, and stirred for 40 min to ensure that the ruthenium dioxide nanoparticles are uniformly loaded on the surface of the composite material. After completion, the powder is centrifuged and washed three times with ethanol to remove unadsorbed ruthenium dioxide nanoparticles. The powder is then placed in a vacuum drying oven at 60℃ for 6 h to obtain the UiO-66@TiO2 / WO3 / RuO2 composite material. The specific process of step five is as follows: The UiO-66@TiO2 / WO3 / RuO2 composite material obtained in step four is dispersed in anhydrous DMF and ultrasonically dispersed for 5 min to obtain a sample DMF suspension; at the same time, PDI-COOH is dissolved in anhydrous DMF in another light-proof container to ensure complete dissolution, then NHS is added to the solution and dissolved, EDC·HCl is added, and the mixture is stirred at room temperature for 4 hours to obtain an activated PDI-NHS solution; the activated PDI-NHS solution is added dropwise to the sample DMF suspension being stirred, and stirring is continued for 4 h after the addition is complete. After the reaction is completed, the mixture is centrifuged and the supernatant is discarded. The mixture was washed twice with DMF and then twice with ethanol to remove residual small organic molecules. It was then dried at 60°C for 6 hours in a vacuum drying oven. After the reaction, it was centrifuged, washed with ethanol, and vacuum dried to obtain the UiO-66@TiO2 / WO3 / RuO2 / PDI composite material, which is the cleaning modifier.

10. The method for preparing long-lasting, high-quality, and clean asphalt material for road use as described in claim 6, characterized in that, The specific process of step six is ​​as follows: Heat the deasphalted oil to 110℃ and mechanically stir it. While heating and stirring, gradually add the cleaning modifier obtained in step five to the deasphalted oil. After adding, shear at 6000 rpm for 10-20 minutes. After completion, transfer the masterbatch to a heat-resistant container for heat preservation. Then heat the asphalt to 160-180℃. After the temperature stabilizes, stir for 5 minutes to remove air bubbles. Inject the masterbatch into the asphalt and start the high-shear mixer at 3000-6000 rpm for 10-30 minutes. At the same time, maintain the temperature at 160-180℃. After the high shear is completed, reduce the stirring speed to 300-500 rpm and maintain it for 5-10 minutes to eliminate air bubbles and fine-tune the uniformity. The self-cleaning modified asphalt preparation is now complete.

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