WO2023193472A1 - K, rb co-doped c3n4 photocatalyst and application thereof in preparation of acetaldehyde by synergistic photocatalytic co2 reduction and ethanol oxidation - Google Patents

K, rb co-doped c3n4 photocatalyst and application thereof in preparation of acetaldehyde by synergistic photocatalytic co2 reduction and ethanol oxidation Download PDF

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WO2023193472A1
WO2023193472A1 PCT/CN2022/139950 CN2022139950W WO2023193472A1 WO 2023193472 A1 WO2023193472 A1 WO 2023193472A1 CN 2022139950 W CN2022139950 W CN 2022139950W WO 2023193472 A1 WO2023193472 A1 WO 2023193472A1
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汪福宪
刘琼
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广东省科学院测试分析研究所(中国广州分析测试中心)
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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    • B01D2257/504—Carbon dioxide

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  • the invention relates to the field of photocatalysis technology, and specifically relates to a K, Rb co-doped C 3 N 4 photocatalyst and its application in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde.
  • Adding hole sacrificial agents such as triethanolamine (TEOA), sodium sulfite (Na 2 SO 3 ), and N,N,N,N'-tetramethyl-p-phenylenediamine (TMPD) can effectively promote CO 2 photoreduction, but this is This is achieved at the expense of consuming sacrificial agents and wasting the oxidizing ability of photogenerated holes.
  • Another option is to combine CO2 reduction with thermodynamically and kinetically more favorable organic synthesis, which can synergistically exploit photogenerated electrons and holes while ensuring the added value of the oxidative half-reaction.
  • the oxidation products of this type of reaction are different from the reduction products, resulting in complex composition of the final product, thereby increasing the difficulty of product isolation and purification.
  • the ideal reaction should be to simultaneously obtain the same target product from CO reduction reaction and organic oxidation reaction in a single photocatalytic system.
  • the field of electrocatalytic synthesis research has pioneered the possibility of producing formic acid through simultaneous anode methanol oxidation and cathode CO reduction .
  • this strategy has not yet been applied in the field of photocatalytic CO reduction .
  • the present invention solves the problems existing in the prior art and provides a K, Rb co-doped C 3 N 4 photocatalyst and its application in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde.
  • the K, Rb proposed by the present invention Rb co-doped C 3 N 4 photocatalyst can simultaneously photocatalyze CO 2 reduction and ethanol oxidation, and the generated product acetaldehyde has the advantages of high yield and high selectivity.
  • the object of the present invention is to provide a preparation method of K, Rb co-doped C 3 N 4 photocatalyst, which includes the following steps:
  • step (2) Mix the C 3 N 4 obtained in step (1) with potassium salt and rubidium salt in deionized water and ultrasonicate to obtain a mixed solution, stir evenly at room temperature and then dry to obtain a solid mixture;
  • step (3) Pass the mixture solid described in step (2) into an inert gas for pyrolysis treatment, cool to room temperature, wash, and dry to obtain K and Rb co-doped C 3 N 4 .
  • the high-temperature polymerization temperature in step (1) is 200°C to 700°C, the high-temperature polymerization time is 1 to 10 h, and the inert gas flow rate is 5 to 100 mL/min. More preferably, the high-temperature polymerization temperature in step (1) is 570°C to 700°C, the high-temperature polymerization time is 2 to 4 hours, and the inert gas flow rate is 7 to 15 mL/min.
  • the potassium salt in step (2) is potassium chloride (KCl), and the rubidium salt is rubidium chloride (RbCl).
  • the inert gas described in steps (1) and (3) is argon.
  • the concentration of C 3 N 4 in the mixed solution described in step (2) is 10 to 40 mg/mL, the concentration of potassium chloride is 1 to 10 mg/mL, and the concentration of rubidium chloride is 1 to 10 mg/mL,
  • the ultrasonic time is 10 ⁇ 30min, the stirring time is 3 ⁇ 8h, the drying temperature is 50°C ⁇ 200°C, and the drying time is 5 ⁇ 10h.
  • the concentration of C 3 N 4 in the mixed solution described in step (2) is 20 to 40 mg/mL, the concentration of potassium chloride is 3 to 10 mg/mL, and the concentration of rubidium chloride is 3 to 10 mg/mL.
  • the ultrasonic time is 15 ⁇ 30min, the stirring time is 4 ⁇ 8h, the drying temperature is 100°C ⁇ 200°C, and the drying time is 5 ⁇ 6h.
  • the inert gas flow rate in step (3) is 5 to 100 mL/min
  • the temperature of the pyrolysis treatment is 200°C to 1000°C
  • the time of the pyrolysis treatment is 3 to 10h
  • the drying temperature is 80°C to 200°C.
  • drying time is 2 ⁇ 10h.
  • the inert gas flow rate in step (3) is 7 to 15 mL/min
  • the temperature of the pyrolysis treatment is 570°C to 700°C
  • the time of the pyrolysis treatment is 3 to 4h
  • the drying temperature is 80°C to 100°C.
  • drying time is 2 ⁇ 10h.
  • the invention also protects the K and Rb co-doped C 3 N 4 photocatalyst obtained by the above preparation method.
  • the invention also protects the application of the above-mentioned K and Rb co-doped C 3 N 4 photocatalyst in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde, and includes the following steps: co-doping the K and Rb with C 3 N 4.
  • the photocatalyst is dispersed in a reactor filled with ethanol and acetonitrile aqueous solutions. Inert gas is blown into the mixed liquid in the reactor to remove residual air, and then pure CO 2 gas is filled into the mixed liquid to achieve CO 2 dissolution saturation. Then, the photocatalytic CO 2 reduction and ethanol oxidation synergistic reactions are driven under light. During the reaction, CO 2 is bubbled into the mixed solution to keep the CO 2 dissolved and saturated, and ethanol is added in real time to keep its concentration constant.
  • the photocatalyst concentration in the mixed solution is 1-30 mg/mL
  • the volume fraction of ethanol is 5%-40%
  • the volume fraction of acetonitrile is 5%-40%.
  • the inert gas is nitrogen or argon, and the inert gas introduction time is 1 to 10 minutes.
  • the CO 2 gas introduction time is 1 to 10 minutes to ensure CO 2 dissolution and saturation.
  • the wavelength of the illumination source is 280-780 nm, and the reaction temperature is controlled at 5°C-25°C.
  • the present invention Compared with the existing technology, the present invention has the following advantages: for the first time, the present invention synthesizes a K, Rb co-doped C 3 N 4 photocatalyst.
  • the photocatalyst can simultaneously photocatalyze CO 2 reduction and ethanol oxidation, and the generated product acetaldehyde has The advantages of high yield and high selectivity.
  • This photocatalyst makes full use of photogenerated electrons and holes, providing a new way to co-design CO reduction and organic oxidation reaction pathways to obtain the same products.
  • Figure 1 is the X-ray diffraction pattern (XRD) of CN and CN-KRb prepared in Example 1.
  • Figure 2 is an X-ray photoelectron spectrum (XPS) of CN-KRb prepared in Example 1.
  • Figure 3 is a mass spectrum (MS) of the product of photocatalytic CO 2 reduction and ethanol oxidation using CN-KRb prepared in Example 1.
  • Figure 4 is a diagram showing the performance test results of photocatalytic CO 2 reduction and synergistic ethanol oxidation products using CN-KRb prepared in Example 1.
  • a preparation method of K, Rb co-doped C 3 N 4 photocatalyst including the following steps:
  • step (3) Put the solid mixture prepared in step (2) into a tube furnace, pass argon gas at a flow rate of 7 mL/min, heat to 570°C for pyrolysis treatment for 4 hours, cool to room temperature, and wash with water and ethanol. 3 times to remove residual metal salts and dried in an oven at 100°C for 2 h. Finally, a K and Rb co-doped C 3 N 4 photocatalyst was obtained, which was recorded as CN-KRb.
  • the CN prepared in step (1) and the CN-KRb prepared in step (3) were characterized using an X-ray diffractometer, and the results are shown in Figure 1. It can be seen from the figure that the structure of CN-KRb is basically similar to that of CN, with two characteristic peaks (100) and (002), indicating that its main structure remains basically unchanged after the introduction of K and Rb.
  • step (1) the argon gas flow rate is 15 mL/min, the high-temperature polymerization temperature is 700°C, and the high-temperature polymerization time is 2 hours.
  • the difference is that: the concentration of carbon nitride (C 3 N 4 ) in the mixed solution in step (2) is 40 mg/mL, the concentration of potassium chloride (KCl) is 10 mg/mL, and the concentration of rubidium chloride ( The concentration of RbCl) was 10 mg/mL, the ultrasonic time was 30 min, the stirring time was 8 h, the drying temperature was 200°C, and the drying time was 5 h.
  • the difference is that: in step (3), the argon flow rate is 15 mL/min, the pyrolysis temperature is 700°C, the pyrolysis time is 3h, the drying temperature in the oven is 80°C, and the drying time is 10h.
  • step (2) mixing the carbon nitride (C 3 N 4 ) prepared in step (1) and potassium chloride (KCl) in deionized water and ultrasonic for 15 minutes to obtain Mix the solution.
  • the concentration of carbon nitride (C 3 N 4 ) in the mixed solution is 20 mg/mL, and the concentration of potassium chloride (KCl) is 6 mg/mL.
  • KCl potassium chloride
  • step (2) are: mixing the carbon nitride (C 3 N 4 ) and rubidium chloride (RbCl) prepared in step (1) in deionized water and ultrasonic for 15 minutes to obtain Mix the solution.
  • the concentration of carbon nitride (C 3 N 4 ) in the mixed solution is 20 mg/mL, and the concentration of rubidium chloride (RbCl) is 6 mg/mL.
  • RbCl rubidium chloride
  • the photocatalytic CO 2 reduction and ethanol oxidation synergistic reactions are driven under the illumination of LED white light (light source wavelength is 280-780 nm).
  • LED white light light source wavelength is 280-780 nm.
  • CO 2 is bubbled into the mixed solution to keep the CO 2 dissolved and saturated, and ethanol is added in real time to keep it saturated.
  • the concentration is constant.
  • the reaction temperature was maintained at 25°C throughout the experiment.

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Abstract

Provided are a K, Rb co-doped C3N4 photocatalyst and an application thereof in the preparation of acetaldehyde by synergistic photocatalytic CO2 reduction and ethanol oxidation. The preparation method for the photocatalyst comprises the following steps: (1) carrying out high-temperature polymerization on dicyanodiamide in an inert atmosphere, cooling to room temperature, and grinding an obtained product to obtain carbon nitride C3N4; (2) mixing the C3N4 with potassium salt and rubidium salt in deionized water and ultrasonically obtaining a mixed solution, uniformly stirring at room temperature, then drying to obtain mixture solids; and (3) introducing an inert gas to the mixture solids and performing pyrolysis, cooling to room temperature, washing, and drying to obtain the photocatalyst. The provided K and RB co-doped C3N4 photocatalyst innovatively realizes synergistic photocatalytic CO2 reduction and ethanol oxidation, the produced acetaldehyde product has the advantages of high yield and high selectivity, raw materials are easy to obtain, and the reaction process is simple.

Description

K、Rb共掺杂C 3N 4光催化剂及其在光催化CO 2还原协同乙醇氧化制乙醛中的应用 K, Rb co-doped with C 3N 4 Photocatalysts and their role in photocatalytic CO 2Application of reduction and synergistic ethanol oxidation to produce acetaldehyde 技术领域：Technical areas:
本发明涉及光催化技术领域，具体涉及一种K、Rb共掺杂C 3N 4光催化剂及其在光催化CO 2还原协同乙醇氧化制乙醛中的应用。 The invention relates to the field of photocatalysis technology, and specifically relates to a K, Rb co-doped C 3 N 4 photocatalyst and its application in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde.
背景技术：Background technique:
利用光催化将CO 2还原为燃料或高附加值化学品是减轻温室效应和创造可再生碳循环的一种极具发展潜力的方法。模仿自然光合作用，人工光催化CO 2还原和H 2O氧化已被证实可行。然而，在这种人工光催化CO 2还原过程中，4电子的H 2O氧化反应动力学缓慢，因此析氧反应需要很大的过电位。此外，H 2O和O 2可以接受光生电子，导致竞争性析氢反应和活性氧的产生(例如O 2-)。因此，用热力学上更有利的氧化半反应代替析氧反应成为研究热点。 The use of photocatalysis to reduce CO into fuels or high value-added chemicals is a promising approach to mitigating the greenhouse effect and creating a renewable carbon cycle. Mimicking natural photosynthesis, artificial photocatalytic CO 2 reduction and H 2 O oxidation have been proven feasible. However, in this artificial photocatalytic CO2 reduction process, the 4-electron H2O oxidation reaction kinetics is slow, so the oxygen evolution reaction requires a large overpotential. In addition, H 2 O and O 2 can accept photogenerated electrons, leading to competitive hydrogen evolution reactions and the generation of reactive oxygen species (such as O 2- ). Therefore, replacing the oxygen evolution reaction with a thermodynamically more favorable oxidation half-reaction has become a research hotspot.
添加三乙醇胺(TEOA)、亚硫酸钠(Na 2SO 3)和N,N,N,N'-四甲基对苯二胺(TMPD)等空穴牺牲剂可以有效促进CO 2光还原，但是这是以消耗牺牲剂和浪费光生空穴的氧化能力为代价实现的。另一种方案是将CO 2还原与热力学和动力学上更有利的有机合成相结合，可以协同利用光生电子和空穴，同时确保氧化半反应的附加值。然而，这类反应氧化产物与还原产物不同，导致最终产品成分复杂，从而增加了产物分离和提纯的难度。 Adding hole sacrificial agents such as triethanolamine (TEOA), sodium sulfite (Na 2 SO 3 ), and N,N,N,N'-tetramethyl-p-phenylenediamine (TMPD) can effectively promote CO 2 photoreduction, but this is This is achieved at the expense of consuming sacrificial agents and wasting the oxidizing ability of photogenerated holes. Another option is to combine CO2 reduction with thermodynamically and kinetically more favorable organic synthesis, which can synergistically exploit photogenerated electrons and holes while ensuring the added value of the oxidative half-reaction. However, the oxidation products of this type of reaction are different from the reduction products, resulting in complex composition of the final product, thereby increasing the difficulty of product isolation and purification.
因此，理想的反应应该是在单个光催化系统中同时从CO 2还原反应和有机氧化反应中获得相同的目标产物。在电催化合成领域，已有研究开创性地证明了通过同时阳极甲醇氧化和阴极CO 2还原生产甲酸的可能性。然而，该策略尚未应用于光催化CO 2还原领域。 Therefore, the ideal reaction should be to simultaneously obtain the same target product from CO reduction reaction and organic oxidation reaction in a single photocatalytic system. In the field of electrocatalytic synthesis, research has pioneered the possibility of producing formic acid through simultaneous anode methanol oxidation and cathode CO reduction . However, this strategy has not yet been applied in the field of photocatalytic CO reduction .
发明内容：Contents of the invention:
本发明解决了现有技术存在的问题，提供一种K、Rb共掺杂C 3N 4光催化剂及其在光催 化CO 2还原协同乙醇氧化制乙醛中的应用，本发明提出的K、Rb共掺杂C 3N 4光催化剂可同时光催化CO 2还原和乙醇氧化，生成的产物乙醛具有产率高和高选择性的优点。 The present invention solves the problems existing in the prior art and provides a K, Rb co-doped C 3 N 4 photocatalyst and its application in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde. The K, Rb proposed by the present invention Rb co-doped C 3 N 4 photocatalyst can simultaneously photocatalyze CO 2 reduction and ethanol oxidation, and the generated product acetaldehyde has the advantages of high yield and high selectivity.
本发明的目的是提供一种K、Rb共掺杂C 3N 4光催化剂的制备方法，包括以下步骤： The object of the present invention is to provide a preparation method of K, Rb co-doped C 3 N 4 photocatalyst, which includes the following steps:
(1)将双氰胺(DCDA)在惰性气氛中高温聚合，冷却至室温后所得产物研磨，得到氮化碳C 3N 4； (1) Polymerize dicyandiamide (DCDA) at high temperature in an inert atmosphere, and then grind the product after cooling to room temperature to obtain carbon nitride C 3 N 4 ;
(2)将步骤(1)得到的C 3N 4与钾盐、铷盐在去离子水中混合超声得到混合溶液，室温下搅拌均匀后干燥，得到混合物固体； (2) Mix the C 3 N 4 obtained in step (1) with potassium salt and rubidium salt in deionized water and ultrasonicate to obtain a mixed solution, stir evenly at room temperature and then dry to obtain a solid mixture;
(3)将步骤(2)所述的混合物固体通入惰性气体进行热解处理，冷却至室温后洗涤，干燥得到K、Rb共掺杂C 3N 4。 (3) Pass the mixture solid described in step (2) into an inert gas for pyrolysis treatment, cool to room temperature, wash, and dry to obtain K and Rb co-doped C 3 N 4 .
优选地，步骤(1)所述的高温聚合温度为200℃～700℃，高温聚合时间为1～10h，惰性气体流量为5～100mL/min。进一步优选，步骤(1)所述的高温聚合温度为570℃～700℃，高温聚合时间为2～4h，惰性气体流量为7～15mL/min。Preferably, the high-temperature polymerization temperature in step (1) is 200°C to 700°C, the high-temperature polymerization time is 1 to 10 h, and the inert gas flow rate is 5 to 100 mL/min. More preferably, the high-temperature polymerization temperature in step (1) is 570°C to 700°C, the high-temperature polymerization time is 2 to 4 hours, and the inert gas flow rate is 7 to 15 mL/min.
优选地，步骤(2)所述的钾盐为氯化钾(KCl)，铷盐为氯化铷(RbCl)。步骤(1)和(3)所述的惰性气体为氩气。Preferably, the potassium salt in step (2) is potassium chloride (KCl), and the rubidium salt is rubidium chloride (RbCl). The inert gas described in steps (1) and (3) is argon.
进一步优选，步骤(2)所述的混合溶液中C 3N 4的浓度为10～40mg/mL，氯化钾的浓度为1～10mg/mL，氯化铷的浓度为1～10mg/mL，超声时间为10～30min，搅拌时间为3～8h，干燥温度为50℃～200℃，干燥时间为5～10h。再进一步优选，步骤(2)所述的混合溶液中C 3N 4的浓度为20～40mg/mL，氯化钾的浓度为3～10mg/mL，氯化铷的浓度为3～10mg/mL，超声时间为15～30min，搅拌时间为4～8h，干燥温度为100℃～200℃，干燥时间为5～6h。 Further preferably, the concentration of C 3 N 4 in the mixed solution described in step (2) is 10 to 40 mg/mL, the concentration of potassium chloride is 1 to 10 mg/mL, and the concentration of rubidium chloride is 1 to 10 mg/mL, The ultrasonic time is 10~30min, the stirring time is 3~8h, the drying temperature is 50℃~200℃, and the drying time is 5~10h. Still further preferably, the concentration of C 3 N 4 in the mixed solution described in step (2) is 20 to 40 mg/mL, the concentration of potassium chloride is 3 to 10 mg/mL, and the concentration of rubidium chloride is 3 to 10 mg/mL. , the ultrasonic time is 15~30min, the stirring time is 4~8h, the drying temperature is 100℃~200℃, and the drying time is 5~6h.
优选地，步骤(3)所述的惰性气体流量为5～100mL/min，热解处理的温度为 200℃～1000℃，热解处理的时间为3～10h，干燥温度为80℃～200℃，干燥时间为2～10h。进一步优选，步骤(3)所述的惰性气体流量为7～15mL/min，热解处理的温度为570℃～700℃，热解处理的时间为3～4h，干燥温度为80℃～100℃，干燥时间为2～10h。Preferably, the inert gas flow rate in step (3) is 5 to 100 mL/min, the temperature of the pyrolysis treatment is 200°C to 1000°C, the time of the pyrolysis treatment is 3 to 10h, and the drying temperature is 80°C to 200°C. , drying time is 2~10h. Further preferably, the inert gas flow rate in step (3) is 7 to 15 mL/min, the temperature of the pyrolysis treatment is 570°C to 700°C, the time of the pyrolysis treatment is 3 to 4h, and the drying temperature is 80°C to 100°C. , drying time is 2~10h.
本发明还保护上述制备方法得到的K、Rb共掺杂C 3N 4光催化剂。 The invention also protects the K and Rb co-doped C 3 N 4 photocatalyst obtained by the above preparation method.
本发明还保护上述K、Rb共掺杂C 3N 4光催化剂在光催化CO 2还原协同乙醇氧化制乙醛中的应用，包括以下步骤：将所述的K、Rb共掺杂C 3N 4光催化剂分散在装有乙醇和乙腈水溶液的反应器中，向反应器内的混合液中吹入惰性气体以除去残留空气，随后向混合液中充入纯CO 2气体达到CO 2溶解饱和，然后在光照下驱动光催化CO 2还原和乙醇氧化协同反应，反应过程中向混合溶液中鼓入CO 2保持CO 2溶解饱和，并实时添加乙醇保持其浓度恒定。 The invention also protects the application of the above-mentioned K and Rb co-doped C 3 N 4 photocatalyst in photocatalytic CO 2 reduction and synergistic ethanol oxidation to produce acetaldehyde, and includes the following steps: co-doping the K and Rb with C 3 N 4. The photocatalyst is dispersed in a reactor filled with ethanol and acetonitrile aqueous solutions. Inert gas is blown into the mixed liquid in the reactor to remove residual air, and then pure CO 2 gas is filled into the mixed liquid to achieve CO 2 dissolution saturation. Then, the photocatalytic CO 2 reduction and ethanol oxidation synergistic reactions are driven under light. During the reaction, CO 2 is bubbled into the mixed solution to keep the CO 2 dissolved and saturated, and ethanol is added in real time to keep its concentration constant.
优选地，所述的混合液中光催化剂浓度为1～30mg/mL，乙醇体积分数为5％～40％，乙腈体积分数为5％～40％。Preferably, the photocatalyst concentration in the mixed solution is 1-30 mg/mL, the volume fraction of ethanol is 5%-40%, and the volume fraction of acetonitrile is 5%-40%.
优选地，所述的惰性气体为氮气或氩气，惰性气体通入时间为1～10min。所述的CO 2气体通入时间为1～10min，确保CO 2溶解饱和。 Preferably, the inert gas is nitrogen or argon, and the inert gas introduction time is 1 to 10 minutes. The CO 2 gas introduction time is 1 to 10 minutes to ensure CO 2 dissolution and saturation.
优选地，所述的光照光源波长为280～780nm，反应温度控制在5℃～25℃。Preferably, the wavelength of the illumination source is 280-780 nm, and the reaction temperature is controlled at 5°C-25°C.
本发明与现有技术相比，具有如下优点：本发明首次合成K、Rb共掺杂C 3N 4光催化剂，该光催化剂可同时光催化CO 2还原和乙醇氧化，生成的产物乙醛具有产率高和高选择性的优点。该光催化剂充分利用了光生电子和空穴，为共同设计CO 2还原和有机氧化反应途径以获得相同产品提供了新的途径。 Compared with the existing technology, the present invention has the following advantages: for the first time, the present invention synthesizes a K, Rb co-doped C 3 N 4 photocatalyst. The photocatalyst can simultaneously photocatalyze CO 2 reduction and ethanol oxidation, and the generated product acetaldehyde has The advantages of high yield and high selectivity. This photocatalyst makes full use of photogenerated electrons and holes, providing a new way to co-design CO reduction and organic oxidation reaction pathways to obtain the same products.
附图说明Description of the drawings
图1为实施例1制备得到的CN和CN-KRb的X射线衍射图(XRD)。Figure 1 is the X-ray diffraction pattern (XRD) of CN and CN-KRb prepared in Example 1.
图2为实施例1制备得到CN-KRb的X射线光电子能谱图(XPS)。Figure 2 is an X-ray photoelectron spectrum (XPS) of CN-KRb prepared in Example 1.
图3为利用实施例1制备得到的CN-KRb进行光催化CO 2还原协同乙醇氧化产物的质谱图(MS)。 Figure 3 is a mass spectrum (MS) of the product of photocatalytic CO 2 reduction and ethanol oxidation using CN-KRb prepared in Example 1.
图4为利用实施例1制备得到的CN-KRb进行光催化CO 2还原协同乙醇氧化产物的性能测试结果图。 Figure 4 is a diagram showing the performance test results of photocatalytic CO 2 reduction and synergistic ethanol oxidation products using CN-KRb prepared in Example 1.
具体实施方式：Detailed ways:
以下实施例是对本发明的进一步说明，而不是对本发明的限制。The following examples further illustrate the present invention, rather than limiting the present invention.
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。除特别说明，本文中的实验材料和试剂均为本技术领域常规市购产品。Unless otherwise defined, all technical terms used below have the same meanings as commonly understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental materials and reagents in this article are all conventional commercial products in this technical field.
实施例1Example 1
一种K、Rb共掺杂C 3N 4光催化剂的制备方法，包括以下步骤： A preparation method of K, Rb co-doped C 3 N 4 photocatalyst, including the following steps:
(1)将双氰胺(DCDA)放入管式炉中在7mL/min的氩气气氛中经570℃高温聚合4h，冷却至室温后所得产物研磨成细粉，得到氮化碳(C 3N 4)记为CN。 (1) Put dicyandiamide (DCDA) into a tube furnace and polymerize it at a high temperature of 570°C for 4 hours in an argon atmosphere of 7 mL/min. After cooling to room temperature, the resulting product is ground into fine powder to obtain carbon nitride (C 3 N 4 ) is denoted as CN.
(2)将步骤(1)制备得到的氮化碳(C 3N 4)与氯化钾(KCl)、氯化铷(RbCl)在去离子水中混合超声15min得到混合溶液，混合溶液中氮化碳(C 3N 4)的浓度为20mg/mL，氯化钾(KCl)的浓度为3mg/mL，氯化铷(RbCl)的浓度为3mg/mL，室温下搅拌4h后，在100℃下彻底干燥以释放水分6h，得到混合物固体。 (2) Mix the carbon nitride (C 3 N 4 ) prepared in step (1) with potassium chloride (KCl) and rubidium chloride (RbCl) in deionized water and sonicate for 15 minutes to obtain a mixed solution. Nitride the mixed solution The concentration of carbon (C 3 N 4 ) is 20 mg/mL, the concentration of potassium chloride (KCl) is 3 mg/mL, and the concentration of rubidium chloride (RbCl) is 3 mg/mL. After stirring for 4 hours at room temperature, stir at 100°C. Dry thoroughly to release water for 6 hours to obtain a solid mixture.
(3)将步骤(2)制备得到的混合物固体放入管式炉中，以7mL/min的流量通入氩气，加热至570℃进行热解处理4h后，冷却至室温，用水和乙醇洗涤3次以去除残留的金属盐， 并在100℃的烘箱中干燥2h。最后，得到K、Rb共掺杂C 3N 4光催化剂，记为CN-KRb。 (3) Put the solid mixture prepared in step (2) into a tube furnace, pass argon gas at a flow rate of 7 mL/min, heat to 570°C for pyrolysis treatment for 4 hours, cool to room temperature, and wash with water and ethanol. 3 times to remove residual metal salts and dried in an oven at 100°C for 2 h. Finally, a K and Rb co-doped C 3 N 4 photocatalyst was obtained, which was recorded as CN-KRb.
使用X射线衍射仪表征步骤(1)制备得到的CN及步骤(3)制备得到的CN-KRb，结果如图1所示。从图中可以看出，CN-KRb的结构与CN基本类似，有(100)和(002)两个特征峰，说明其主体结构在引入K和Rb之后基本保持不变。The CN prepared in step (1) and the CN-KRb prepared in step (3) were characterized using an X-ray diffractometer, and the results are shown in Figure 1. It can be seen from the figure that the structure of CN-KRb is basically similar to that of CN, with two characteristic peaks (100) and (002), indicating that its main structure remains basically unchanged after the introduction of K and Rb.
使用X射线光电子能谱仪表征CN-KRb，结果如图2所示。从图中可以看到明显的K 2p和Rb 3d的能谱峰，说明K和Rb都成功地插入到CN的结构中，同时从其结合能的位置可以推断出K和Rb在CN中以金属离子的形式存在。X-ray photoelectron spectroscopy was used to characterize CN-KRb, and the results are shown in Figure 2. From the figure, we can see obvious energy spectrum peaks of K 2p and Rb 3d, indicating that both K and Rb have been successfully inserted into the structure of CN. At the same time, it can be inferred from the position of their binding energy that K and Rb are metal-based in CN. exist in the form of ions.
实施例2Example 2
参考实施例1，不同之处在于：步骤(1)氩气流量为15mL/min，高温聚合温度为700℃，高温聚合时间为2h。Referring to Example 1, the difference is that: in step (1), the argon gas flow rate is 15 mL/min, the high-temperature polymerization temperature is 700°C, and the high-temperature polymerization time is 2 hours.
实施例3Example 3
参考实施例1，不同之处在于：步骤(2)混合溶液中氮化碳(C 3N 4)的浓度为40mg/mL，氯化钾(KCl)的浓度为10mg/mL，氯化铷(RbCl)的浓度为10mg/mL，超声时间为30min，搅拌时间为8h，干燥温度为200℃，干燥时间为5h。 Referring to Example 1, the difference is that: the concentration of carbon nitride (C 3 N 4 ) in the mixed solution in step (2) is 40 mg/mL, the concentration of potassium chloride (KCl) is 10 mg/mL, and the concentration of rubidium chloride ( The concentration of RbCl) was 10 mg/mL, the ultrasonic time was 30 min, the stirring time was 8 h, the drying temperature was 200°C, and the drying time was 5 h.
实施例4Example 4
参考实施例1，不同之处在于：步骤(3)氩气流量为15mL/min，热解处理的温度为700℃，热解处理的时间为3h，烘箱中干燥温度为80℃，干燥时间为10h。Referring to Example 1, the difference is that: in step (3), the argon flow rate is 15 mL/min, the pyrolysis temperature is 700°C, the pyrolysis time is 3h, the drying temperature in the oven is 80°C, and the drying time is 10h.
对比例1Comparative example 1
参考实施例1，不同之处在于：步骤(2)具体步骤为：将步骤(1)制备得到的氮化碳(C 3N 4)与氯化钾(KCl)在去离子水中混合超声15min得到混合溶液，混合溶液中氮化碳(C 3N 4)的浓度为20mg/mL，氯化钾(KCl)的浓度为6mg/mL，室温下搅拌4h后，在100℃ 下彻底干燥以释放水分6h，得到混合物固体。最终得到K掺杂C 3N 4光催化剂，记为CN-K。 Referring to Example 1, the difference is that: the specific steps of step (2) are: mixing the carbon nitride (C 3 N 4 ) prepared in step (1) and potassium chloride (KCl) in deionized water and ultrasonic for 15 minutes to obtain Mix the solution. The concentration of carbon nitride (C 3 N 4 ) in the mixed solution is 20 mg/mL, and the concentration of potassium chloride (KCl) is 6 mg/mL. After stirring at room temperature for 4 hours, dry it thoroughly at 100°C to release water. After 6h, the mixture solid was obtained. Finally, a K-doped C 3 N 4 photocatalyst was obtained, designated as CN-K.
对比例2Comparative example 2
参考实施例1，不同之处在于：步骤(2)具体步骤为：将步骤(1)制备得到的氮化碳(C 3N 4)与氯化铷(RbCl)在去离子水中混合超声15min得到混合溶液，混合溶液中氮化碳(C 3N 4)的浓度为20mg/mL，氯化铷(RbCl)的浓度为6mg/mL，室温下搅拌4h后，在100℃下彻底干燥以释放水分6h，得到混合物固体。最终得到Rb掺杂C 3N 4光催化剂，记为CN-Rb。 Referring to Example 1, the difference is that: the specific steps of step (2) are: mixing the carbon nitride (C 3 N 4 ) and rubidium chloride (RbCl) prepared in step (1) in deionized water and ultrasonic for 15 minutes to obtain Mix the solution. The concentration of carbon nitride (C 3 N 4 ) in the mixed solution is 20 mg/mL, and the concentration of rubidium chloride (RbCl) is 6 mg/mL. After stirring at room temperature for 4 hours, dry it thoroughly at 100°C to release moisture. After 6h, the mixture solid was obtained. Finally, an Rb-doped C 3 N 4 photocatalyst was obtained, designated as CN-Rb.
应用例1Application example 1
取上述实施例1步骤(1)所得的CN 10mg、实施例1步骤(3)所得的CN-KRb 10mg、对比例1所得的CN-K 10mg、对比例2所得的CN-Rb 10mg，分别分散在装有5mL 10％乙醇(EtOH)/10％乙腈(MeCN)水溶液的反应器中，超声处理15min以确保固体催化剂均匀分散在溶液中。向混合液中吹入氩气5min以除去残留空气，随后向混合溶液中充入纯CO 2气体5min以达到CO 2溶解饱和。然后在LED白光(光照光源波长为280～780nm)光照下驱动光催化CO 2还原和乙醇氧化协同反应，反应过程中向混合溶液中鼓入CO 2保持CO 2溶解饱和，并实时添加乙醇保持其浓度恒定。在整个实验过程中，反应温度保持在25℃。 Take 10 mg of CN obtained in step (1) of Example 1, 10 mg of CN-KRb obtained in step (3) of Example 1, 10 mg of CN-K obtained in Comparative Example 1, and 10 mg of CN-Rb obtained in Comparative Example 2, and disperse them respectively. In a reactor filled with 5 mL of 10% ethanol (EtOH)/10% acetonitrile (MeCN) aqueous solution, ultrasonic treatment was performed for 15 min to ensure that the solid catalyst was evenly dispersed in the solution. Argon gas was blown into the mixed solution for 5 min to remove residual air, and then pure CO 2 gas was charged into the mixed solution for 5 min to achieve CO 2 dissolution saturation. Then, the photocatalytic CO 2 reduction and ethanol oxidation synergistic reactions are driven under the illumination of LED white light (light source wavelength is 280-780 nm). During the reaction process, CO 2 is bubbled into the mixed solution to keep the CO 2 dissolved and saturated, and ethanol is added in real time to keep it saturated. The concentration is constant. The reaction temperature was maintained at 25°C throughout the experiment.
使用质谱仪表征CN-KRb进行光催化CO 2还原协同乙醇氧化产物，结果如图3。 Mass spectrometry was used to characterize the synergistic ethanol oxidation products of photocatalytic CO reduction by CN-KRb, and the results are shown in Figure 3.
CN、CN-KRb、CN-K和CN-Rb进行光催化CO 2还原协同乙醇氧化产物性能测试结果如图4所示，从图4中可以看出，相同的光催化剂用量条件下，CN-KRb生成的产物乙醛产率远高于CN-K或CN-Rb，反应中CN-KRb产生1212μmol/h/g的乙醛，同时其具有93.2％的乙醛高选择性。 The performance test results of CN, CN-KRb, CN-K and CN-Rb for photocatalytic CO 2 reduction and synergistic ethanol oxidation product are shown in Figure 4. It can be seen from Figure 4 that under the same photocatalyst dosage, CN- The yield of acetaldehyde generated by KRb is much higher than that of CN-K or CN-Rb. During the reaction, CN-KRb produces 1212 μmol/h/g acetaldehyde, and it has a high selectivity of 93.2% acetaldehyde.
以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想，应当指出，对于 本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The description of the above embodiments is only used to help understand the technical solutions and core ideas of the present invention. It should be pointed out that for those skilled in the art, several improvements can be made to the present invention without departing from the principles of the present invention. and modifications, these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

  1. K、Rb共掺杂C 3N 4光催化剂的制备方法，其特征在于，包括以下步骤： The preparation method of K, Rb co-doped C 3 N 4 photocatalyst is characterized by including the following steps:
    (1)将双氰胺在惰性气氛中高温聚合，冷却至室温后所得产物研磨，得到氮化碳C 3N 4； (1) Polymerize dicyandiamide at high temperature in an inert atmosphere, and then grind the product after cooling to room temperature to obtain carbon nitride C 3 N 4 ;
    (2)将步骤(1)得到的C 3N 4与钾盐、铷盐在去离子水中混合超声得到混合溶液，室温下搅拌均匀后干燥，得到混合物固体； (2) Mix the C 3 N 4 obtained in step (1) with potassium salt and rubidium salt in deionized water and ultrasonicate to obtain a mixed solution, stir evenly at room temperature and then dry to obtain a solid mixture;
    (3)将步骤(2)所述的混合物固体通入惰性气体进行热解处理，冷却至室温后洗涤，干燥得到K、Rb共掺杂C 3N 4光催化剂。 (3) Pass the mixture solid described in step (2) into an inert gas for pyrolysis treatment, cool to room temperature, wash, and dry to obtain a K and Rb co-doped C 3 N 4 photocatalyst.
  2. 根据权利要求1所述的制备方法，其特征在于，步骤(1)所述的高温聚合温度为200℃～700℃，高温聚合时间为1～10h，惰性气体流量为5～100mL/min。The preparation method according to claim 1, characterized in that the high-temperature polymerization temperature in step (1) is 200°C-700°C, the high-temperature polymerization time is 1-10h, and the inert gas flow rate is 5-100mL/min.
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(2)所述的钾盐为氯化钾，铷盐为氯化铷。The preparation method according to claim 1, characterized in that the potassium salt in step (2) is potassium chloride, and the rubidium salt is rubidium chloride.
  4. 根据权利要求3所述的制备方法，其特征在于，步骤(2)所述的混合溶液中C 3N 4的浓度为10～40mg/mL，氯化钾的浓度为1～10mg/mL，氯化铷的浓度为1～10mg/mL，超声时间为10～30min，搅拌时间为3～8h，干燥温度为50℃～200℃，干燥时间为5～10h。 The preparation method according to claim 3, characterized in that the concentration of C 3 N 4 in the mixed solution described in step (2) is 10 to 40 mg/mL, the concentration of potassium chloride is 1 to 10 mg/mL, and the concentration of chlorine is 1 to 10 mg/mL. The concentration of rubidium is 1~10mg/mL, the ultrasonic time is 10~30min, the stirring time is 3~8h, the drying temperature is 50℃~200℃, and the drying time is 5~10h.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(3)所述的惰性气体流量为5～100mL/min，热解处理的温度为200℃～1000℃，热解处理的时间为3～10h，干燥温度为80℃～200℃，干燥时间为2～10h。The preparation method according to claim 1, characterized in that the inert gas flow rate in step (3) is 5 to 100 mL/min, the temperature of the pyrolysis treatment is 200°C to 1000°C, and the time of the pyrolysis treatment is 3 ~10h, drying temperature is 80℃~200℃, drying time is 2~10h.
  6. 权利要求1-5任一项所述的制备方法得到的K、Rb共掺杂C 3N 4光催化剂。 The K, Rb co-doped C 3 N 4 photocatalyst obtained by the preparation method according to any one of claims 1 to 5.
  7. 权利要求6所述的K、Rb共掺杂C 3N 4光催化剂在光催化CO 2还原协同乙醇氧化制乙醛中的应用，其特征在于，包括以下步骤：将所述的光催化剂分散在装有乙醇和乙腈水溶液的反 应器中，向反应器内的混合液中吹入惰性气体以除去残留空气，随后向混合液中充入纯CO 2气体达到CO 2溶解饱和，然后在光照下驱动光催化CO 2还原和乙醇氧化协同反应，反应过程中向混合溶液中鼓入CO 2保持CO 2溶解饱和，并实时添加乙醇保持其浓度恒定。 The application of the K, Rb co-doped C 3 N 4 photocatalyst in claim 6 in the production of acetaldehyde through photocatalytic CO 2 reduction and synergistic ethanol oxidation, characterized in that it includes the following steps: dispersing the photocatalyst in In a reactor filled with ethanol and acetonitrile aqueous solution, inert gas is blown into the mixed liquid in the reactor to remove residual air, and then pure CO 2 gas is filled into the mixed liquid to reach CO 2 dissolution saturation, and then driven under light Photocatalytic CO 2 reduction and ethanol oxidation react synergistically. During the reaction, CO 2 is bubbled into the mixed solution to keep the CO 2 dissolved and saturated, and ethanol is added in real time to keep its concentration constant.
  8. 根据权利要求7所述的应用，其特征在于，所述的混合液中光催化剂浓度为1～30mg/mL，乙醇体积分数为5％～40％，乙腈体积分数为5％～40％。The application according to claim 7, characterized in that the photocatalyst concentration in the mixed solution is 1-30 mg/mL, the ethanol volume fraction is 5%-40%, and the acetonitrile volume fraction is 5%-40%.
  9. 根据权利要求7所述的应用，其特征在于，所述的惰性气体为氮气或氩气，惰性气体通入时间为1～10min。The application according to claim 7, characterized in that the inert gas is nitrogen or argon, and the inert gas introduction time is 1 to 10 minutes.
  10. 根据权利要求7所述的应用，其特征在于，所述的光照光源波长为280～780nm，反应温度控制在5℃～25℃。The application according to claim 7, characterized in that the wavelength of the illumination source is 280-780nm, and the reaction temperature is controlled at 5°C-25°C.
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