Three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and preparation method thereof

Abstract

The invention belongs to the technical field of removal of inorganic advanced materials and pollutants in water, and particularly relates to a three-dimensional pore intercommunicated nano crystal mesoporous photocatalyst and a preparation method thereof. The mesoporous photocatalyst is prepared from a straight-pore and large-aperture nano composite mesoporous oxide material of a two-dimensional hexagonal structure by etching amorphous SiO2 nanoparticles in a pore wall in NaOH solution, washing, drying and activating, wherein the aperture range of the new catalyst is 1-20 nm, the BET specific surface area is 80-900 m<2> / g, and the thermal stability is higher than 400 DEG C. At room temperature and under ultraviolet illumination, the performance for the mesoporous photocatalyst to degrade cationic dyes and anionic dyes in a liquid phase is 2-10 times the performance of the original corresponding straight-pore nano composite mesoporous material of the two-dimensional hexagonal structure; and the performance for degrading algal toxin is 1.3-6 times that of the straight-pore nano composite mesoporous material of the two-dimensional hexagonal structure.

Description

technical field

[0001] The invention belongs to the technical field of inorganic advanced materials and pollutant removal in water. Specifically, it relates to a nano-crystalline mesoporous oxide photocatalyst with different compositions, interconnected three-dimensional pores, large aperture, high specific surface area, high performance, and a preparation method thereof. Background technique

[0002] Highly ordered, two-dimensional hexagonal structure, straight channels, large pore size, high specific surface area, nanocomposite mesoporous xTiO 2 –ySiO 2 [x / y (molar ratio) = (99–1) / (1–99)] The material consists of TiO 2 Nanocrystalline and Amorphous SiO 2 Nanoparticle composition, TiO 2 Nanocrystalline grains and SiO 2 The nanoparticles are connected to each other in the framework and coexist between phases, forming a very unique mesoporous framework structure. Its large pore size allows the reactants and product molecules to easily diffuse in and out before and afte...

Examples

Embodiment 1

[0025] Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous titania-silicon [xTiO 2 –ySiO 2 , x / y (molar ratio) = (95–60) / (5–40)] Synthesis: Dissolve 1 g of P123 template in 10–30 g of ethanol and stir for 2–4 hours. Add 0.0095–0.0060 mol of ethyl titanate or isopropyl titanate or butyl titanate, 0.0005–0.0040 mol of ethyl orthosilicate and 0.02–8 g of sulfuric acid or nitric acid or hydrochloric acid, and continue stirring for 1–3 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 80–100% relative humidity and 60–80 oC. After 2–5 days, transfer it to an oven at 90–100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 350 oC for 6 hours, and then crystallize it at 450–900 oC for 2– A series of required materials can be obtained in 20 hours. Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous ni...

Embodiment 2

[0032] Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous titania-silicon [xTiO 2 –ySiO 2 , x / y = (90–15) / (10–85)] Synthesis of composite materials: Dissolve 1 g of P123 template in 10–30 g of ethanol and stir for 2–4 hours. Add 0.0090-0.0015 moles of ethyl titanate or isopropyl titanate or butyl titanate, 0.0010-0.0085 moles of ethyl orthosilicate and 0.02-8 grams of sulfuric acid or nitric acid or hydrochloric acid, and continue stirring for 3-5 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 20–40% relative humidity and 70–90 oC. After 2–5 days, transfer it to an oven at 100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 400 oC for 6 hours, and then crystallize it at 650–900 oC for 2–24 hours. Obtain a series of required materials. Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous ...

Embodiment 3

[0036] Highly ordered, two-dimensional hexagonal structure, straight channels, and large-aperture nanocomposite mesoporous titanium-niobium-silicon oxide [xTiO 2 –yNb 2 o 5 –zSiO 2 , x / y = (100–0) / (0–100), (x+y) / z = (95–60) / (5–40)] Synthesis: Dissolve 1 g of P123 template in 10– 30 g of ethanol and stirred for 2–4 hours. Add [(0–0.0095) – (0–0.0060)] moles of ethyl titanate or isopropyl titanate or butyl titanate, [(0.0095–0) – (0.0060–0)] moles of ethyl niobate , 0.0005-0.0040 mole ortho-ethyl orthosilicate and 0.02-8 grams of sulfuric acid or nitric acid or hydrochloric acid, and continue to stir for 2-5 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 70–100% relative humidity and 10–20 oC. After 2–5 days, transfer it to an oven at 80–100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 380 oC for 6 hours, and then crystallize it at 450–900 oC for 2– A series of required materials can be obtained withi...

technical field

[0001] The invention belongs to the technical field of inorganic advanced materials and pollutant removal in water. Specifically, it relates to a nano-crystalline mesoporous oxide photocatalyst with different compositions, interconnected three-dimensional pores, large aperture, high specific surface area, high performance, and a preparation method thereof. Background technique

[0002] Highly ordered, two-dimensional hexagonal structure, straight channels, large pore size, high specific surface area, nanocomposite mesoporous xTiO 2 –ySiO 2 [x / y (molar ratio) = (99–1) / (1–99)] The material consists of TiO 2 Nanocrystalline and Amorphous SiO 2 Nanoparticle composition, TiO 2 Nanocrystalline grains and SiO 2 The nanoparticles are connected to each other in the framework and coexist between phases, forming a very unique mesoporous framework structure. Its large pore size allows the reactants and product molecules to easily diffuse in and out before and afte...

Examples

Embodiment 1

[0025] Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous titania-silicon [xTiO 2 –ySiO 2 , x / y (molar ratio) = (95–60) / (5–40)] Synthesis: Dissolve 1 g of P123 template in 10–30 g of ethanol and stir for 2–4 hours. Add 0.0095–0.0060 mol of ethyl titanate or isopropyl titanate or butyl titanate, 0.0005–0.0040 mol of ethyl orthosilicate and 0.02–8 g of sulfuric acid or nitric acid or hydrochloric acid, and continue stirring for 1–3 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 80–100% relative humidity and 60–80 oC. After 2–5 days, transfer it to an oven at 90–100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 350 oC for 6 hours, and then crystallize it at 450–900 oC for 2– A series of required materials can be obtained in 20 hours. Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous ni...

Embodiment 2

[0032] Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous titania-silicon [xTiO 2 –ySiO 2 , x / y = (90–15) / (10–85)] Synthesis of composite materials: Dissolve 1 g of P123 template in 10–30 g of ethanol and stir for 2–4 hours. Add 0.0090-0.0015 moles of ethyl titanate or isopropyl titanate or butyl titanate, 0.0010-0.0085 moles of ethyl orthosilicate and 0.02-8 grams of sulfuric acid or nitric acid or hydrochloric acid, and continue stirring for 3-5 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 20–40% relative humidity and 70–90 oC. After 2–5 days, transfer it to an oven at 100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 400 oC for 6 hours, and then crystallize it at 650–900 oC for 2–24 hours. Obtain a series of required materials. Highly ordered, two-dimensional hexagonal structure, straight channels, large-aperture nanocomposite mesoporous ...

Embodiment 3

[0036] Highly ordered, two-dimensional hexagonal structure, straight channels, and large-aperture nanocomposite mesoporous titanium-niobium-silicon oxide [xTiO 2 –yNb 2 o 5 –zSiO 2 , x / y = (100–0) / (0–100), (x+y) / z = (95–60) / (5–40)] Synthesis: Dissolve 1 g of P123 template in 10– 30 g of ethanol and stirred for 2–4 hours. Add [(0–0.0095) – (0–0.0060)] moles of ethyl titanate or isopropyl titanate or butyl titanate, [(0.0095–0) – (0.0060–0)] moles of ethyl niobate , 0.0005-0.0040 mole ortho-ethyl orthosilicate and 0.02-8 grams of sulfuric acid or nitric acid or hydrochloric acid, and continue to stir for 2-5 hours. Transfer the reaction mother liquor to a Petri dish, and evaporate to dryness at 70–100% relative humidity and 10–20 oC. After 2–5 days, transfer it to an oven at 80–100 oC for drying, then place it in a tube furnace or muffle furnace, bake it at 380 oC for 6 hours, and then crystallize it at 450–900 oC for 2– A series of required materials can be obtained withi...