CN-121988395-A - High-stability CuS-based photocatalyst and preparation method and application thereof

Abstract

The invention provides a high-stability CuS-based photocatalyst, a preparation method and application thereof, wherein the photocatalyst takes NH 2 -MIL-125 (Ti) as a substrate, and CuS is uniformly anchored on the surface of NH 2 -MIL-125 (Ti) through coordination. The invention adopts a coordination driving strategy, utilizes the higher specific surface area of Ti-MOF and rich amino reaction active sites to provide rich anchoring sites for Cu 2+ ions, so that CuS NP is uniformly anchored on the surface of Ti-MOF, the interface contact area between Ti-MOF and CuS NPs is increased to the greatest extent by the uniformly dispersed geometric structure, the efficient migration of photogenerated carriers through Cu-N coordination bonds among interfaces is facilitated, the separation of electrons and holes is promoted, the anti-photo-corrosion performance is enhanced, and the photo-catalytic activity and the photo-stability are improved. The photocatalytic oxidation system utilizes natural light as a light source and air as an oxidant, efficiently catalyzes and synthesizes benzimidazole compounds under mild conditions, has the yield of more than 90 percent, and realizes sustainable green synthesis of fine chemicals.

Inventors

• LIU ZEWEI
• ZENG XIPING
• YU DONGXU

Assignees

• 深圳市华科创智技术股份有限公司

Dates

Publication Date

20260508

Application Date

20251204

Claims (9)

1. 1. A high-stability CuS-based photocatalyst is characterized in that NH 2 -MIL-125 (Ti) is taken as a substrate, and CuS is uniformly anchored on the surface of NH 2 -MIL-125 (Ti) through coordination.
2. 2. The high-stability CuS-based photocatalyst according to claim 1, wherein the mass percentage of CuS is 3-16%.
3. 3. The method for preparing the high-stability CuS-based photocatalyst according to claim 1 or 2, comprising the steps of: Step 1) dispersing NH 2 -MIL-125 (Ti) in ethanol by ultrasonic, adding CuSO 4 ·5H 2 O, and stirring the mixed solution at 75-85 ℃ for 1-1.5h to form a suspension; Step 2) dissolving thioacetamide in ethanol, adding the suspension under stirring, and continuing stirring for 15-20min at 75-85 ℃; step 3) centrifuging and collecting the obtained solid, and washing and drying to obtain CuS-based photocatalyst Ti-MOF@CuS (x) powder; Wherein x represents the mass percent of CuS in the catalyst.
4. 4. The method for preparing a high-stability CuS-based photocatalyst according to claim 3, wherein the mass ratio of NH 2 -MIL-125 (Ti) to CuSO 4 ·5H 2 O is 10:1-4.8; the mass ratio of NH 2 -MIL-125 (Ti) to thioacetamide is 80:3-11.
5. 5. The method for preparing a high-stability CuS-based photocatalyst according to claim 3, wherein the mass ratio of the ethanol to NH 2 -MIL-125 (Ti) in the step 1) is 180-200:1; The mass ratio of the ethanol to the thioacetamide in the step 2) is 143-526:1.
6. 6. Use of a highly stable CuS-based photocatalyst according to claim 1 or 2 in a natural light induced phillips-radenberg reaction.
7. 7. The use of a highly stable CuS-based photocatalyst according to claim 6 for the preparation of benzimidazole compounds in natural light-induced phillips-radenberg reactions.
8. 8. The use of a highly stable CuS-based photocatalyst according to claim 7 in a natural light induced phillips-radenberg reaction, characterized by the following procedure: dissolving aromatic aldehyde and o-phenylenediamine in acetonitrile, adding a CuS-based photocatalyst Ti-MOF@CuS (x), and stirring in a reactor under dark conditions for 25-30min; Taking natural light as a light source, reacting under the atmospheric condition, centrifuging after the reaction is finished, recovering a catalyst Ti-MOF@CuS (x) from a reaction system, and washing with acetonitrile for recycling.
9. 9. The use of a highly stable CuS-based photocatalyst according to claim 8 for natural light-induced phillips-radenberg reaction, characterized in that the progress of the reaction is monitored by Thin Layer Chromatography (TLC) during the reaction; after the completion of the reaction, the reaction solution and an eluent of thin layer chromatography were mixed, acetonitrile was distilled off under reduced pressure, and then the crude product was purified by silica gel chromatography.

Description

High-stability CuS-based photocatalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of photocatalysis, and particularly relates to a high-stability CuS-based photocatalyst, and a preparation method and application thereof. Background Benzimidazole derivatives are valuable pharmacological active compounds and are widely applied to the production of various medicaments such as anticancer, antifungal or antiulcer medicaments. The Philips-Ladenburg reaction utilizes o-phenylenediamine and aromatic aldehyde to generate oxidative condensation-cyclization tandem reaction to generate phenylbenzimidazole, is an effective method for synthesizing benzimidazole compounds, and has cheap and easily obtained reaction raw materials. However, in conventional thermocatalytic Phillips-Lardngburg reaction systems, the use of excessive amounts of oxidants (such as sodium sulfite and sodium hypochlorite) or higher reaction temperatures (> 120 ℃) is often required, severely limiting its large-scale industrial application. The natural light-driven photocatalysis reaction can fully utilize inexhaustible solar energy, realizes chemical reaction which is difficult to be completed by traditional thermocatalysis under mild conditions, and is widely focused. Copper sulfide (CuS) exhibits great potential for use in natural light driven photocatalytic reactions due to its excellent light absorption capability in the visible region and even in the near infrared region. However, the hole-induced photo-corrosion phenomenon of CuS easily occurs under illumination, and S 2- on the surface is oxidized into simple substance S or SO 42- ions by the photo-generated holes on the valence band, which significantly reduces the photocatalytic activity and the photostability. Disclosure of Invention In order to solve the technical problems in the prior art, the invention provides a high-stability CuS-based photocatalyst, which takes NH 2 -MIL-125 (Ti) (called Ti-MOF for short) as a substrate, and CuS is uniformly anchored on the surface of NH 2 -MIL-125 (Ti) through coordination. According to the invention, cuS is anchored on the surface of the energy band matched organic semiconductor NH 2 -MIL-125 (Ti), and NH 2 -MIL-125 (Ti) is used as a hole acceptor or electron donor, so that the transfer or consumption of photo-generated holes on the CuS is facilitated, the photo-corrosion phenomenon of the CuS, which is easy to generate hole induction under illumination, is effectively relieved, and the photo-catalytic activity and the photo-stability are improved. Further, the mass percentage of CuS is 3-16%. The invention also provides a preparation method of the high-stability CuS-based photocatalyst, which comprises the following steps: Step 1) dispersing NH 2 -MIL-125 (Ti) in ethanol by ultrasonic, adding CuSO 4·5H2 O, and stirring the mixed solution at 75-85 ℃ for 1-1.5h to form a suspension; Step 2) dissolving thioacetamide in ethanol, adding the suspension under stirring, and continuing stirring for 15-20min at 75-85 ℃; step 3) centrifuging and collecting the obtained solid, and washing and drying to obtain CuS-based photocatalyst Ti-MOF@CuS (x) powder; Wherein x represents the mass percent of CuS in the catalyst. The invention provides rich anchoring sites for Cu 2+ ions by utilizing rich amino (NH 2) functional groups on the surface of NH 2 -MIL-125 (Ti), thereby promoting CuS to be uniformly anchored on the surface of Ti-MOF through coordination, in addition, NH 2 is used as an electron donor to help stabilize photogenerated holes, so that Ti-MOF serves as an ideal hole acceptor in a CuS-based hybrid material, thereby effectively relieving the photodecomposition phenomenon of CuS, and a coordination driving strategy is adopted to hybridize CuS nano particles with the surface of NH 2 -MIL-125 (Ti), so that the Ti-MOF@CuS (x) photocatalyst with high stability is prepared. Further, the mass ratio of the NH 2 -MIL-125 (Ti) to the CuSO 4·5H2 O is 10:1-4.8; the mass ratio of NH 2 -MIL-125 (Ti) to thioacetamide is 80:3-11. Further, in the step 1), the mass ratio of the ethanol to the NH 2 -MIL-125 (Ti) is 180-200:1; The mass ratio of the ethanol to the thioacetamide in the step 2) is 143-526:1. The invention also provides application of the high-stability CuS-based photocatalyst in natural light-induced Philips-Lardngburg reaction. Further, the method is used for preparing benzimidazole compounds. The invention synthesizes benzimidazole compound under the catalysis of Ti-MOF@CuS (x) photocatalyst with high stability and high efficiency under the drive of natural light. Further, the process is as follows: dissolving aromatic aldehyde and o-phenylenediamine in acetonitrile, adding a CuS-based photocatalyst Ti-MOF@CuS (x), and stirring in a reactor under dark conditions for 25-30min; Taking natural light as a light source, reacting under the atmospheric condition, centrifuging after the reaction is f