WO2024146222A1 - Method for preparing highly-dispersed pt/ceo2 by using atomically dispersed platinum as precursor and use - Google Patents

Method for preparing highly-dispersed pt/ceo2 by using atomically dispersed platinum as precursor and use Download PDF

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WO2024146222A1
WO2024146222A1 PCT/CN2023/127217 CN2023127217W WO2024146222A1 WO 2024146222 A1 WO2024146222 A1 WO 2024146222A1 CN 2023127217 W CN2023127217 W CN 2023127217W WO 2024146222 A1 WO2024146222 A1 WO 2024146222A1
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ceo2
dispersed
temperature
platinum
precursor
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任泉明
赵晓雅
刘鹏
付名利
叶代启
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华南理工大学
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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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the CeO2 prepared in step (1) is weighed and dispersed in deionized water containing a certain amount of platinum salt of a certain concentration.
  • the resulting suspension D is sonicated at room temperature, dried in a shaker, and then transferred to a tube furnace for high-temperature calcination to obtain a single-atom dispersed Pt/ CeO2 sample;
  • the single-atom dispersed Pt/ CeO2 sample prepared in step (2) is calcined in a high-temperature reducing atmosphere to obtain a black highly dispersed Pt/ CeO2 sample.
  • the mass of CeO2 is 0.75 ⁇ 1.25 g; the platinum salt is tetraammine platinum nitrate; the concentration of the platinum salt solution is 4.84 ⁇ 8.06 mmol/mL; the volume of the platinum salt solution is 1.5 ⁇ 2.5 mL; the ultrasonic time is 0.5 ⁇ 1 h; the ultrasonic frequency is 20 ⁇ 40 kHz, and the ultrasonic power is 280 ⁇ 560 W; the shaking table speed is 120 ⁇ 180 rmp; the shaking table temperature is 60 ⁇ 80 °C; the shaking table drying time is 8 ⁇ 16 h; the high-temperature calcination method in the tubular furnace is as follows: in a dry air atmosphere, the gas flow rate is 80 mL/min, the temperature is increased from room temperature to 400 ⁇ 900 °C at a rate of 3 ⁇ 5 °C/min, the temperature is kept constant for 5 ⁇ 10 h, then the temperature is reduced to room temperature, and the dry air is turned off.
  • the high temperature calcination method is to increase the temperature from room temperature to 250-350°C at a rate of 3-5°C/min under a 5-15 vol.% H2 /Ar atmosphere with a gas flow rate of 60-100 mL/min, maintain the temperature for 2-4 h, then cool to room temperature and turn off the reducing gas.
  • the toluene/dry air concentration is 200 ⁇ 2000 ppm, and the carbon monoxide/dry air concentration is 1000 ⁇ 10000 ppm;
  • the heating furnace temperature is 30 ⁇ 450°C, each reaction temperature point is retained for 50 min, and the temperature is increased to the next reaction temperature point at a rate of 1°C/min for 10 min;
  • the toluene/dry air and carbon monoxide/dry air flow rates are both 50 ⁇ 100 mL;
  • the amount of catalyst used in the toluene catalytic purification and carbon monoxide complete oxidation reactions is 50 ⁇ 150 mg.
  • the preparation process is simple and easy, and the preparation conditions are relatively mild, which can achieve large-scale preparation.
  • the preparation process does not require the addition of additional surfactants, organic solvents, etc., which greatly reduces the preparation cost of the catalyst.
  • FIG1 is a SEM of the CeO 2 carrier prepared in Example 1;
  • FIG2 is a high-resolution transmission electron micrograph of a single-atom dispersed Pt/CeO 2 sample (with a loading amount of the noble metal active component of 0.5 wt.%) prepared in Example 2;
  • FIG3 is a high-angle annular dark field image of a highly dispersed Pt/CeO 2 sample prepared in Example 3;
  • Figure 5 is a catalytic activity curve of the prepared Pt/ CeO2 samples for catalytic oxidation of toluene and complete oxidation of carbon monoxide; wherein a) is the single-atom dispersed Pt/ CeO2 sample prepared in Example 2; b) is the highly dispersed Pt/ CeO2 sample prepared in Example 3.
  • the initial concentration of toluene was 1000 ppm, the space velocity was 60000 mL h -1 g -1 , and the reaction activity curve was shown in Figure 5a.
  • the conversion rate of toluene (T 90% ) was 239 °C.
  • the gas flow rate was 80 mL/min, and the temperature was raised from room temperature to 800 °C at a rate of 3-5 °C/min. The temperature was maintained constant for 10 h, and then the suspension was cooled to room temperature. The dry air was closed to obtain a single-atom dispersed Pt/ CeO2 sample.
  • the initial carbon monoxide concentration was 5000 ppm
  • the space velocity was 33000 mL h -1 g -1
  • the reaction activity curve was shown in Figure 5b.
  • the carbon monoxide conversion rate (T 90% ) was 75 °C.

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Abstract

A method for preparing highly-dispersed Pt/CeO2 by using atomically dispersed platinum as a precursor and the use. The method comprises: by means of a high-temperature heat treatment method, roasting at a high temperature Pt/CeO2 prepared in advance by using an impregnation method, so as to obtain atomically dispersed Pt on the surface of CeO2; and then reducing the atomically dispersed Pt/CeO2 in a reducing atmosphere so as to obtain highly-dispersed Pt/CeO2, and using same for catalytic purification of volatile organic compounds and complete oxidation of carbon monoxide. The method for preparing the highly-dispersed Pt/CeO2 is easy to implement and can achieve large-scale preparation; and more importantly, the preparation process does not require the addition of extra surfactants to achieve the preparation of the highly-dispersed Pt/CeO2, thereby greatly reducing the preparation cost of the catalyst. In addition, the highly-dispersed Pt/CeO2 exhibits excellent catalytic oxidation performance.

Description

一种以单原子分散铂为前体物制备高分散Pt/CeO 2的方法与应用 A method and application for preparing highly dispersed Pt/CeO 2 using single-atom dispersed platinum as a precursor 技术领域Technical Field
本发明涉及一种以单原子分散铂为前体物制备高分散Pt/CeO 2的方法，并将其用于挥发性有机物的催化净化、一氧化碳完全氧化，属于热催化材料技术领域。 The invention relates to a method for preparing highly dispersed Pt/ CeO2 by using single-atom dispersed platinum as a precursor, and using the method for catalytic purification of volatile organic matter and complete oxidation of carbon monoxide, belonging to the technical field of thermal catalytic materials.
背景技术Background technique
随着社会经济和工业技术的快速发展，大气环境中细颗粒物（PM 2.5）和臭氧（O 3）浓度逐年增加，由此导致城市空气质量问题是我国当前迫切需要解决的重要环境问题。挥发性有机物（VOCs）作为PM 2.5和O 3形成的重要前体物，“十四五”期间国家对VOCs排放总量设定为下降10%的目标，目前VOCs排放总量虽有所下降，但仍处高位，VOCs的减排仍是目前我国大气复合污染控制面临重要环境问题之一。另一方面，据我国公安部统计数据，截至2022年9月底，全国汽车保有量高达3.15亿辆，其中新能源汽车保有量仅占汽车保有量的3.65%，表明燃油汽车保有量仍超过3亿辆。据报道，尾气中排放的一氧化碳（CO）不仅危害健康，而且污染环境。因此，如何高效净化挥发性有机污染物和一氧化碳，是目前提升大气环境质量亟待解决的问题，而且契合我国建设生态文明建设的奋斗目标，具有极其重要的战略意义。 With the rapid development of social economy and industrial technology, the concentration of fine particulate matter (PM 2.5 ) and ozone (O 3 ) in the atmospheric environment has increased year by year, resulting in the problem of urban air quality, which is an important environmental problem that China urgently needs to solve. Volatile organic compounds (VOCs) are important precursors to the formation of PM 2.5 and O 3. During the 14th Five-Year Plan period, the country has set a target of reducing the total amount of VOCs emissions by 10%. Although the total amount of VOCs emissions has decreased, it is still at a high level. The reduction of VOCs is still one of the important environmental problems facing China's current atmospheric complex pollution control. On the other hand, according to statistics from the Ministry of Public Security of China, as of the end of September 2022, the number of cars in the country will reach 315 million, of which the number of new energy vehicles accounts for only 3.65% of the total number of cars, indicating that the number of fuel vehicles is still more than 300 million. It is reported that carbon monoxide (CO) emitted in exhaust gas is not only harmful to health, but also pollutes the environment. Therefore, how to efficiently purify volatile organic pollutants and carbon monoxide is an urgent problem to be solved in order to improve the quality of the atmospheric environment. It is also in line with my country's goal of building an ecological civilization and has extremely important strategic significance.
目前，VOCs的末端治理技术有热力焚烧技术、臭氧催化氧化技术、吸附技术、非热等离子体技术、生物降解技术、光催化技术、以及催化氧化技术等，其中催化氧化技术因具有净化效率高、二次污染少、占地面积小等诸多优势，而被受到广泛关注。在催化氧化技术中，其核心是高效、稳定催化剂的设计与制备。针对目前应用的催化剂存在长期稳定较差、催化活性较低、抗水性较弱、制备成本较高等缺点，因此亟待研发一种长期稳定较好、催化活性较高、抗水性较强、制备成本较低的VOCs净化催化剂。目前，已有大量的催化剂用于VOCs的降解，尤其是Pt/CeO 2催化剂因其载体具有良好的储氧能力和热稳定性、Pt与CeO 2之间有丰富的活性位点，因此，Pt/CeO 2催化剂被广泛应用。当前，为了进一步降低Pt颗粒的尺寸，增加Pt与CeO 2之间活性位点的数量，从而进一步提升催化剂的催化性能，许多报道采用表面活性剂、有机溶剂等来制备近亚纳米尺度的Pt颗粒，然而这些方法不仅繁琐，而且严重增加了催化剂的制备成本。 At present, the end-of-pipe treatment technologies for VOCs include thermal incineration technology, ozone catalytic oxidation technology, adsorption technology, non-thermal plasma technology, biodegradation technology, photocatalytic technology, and catalytic oxidation technology. Among them, catalytic oxidation technology has attracted widespread attention due to its many advantages such as high purification efficiency, less secondary pollution, and small footprint. In catalytic oxidation technology, the core is the design and preparation of efficient and stable catalysts. In view of the shortcomings of the currently used catalysts, such as poor long-term stability, low catalytic activity, weak water resistance, and high preparation cost, it is urgent to develop a VOCs purification catalyst with good long-term stability, high catalytic activity, strong water resistance, and low preparation cost. At present, a large number of catalysts have been used for the degradation of VOCs, especially Pt/ CeO2 catalysts, because their carriers have good oxygen storage capacity and thermal stability, and there are abundant active sites between Pt and CeO2 . Therefore, Pt/ CeO2 catalysts are widely used. Currently, in order to further reduce the size of Pt particles and increase the number of active sites between Pt and CeO2 , thereby further improving the catalytic performance of the catalyst, many reports have used surfactants, organic solvents, etc. to prepare near-subnanometer-scale Pt particles. However, these methods are not only cumbersome, but also seriously increase the preparation cost of the catalyst.
技术解决方案Technical Solutions
考虑到上述情况，本发明开发了以一种以单原子分散铂为前体物制备高分散Pt/CeO 2的方法，该方法制备过程无需额外添加表面活性剂、有机溶剂等，极大降低催化剂的制备成本，且制备方法简单，制备出的催化剂Pt颗粒尺寸接近亚纳米尺度，而且尺寸均一，此外催化剂对甲苯和一氧化碳均表现出优异的催化性能。该方法能够实现规模化制备，且在挥发性有机污染物的净化和一氧化碳的完全氧化等催化氧化领域有着巨大的应用潜力。 Taking the above into consideration, the present invention has developed a method for preparing highly dispersed Pt/ CeO2 using single-atom dispersed platinum as a precursor. The preparation process of this method does not require the addition of additional surfactants, organic solvents, etc., which greatly reduces the preparation cost of the catalyst. The preparation method is simple, and the prepared catalyst Pt particle size is close to the sub-nanometer scale and the size is uniform. In addition, the catalyst exhibits excellent catalytic performance for toluene and carbon monoxide. This method can achieve large-scale preparation and has great application potential in the field of catalytic oxidation such as purification of volatile organic pollutants and complete oxidation of carbon monoxide.
本发明的目的在于克服现有制备成本高、需额外添加表面活性剂、有机溶剂制备近亚纳米铂颗粒方法的不足，提供一种简单可行，能够实现规模化制备接近亚纳米尺度的铂颗粒，而且铂颗粒尺寸均一，此外制备的Pt/CeO 2催化剂对甲苯和一氧化碳均表现出优异的催化性能。 The purpose of the present invention is to overcome the shortcomings of the existing methods for preparing near-subnanometer platinum particles, such as high preparation cost and the need for additional addition of surfactants and organic solvents, and to provide a simple and feasible method that can achieve large-scale preparation of platinum particles close to the subnanometer scale, and the platinum particles have uniform size. In addition, the prepared Pt/ CeO2 catalyst exhibits excellent catalytic performance for both toluene and carbon monoxide.
一种以单原子分散铂为前体物制备高分散Pt/CeO 2的方法，制备方法包括以下步骤： A method for preparing highly dispersed Pt/ CeO2 using single atomic dispersed platinum as a precursor, the preparation method comprising the following steps:
（1）CeO 2的制备： (1) Preparation of CeO2 :
室温搅拌下，称取醋酸铈和氢氧化钠分别溶解在去离子水中，形成溶液A和溶液B；随后将溶液B缓慢加入溶液A中混合搅拌得到浅紫色悬浮液C，将所得悬浮液C在室温下搅拌均匀后，转移至水热反应釜内进行水热反应，待降至室温后将水热后的悬浮液离心、洗涤数次至洗涤液pH为中性、烘干得到淡黄色粉末CeO 2载体备用； Under stirring at room temperature, cerium acetate and sodium hydroxide were weighed and dissolved in deionized water respectively to form solution A and solution B; then solution B was slowly added to solution A and mixed and stirred to obtain a light purple suspension C; the obtained suspension C was stirred evenly at room temperature, and then transferred to a hydrothermal reactor for hydrothermal reaction; after cooling to room temperature, the hydrothermal suspension was centrifuged, washed several times until the pH of the washing solution was neutral, and dried to obtain a light yellow powder CeO2 carrier for standby use;
（2）单原子分散Pt/CeO 2的制备： (2) Preparation of single-atom dispersed Pt/CeO 2 :
称取步骤（1）所制备的CeO 2分散在含有一定量某浓度铂盐的去离子水中，所得的悬浮液D在室温下超声，并在摇床中烘干，再转移至管式炉高温焙烧，得到单原子分散Pt/CeO 2样品； The CeO2 prepared in step (1) is weighed and dispersed in deionized water containing a certain amount of platinum salt of a certain concentration. The resulting suspension D is sonicated at room temperature, dried in a shaker, and then transferred to a tube furnace for high-temperature calcination to obtain a single-atom dispersed Pt/ CeO2 sample;
（3）高分散Pt/CeO 2的制备： (3) Preparation of highly dispersed Pt/ CeO2 :
将步骤（2）中制备的单原子分散Pt/CeO 2样品，通过高温还原气氛焙烧，获得黑色高分散Pt/CeO 2样品。 The single-atom dispersed Pt/ CeO2 sample prepared in step (2) is calcined in a high-temperature reducing atmosphere to obtain a black highly dispersed Pt/ CeO2 sample.
（4）将步骤（2）和（3）中的Pt/CeO 2样品，在压片机设定压强下压片，过筛，得到40~60目的催化剂。 (4) The Pt/ CeO2 samples in steps (2) and (3) are pressed into tablets at a set pressure on a tablet press, and sieved to obtain a catalyst with a mesh size of 40 to 60.
上述方法，步骤（1）中，所述醋酸铈质量为0.79~2.37 g，所述氢氧化钠的质量为7.7~23.1 g，所述溶液A和溶液B中去离子水的体积分别为10~30 mL和27.5~82.5 mL，悬浮液C中去离子水的体积为37.5~112.5 mL；所述搅拌温度为20~35 ℃；所述搅拌时间为0.5~1 h；所述搅拌速率100~200 r/min；所述反应釜体积规格为60～100 mL；所述水热反应温度为120～140 ℃，反应压力0.1～0.3 MPa，反应时间为3～7 h，离心转速为3500～4000 r/min；所述pH为7～8；所述烘干温度为60~80 ℃，所述烘干时间为8~16 h。In the above method, in step (1), the mass of cerium acetate is 0.79-2.37 g, the mass of sodium hydroxide is 7.7-23.1 g, the volumes of deionized water in solution A and solution B are 10-30 mL and 27.5-82.5 mL respectively, and the volume of deionized water in suspension C is 37.5-112.5 mL; the stirring temperature is 20-35°C; the stirring time is 0.5-1 h; the stirring rate is 100-200 r/min; the volume specification of the reactor is 60-100 mL; the hydrothermal reaction temperature is 120-140°C, the reaction pressure is 0.1-0.3 MPa, the reaction time is 3-7 h, and the centrifugal speed is 3500-4000 r/min; the pH is 7-8; the drying temperature is 60-80°C, and the drying time is 8-16 h.
上述方法，步骤（2）中，所述CeO 2的质量为0.75~1.25 g；所述铂盐为四氨合硝酸铂；所述铂盐溶液浓度为4.84~8.06 mmol/mL；所述铂盐溶液体积为1.5~2.5 mL；所述超声时间为0.5~1 h；所述超声频率为20~40 kHz，超声功率为280~560 W；所述摇床转速120~180 rmp；所述摇床温度60~80 ℃；所述摇床干燥时间为8~16 h；所述管式炉高温焙烧方法为，在干空气氛下，气体流速为80 mL/min，从室温以3~5 ℃/min的速率升温至400~900 ℃，恒温5~10 h，随后降至室温，关闭干空。 In the above method, in step (2), the mass of CeO2 is 0.75~1.25 g; the platinum salt is tetraammine platinum nitrate; the concentration of the platinum salt solution is 4.84~8.06 mmol/mL; the volume of the platinum salt solution is 1.5~2.5 mL; the ultrasonic time is 0.5~1 h; the ultrasonic frequency is 20~40 kHz, and the ultrasonic power is 280~560 W; the shaking table speed is 120~180 rmp; the shaking table temperature is 60~80 °C; the shaking table drying time is 8~16 h; the high-temperature calcination method in the tubular furnace is as follows: in a dry air atmosphere, the gas flow rate is 80 mL/min, the temperature is increased from room temperature to 400~900 °C at a rate of 3~5 °C/min, the temperature is kept constant for 5~10 h, then the temperature is reduced to room temperature, and the dry air is turned off.
上述方法，步骤（3）中，所述高温焙烧方法为，在5~15 vol.% H 2/Ar气氛下，气体流速为60~100 mL/min，从室温以3~5 ℃/min的速率升温至250~350 ℃，恒温2~4 h，随后降至室温后，关闭还原气。 In the above method, in step (3), the high temperature calcination method is to increase the temperature from room temperature to 250-350°C at a rate of 3-5°C/min under a 5-15 vol.% H2 /Ar atmosphere with a gas flow rate of 60-100 mL/min, maintain the temperature for 2-4 h, then cool to room temperature and turn off the reducing gas.
上述方法，步骤（4）中，所述的压片机压强为12～16 MPa，稳定时间为1～3 min。In the above method, in step (4), the tablet press pressure is 12 to 16 MPa, and the stabilization time is 1 to 3 min.
一种以单原子分散铂为前体物制备高分散Pt/CeO 2催化剂应用于挥发性有机物的催化净化、一氧化碳完全氧化。对于挥发性有机物的催化净化，选取甲苯为目标污染物，将甲苯/干空通入装有高分散Pt/CeO 2催化剂的石英管，石英管置于带有热偶的管式炉中加热，甲苯经过催化剂，会完全氧化为二氧化碳和水；对于一氧化碳完全氧化，一氧化碳/干空经过催化剂，会完全氧化为二氧化碳。 A highly dispersed Pt/CeO 2 catalyst prepared with single-atom dispersed platinum as a precursor is applied to the catalytic purification of volatile organic compounds and the complete oxidation of carbon monoxide. For the catalytic purification of volatile organic compounds, toluene is selected as the target pollutant, and toluene/dry air is passed through a quartz tube filled with a highly dispersed Pt/CeO 2 catalyst. The quartz tube is placed in a tube furnace with a thermocouple for heating. Toluene will be completely oxidized to carbon dioxide and water after passing through the catalyst; for the complete oxidation of carbon monoxide, carbon monoxide/dry air will be completely oxidized to carbon dioxide after passing through the catalyst.
上述应用中，所述甲苯/干空浓度为200~2000 ppm，所述一氧化碳/干空浓度为1000~10000 ppm；所述加热炉温度30~450 ℃，每个反应温度点保留50 min，以1 ℃/min的速率10min升温至下一个反应温度点；所述甲苯/干空、一氧化碳/干空流速均为50~100 mL；所述甲苯催化净化、一氧化碳完全氧化反应中催化剂的用量均为50~150 mg。In the above application, the toluene/dry air concentration is 200~2000 ppm, and the carbon monoxide/dry air concentration is 1000~10000 ppm; the heating furnace temperature is 30~450°C, each reaction temperature point is retained for 50 min, and the temperature is increased to the next reaction temperature point at a rate of 1°C/min for 10 min; the toluene/dry air and carbon monoxide/dry air flow rates are both 50~100 mL; the amount of catalyst used in the toluene catalytic purification and carbon monoxide complete oxidation reactions is 50~150 mg.
有益效果Beneficial Effects
本发明采用高温热处理方法，将预先采用浸渍法制备好的Pt/CeO 2在高温下焙烧，在CeO 2表面获得单原子分散的Pt，随后将单原子分散的Pt/CeO 2在还原气氛下还原，获得高分散Pt/CeO 2催化剂。该催化剂制备方法的制备过程无需额外添加表面活性剂、有机溶剂等，极大降低催化剂的制备成本，且制备方法简单，制备出的催化剂Pt颗粒尺寸接近亚纳米尺度，而且尺寸均一，此外催化剂对甲苯和一氧化碳均表现出优异的催化性能。 The present invention adopts a high-temperature heat treatment method to calcine Pt/ CeO2 prepared in advance by an impregnation method at a high temperature, obtain monoatomic dispersed Pt on the surface of CeO2 , and then reduce the monoatomic dispersed Pt/ CeO2 in a reducing atmosphere to obtain a highly dispersed Pt/ CeO2 catalyst. The preparation process of the catalyst preparation method does not require the addition of additional surfactants, organic solvents, etc., greatly reducing the preparation cost of the catalyst, and the preparation method is simple. The prepared catalyst Pt particle size is close to the sub-nanometer scale and the size is uniform. In addition, the catalyst exhibits excellent catalytic performance to toluene and carbon monoxide.
与现有技术相比，本发明具有以下优势：Compared with the prior art, the present invention has the following advantages:
（1）制备过程简单易行，制备条件比较温和，可是实现规模化制备，制备过程无需额外添加表面活性剂、有机溶剂等，极大降低催化剂的制备成本。(1) The preparation process is simple and easy, and the preparation conditions are relatively mild, which can achieve large-scale preparation. The preparation process does not require the addition of additional surfactants, organic solvents, etc., which greatly reduces the preparation cost of the catalyst.
（2）将预先采用浸渍法制备好的Pt/CeO 2在高温下焙烧，在CeO 2表面获得单原子分散的Pt，随后将单原子分散的Pt/CeO 2在还原气氛下还原，获得高分散Pt/CeO 2催化剂，Pt颗粒大小均一，且催化氧化性能大幅提升。 (2) The Pt/ CeO2 prepared by the impregnation method is calcined at a high temperature to obtain single-atom dispersed Pt on the surface of CeO2 . The single-atom dispersed Pt/ CeO2 is then reduced in a reducing atmosphere to obtain a highly dispersed Pt/ CeO2 catalyst with uniform Pt particle size and greatly improved catalytic oxidation performance.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1 是实施例1制备CeO 2载体的SEM； FIG1 is a SEM of the CeO 2 carrier prepared in Example 1;
图2 是实施例2制备的单原子分散Pt/CeO 2样品（贵金属活性成分的负载量为0.5 wt.%）的高分辨透射电镜图； FIG2 is a high-resolution transmission electron micrograph of a single-atom dispersed Pt/CeO 2 sample (with a loading amount of the noble metal active component of 0.5 wt.%) prepared in Example 2;
图3 是实施例3制备的高分散Pt/CeO 2样品的高角环形暗场图； FIG3 is a high-angle annular dark field image of a highly dispersed Pt/CeO 2 sample prepared in Example 3;
图4 是制备的Pt/CeO 2样品的一氧化碳作为探针分子的红外吸附图；其中a)为实施例2制备的单原子分散Pt/CeO 2样品；b)为实施例3制备的高分散Pt/CeO 2样品； FIG4 is an infrared adsorption diagram of carbon monoxide as a probe molecule of the prepared Pt/CeO 2 sample; wherein a) is the single-atom dispersed Pt/CeO 2 sample prepared in Example 2; b) is the highly dispersed Pt/CeO 2 sample prepared in Example 3;
图5 是制备的Pt/CeO 2样品的甲苯催化氧化和一氧化碳完全氧化的催化活性曲线图；其中a)为实施例2制备的单原子分散Pt/CeO 2样品；b)为实施例3制备的高分散Pt/CeO 2样品。 Figure 5 is a catalytic activity curve of the prepared Pt/ CeO2 samples for catalytic oxidation of toluene and complete oxidation of carbon monoxide; wherein a) is the single-atom dispersed Pt/ CeO2 sample prepared in Example 2; b) is the highly dispersed Pt/ CeO2 sample prepared in Example 3.
本发明的实施方式Embodiments of the present invention
下面结合本发明实施例中的附图，对实施例中的技术方案进行清楚、完整地阐述，这些仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings in the embodiments of the present invention. These are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
实施例1Example 1
（1）CeO 2载体的制备 (1) Preparation of CeO2 carrier
室温搅拌下，称取1.58 g醋酸铈和15.4 g氢氧化钠分别溶解在20 mL和55 mL去离子水中，形成溶液A和溶液B；随后将溶液B缓慢加入溶液A中混合搅拌得到浅紫色悬浮液C，将所得悬浮液C在室温下搅拌均匀后，转移至100 mL的水热反应釜内，密封后置于鼓风干燥箱，以2 ℃/min的升温速率从室温升至130 ℃，并保留5 h，待反应釜降至室温后将水热后的悬浮液离心，离心机转速为4000 r/min，洗涤数次至洗涤液pH为7~8、随后转移至烘箱80 ℃烘干14 h，研磨后得到淡黄色粉末CeO 2载体。 Under stirring at room temperature, 1.58 g of cerium acetate and 15.4 g of sodium hydroxide were weighed and dissolved in 20 mL and 55 mL of deionized water, respectively, to form solution A and solution B; then solution B was slowly added to solution A and mixed and stirred to obtain a light purple suspension C. The obtained suspension C was stirred evenly at room temperature and transferred to a 100 mL hydrothermal reactor, which was sealed and placed in a blast drying oven. The temperature was raised from room temperature to 130 °C at a rate of 2 °C/min and retained for 5 h. After the reactor was cooled to room temperature, the hydrothermal suspension was centrifuged at a centrifuge speed of 4000 r/min. It was washed several times until the pH of the washing solution was 7-8, and then transferred to an oven at 80 °C for drying for 14 h. After grinding, a light yellow powder CeO2 carrier was obtained.
由图1 SEM图可知，成功制备了纳米棒状的CeO 2载体。 As can be seen from the SEM image in Figure 1, nanorod-shaped CeO 2 carriers were successfully prepared.
实施例2Example 2
（1）单原子分散Pt/CeO 2催化剂的制备 (1) Preparation of single-atom dispersed Pt/CeO 2 catalyst
称取1 g实施例1中制备的CeO 2粉末分散在含有2.0 mL溶液浓度为6.45 mmol四氨合硝酸铂的去离子水中，所得的悬浮液D在室温下超声30 min，超声频率为30 kHz，超声功率420 W，然后转移至摇床中以转速150 rmp，温度70 ℃，干燥时间为14 h，再转移至管式炉高温焙烧，在干空气氛下，气体流速为80 mL/min，以3~5 ℃/min的速率从室温升温至800 ℃，恒温10 h，随后降至室温，关闭干空，得到单原子分散Pt/CeO 2样品。将Pt/CeO 2样品在压片机设定压强下(14 MPa)压片，过筛，得到40~60目的催化剂。 1 g of CeO 2 powder prepared in Example 1 was weighed and dispersed in deionized water containing 2.0 mL of solution with a concentration of 6.45 mmol of tetraammine platinum nitrate. The resulting suspension D was ultrasonicated at room temperature for 30 min, with an ultrasonic frequency of 30 kHz and an ultrasonic power of 420 W, and then transferred to a shaker at a speed of 150 rmp, a temperature of 70 ℃, and a drying time of 14 h, and then transferred to a tube furnace for high-temperature calcination. In a dry air atmosphere, the gas flow rate was 80 mL/min, and the temperature was raised from room temperature to 800 ℃ at a rate of 3~5 ℃/min, and the temperature was kept constant for 10 h, then cooled to room temperature, and the dry air was closed to obtain a single-atom dispersed Pt/CeO 2 sample. The Pt/CeO 2 sample was tableted at the set pressure of the tablet press (14 MPa) and sieved to obtain a catalyst of 40~60 mesh.
由图2 高分辨透射电镜图可知，在CeO 2的{220}晶面上沿A→B、E→F、G→H等方向有明显的Pt单原子；此外，由图4a 一氧化碳在样品上的吸附结果显示，一氧化碳主要吸附在离子态的Pt上，综合上述结果表明成功制备了单原子分散Pt/CeO 2样品。 As can be seen from the high-resolution transmission electron microscopy image in Figure 2, there are obvious Pt single atoms along the A→B, E→F, G→H and other directions on the {220} crystal plane of CeO2 ; in addition, the adsorption results of carbon monoxide on the sample in Figure 4a show that carbon monoxide is mainly adsorbed on ionic Pt. The above results show that the single-atom dispersed Pt/ CeO2 sample was successfully prepared.
（2）将100 mg单原子分散Pt/CeO 2与400 mg石英砂（60-80目）在反应床层混合均匀，在反应温度区间，通入甲苯/干空混合气，每个反应温度点保留50 min，相邻的两个温度点间隔10 ℃，以1 ℃/min的速率升温至下一个反应温度点。反应过程中，反应物甲苯和产物二氧化碳的浓度被岛津气相色谱GC-2014C实时在线检测。其中，甲苯的转化率计算公式如下所示：甲苯转化率 = [(甲苯)进口浓度-(甲苯)出口进口浓度]/(甲苯)进口浓度*100%。甲苯初始浓度为1000 ppm，空速为60000 mL h -1g -1，反应活性曲线如图5a，其甲苯的转化率（T 90%）为239 ℃。 (2) 100 mg of monoatomic dispersed Pt/CeO 2 and 400 mg of quartz sand (60-80 mesh) were mixed evenly in the reaction bed. In the reaction temperature range, a toluene/dry air mixture was introduced. Each reaction temperature point was retained for 50 min. The interval between two adjacent temperature points was 10 °C, and the temperature was raised to the next reaction temperature point at a rate of 1 °C/min. During the reaction, the concentrations of reactant toluene and product carbon dioxide were detected in real time online by Shimadzu gas chromatograph GC-2014C. The conversion rate of toluene was calculated as follows: Toluene conversion rate = [(toluene) inlet concentration - (toluene) outlet inlet concentration] / (toluene) inlet concentration * 100%. The initial concentration of toluene was 1000 ppm, the space velocity was 60000 mL h -1 g -1 , and the reaction activity curve was shown in Figure 5a. The conversion rate of toluene (T 90% ) was 239 °C.
（3）将100 mg单原子分散Pt/CeO 2与400 mg石英砂（60-80目）在反应床层混合均匀，在反应温度区间，通入一氧化碳/干空混合气，每个反应温度点保留50 min，以1 ℃/min的速率升温至下一个反应温度点。反应过程中，反应物一氧化碳和产物二氧化碳的浓度被岛津气相色谱GC-2014C（配有甲烷转化炉）实时在线检测。其中，一氧化碳的转化率计算公式如下所示：一氧化碳转化率 = [(一氧化碳)进口浓度-(一氧化碳)出口进口浓度]/( 一氧化碳)进口浓度*100%。一氧化碳初始浓度为5000 ppm，空速为33000 mL h -1g -1，反应活性曲线如图5b，其一氧化碳的转化率（T 90%）为316 ℃。 (3) 100 mg of monoatomic dispersed Pt/CeO 2 and 400 mg of quartz sand (60-80 mesh) were mixed evenly in the reaction bed. In the reaction temperature range, a carbon monoxide/dry air mixture was introduced. Each reaction temperature point was retained for 50 min, and the temperature was raised to the next reaction temperature point at a rate of 1 °C/min. During the reaction, the concentrations of reactant carbon monoxide and product carbon dioxide were detected online in real time by Shimadzu gas chromatograph GC-2014C (equipped with a methane reformer). The carbon monoxide conversion rate was calculated as follows: carbon monoxide conversion rate = [(carbon monoxide) inlet concentration - (carbon monoxide) outlet inlet concentration] / (carbon monoxide) inlet concentration * 100%. The initial carbon monoxide concentration was 5000 ppm, the space velocity was 33000 mL h -1 g -1 , and the reaction activity curve was shown in Figure 5b. The carbon monoxide conversion rate (T 90% ) was 316 °C.
实施例3Example 3
（1）高分散Pt/CeO 2催化剂的制备 (1) Preparation of highly dispersed Pt/CeO 2 catalyst
（1-1）称取1 g实施例1中制备的CeO 2粉末分散在含有2.0 mL溶液浓度为6.45 mmol四氨合硝酸铂的去离子水中，所得的悬浮液D在室温下超声30 min，超声频率为30 kHz，超声功率420 W，然后转移至摇床中以转速150 rmp，温度70 ℃，干燥时间为14 h，再转移至管式炉高温焙烧，在干空气氛下，气体流速为80 mL/min，以3~5 ℃/min的速率从室温升温至800 ℃，恒温10 h，随后降至室温，关闭干空，得到单原子分散Pt/CeO 2样品 (1-1) 1 g of the CeO2 powder prepared in Example 1 was weighed and dispersed in deionized water containing 2.0 mL of a solution having a concentration of 6.45 mmol of tetraammine platinum nitrate. The resulting suspension D was ultrasonicated at room temperature for 30 min at a frequency of 30 kHz and a power of 420 W. The suspension was then transferred to a shaker and heated at a speed of 150 rmp, a temperature of 70 °C, and a drying time of 14 h. The suspension was then transferred to a tube furnace for high-temperature calcination. In a dry air atmosphere, the gas flow rate was 80 mL/min, and the temperature was raised from room temperature to 800 °C at a rate of 3-5 °C/min. The temperature was maintained constant for 10 h, and then the suspension was cooled to room temperature. The dry air was closed to obtain a single-atom dispersed Pt/ CeO2 sample.
（1-2）称取一定量的单原子分散Pt/CeO 2置于管式炉中，在10vol.% H 2/Ar气氛下，气体流速为80 mL/min，以3~5 ℃/min的速率从室温升温至300 ℃，恒温3 h，随后降至室温后，关闭还原气，得到高分散Pt/CeO 2样品。将Pt/CeO 2样品在压片机设定压强下(14 MPa)压片，过筛，得到40~60目的催化剂。 (1-2) A certain amount of monoatomic dispersed Pt/CeO 2 was weighed and placed in a tube furnace. In a 10 vol.% H 2 /Ar atmosphere, the gas flow rate was 80 mL/min, and the temperature was raised from room temperature to 300 ℃ at a rate of 3~5 ℃/min. The temperature was kept constant for 3 h, and then the temperature was lowered to room temperature. The reducing gas was turned off to obtain a highly dispersed Pt/CeO 2 sample. The Pt/CeO 2 sample was pressed into a tablet at the set pressure of the tablet press (14 MPa) and sieved to obtain a catalyst of 40~60 mesh.
由图3 高角环形暗场图可知，近亚纳米尺度的Pt颗粒高度分散在CeO 2表面；此外，由图4b 一氧化碳在样品上的吸附结果显示，一氧化碳主要吸附在Pt纳米颗粒上，综合上述结果表明成功制备了高分散Pt/CeO 2催化剂。 As can be seen from the high-angle annular dark field image in Figure 3, the nearly sub-nanometer-scale Pt particles are highly dispersed on the CeO2 surface; in addition, the adsorption results of carbon monoxide on the sample in Figure 4b show that carbon monoxide is mainly adsorbed on Pt nanoparticles. The above results show that a highly dispersed Pt/ CeO2 catalyst was successfully prepared.
（2）将100 mg高分散Pt/CeO 2与400 mg石英砂（60-80目）在反应床层混合均匀，在反应温度80~300 ℃区间，通入甲苯/干空混合气，每个反应温度点保留50 min，相邻的两个温度点间隔10 ℃，以1 ℃/min的速率升温至下一个反应温度点。反应过程中，反应物甲苯和产物二氧化碳的浓度被岛津气相色谱GC-2014C实时在线检测。其中，甲苯的转化率计算公式如下所示：甲苯转化率 = [(甲苯)进口浓度-(甲苯)出口进口浓度]/(甲苯)进口浓度*100%。甲苯初始浓度为1000 ppm，空速为60000 mL h -1g -1，反应活性曲线如图5a，其甲苯的转化率（T 90%）为199 ℃。 (2) 100 mg of highly dispersed Pt/CeO 2 and 400 mg of quartz sand (60-80 mesh) were mixed evenly in the reaction bed. In the reaction temperature range of 80~300 ℃, a toluene/dry air mixture was introduced. Each reaction temperature point was retained for 50 min. The interval between two adjacent temperature points was 10 ℃, and the temperature was raised to the next reaction temperature point at a rate of 1 ℃/min. During the reaction, the concentrations of reactant toluene and product carbon dioxide were detected in real time online by Shimadzu gas chromatograph GC-2014C. The conversion rate of toluene was calculated as follows: Toluene conversion rate = [(toluene) inlet concentration - (toluene) outlet inlet concentration] / (toluene) inlet concentration * 100%. The initial concentration of toluene was 1000 ppm, the space velocity was 60000 mL h -1 g -1 , and the reaction activity curve was shown in Figure 5a. The conversion rate of toluene (T 90% ) was 199 ℃.
（3）将100 mg单原子分散Pt/CeO 2与400 mg石英砂（60-80目）在反应床层混合均匀，在反应温度区间，通入一氧化碳/干空混合气，每个反应温度点保留50 min，以1 ℃/min的速率升温至下一个反应温度点。反应过程中，反应物一氧化碳和产物二氧化碳的浓度被岛津气相色谱GC-2014C（配有甲烷转化炉）实时在线检测。其中，一氧化碳的转化率计算公式如下所示：一氧化碳转化率 = [(一氧化碳)进口浓度-(一氧化碳)出口进口浓度]/(一氧化碳)进口浓度*100%。一氧化碳初始浓度为5000 ppm，空速为33000 mL h -1g -1，反应活性曲线如图5b，其一氧化碳的转化率（T 90%）为75 ℃。 (3) 100 mg of monoatomic dispersed Pt/CeO 2 and 400 mg of quartz sand (60-80 mesh) were mixed evenly in the reaction bed. In the reaction temperature range, a carbon monoxide/dry air mixture was introduced. Each reaction temperature point was retained for 50 min, and the temperature was raised to the next reaction temperature point at a rate of 1 °C/min. During the reaction, the concentrations of reactant carbon monoxide and product carbon dioxide were detected online in real time by Shimadzu gas chromatograph GC-2014C (equipped with a methane reformer). The carbon monoxide conversion rate was calculated as follows: carbon monoxide conversion rate = [(carbon monoxide) inlet concentration - (carbon monoxide) outlet inlet concentration] / (carbon monoxide) inlet concentration * 100%. The initial carbon monoxide concentration was 5000 ppm, the space velocity was 33000 mL h -1 g -1 , and the reaction activity curve was shown in Figure 5b. The carbon monoxide conversion rate (T 90% ) was 75 °C.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，将铈盐和沉淀剂分别溶解于去离子水中，然后将两者混合室温搅拌均匀，转移至水热反应釜内进行水热反应，待降至室温后将水热后的悬浮液离心、洗涤、烘干得到CeO 2 载体，将得到的CeO 2 与含有铂盐的去离子水混合均匀，烘干，在高温下焙烧获得单原子分散的Pt/CeO 2 ，在还原气氛下还原，获得高分散Pt/CeO 2 。 A method for preparing highly dispersed Pt/ CeO2 using monoatomic dispersed platinum as a precursor, characterized in that cerium salt and precipitant are respectively dissolved in deionized water, then the two are mixed and stirred evenly at room temperature, transferred to a hydrothermal reactor for hydrothermal reaction, and after cooling to room temperature, the suspension after hydrothermal reaction is centrifuged, washed, and dried to obtain a CeO2 carrier, the obtained CeO2 is evenly mixed with deionized water containing platinum salt, dried, and calcined at high temperature to obtain monoatomic dispersed Pt/ CeO2 , and reduced in a reducing atmosphere to obtain highly dispersed Pt/ CeO2 .
  2. 根据权利要求1所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，所述铈盐为醋酸铈，所述铂盐为四氨合硝酸铂；所述沉淀剂为氢氧化钠。 According to claim 1, a method for preparing highly dispersed Pt/ CeO2 using monoatomically dispersed platinum as a precursor is characterized in that the cerium salt is cerium acetate, the platinum salt is tetraammine platinum nitrate; and the precipitant is sodium hydroxide.
  3. 根据权利要求1所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，具体包括以下步骤： According to claim 1, a method for preparing highly dispersed Pt/ CeO2 using monoatomic dispersed platinum as a precursor is characterized in that it specifically comprises the following steps:
    （1）CeO 2 的制备： (1) Preparation of CeO2 :
    室温搅拌下，称取醋酸铈和氢氧化钠分别溶解在去离子水中，形成溶液A和溶液B；随后将溶液B缓慢加入溶液A中混合搅拌得到浅紫色悬浮液C，将所得悬浮液C在室温下搅拌均匀后，转移至水热反应釜内进行水热反应，待降至室温后将水热后的悬浮液离心、洗涤数次至洗涤液pH为中性、烘干得到淡黄色粉末CeO 2 载体备用； Under stirring at room temperature, cerium acetate and sodium hydroxide were weighed and dissolved in deionized water respectively to form solution A and solution B; then solution B was slowly added to solution A and mixed and stirred to obtain a light purple suspension C; the obtained suspension C was stirred evenly at room temperature, and then transferred to a hydrothermal reactor for hydrothermal reaction; after cooling to room temperature, the hydrothermal suspension was centrifuged, washed several times until the pH of the washing solution was neutral, and dried to obtain a light yellow powder CeO2 carrier for standby use;
    （2）单原子分散Pt/CeO 2 的制备： (2) Preparation of single-atom dispersed Pt/CeO 2 :
    称取步骤（1）所制备的CeO 2 分散在含有铂盐的去离子水中，所得的悬浮液D在室温下超声，并在摇床中烘干，再转移至管式炉高温焙烧，得到单原子分散Pt/CeO 2 样品； Weigh the CeO2 prepared in step (1) and disperse it in deionized water containing platinum salt. The resulting suspension D is sonicated at room temperature, dried in a shaker, and then transferred to a tube furnace for high-temperature calcination to obtain a single-atom dispersed Pt/ CeO2 sample.
    （3）高分散Pt/CeO 2 的制备： (3) Preparation of highly dispersed Pt/ CeO2 :
    将步骤（2）中制备的单原子分散Pt/CeO 2 样品，通过高温还原气氛焙烧，获得黑色高分散Pt/CeO 2 样品； The single-atom dispersed Pt/ CeO2 sample prepared in step (2) is calcined in a high-temperature reducing atmosphere to obtain a black highly dispersed Pt/ CeO2 sample;
    （4）将步骤（2）和（3）中的Pt/CeO 2 样品，在压片机设定压强下压片，过筛，得到40~60目的催化剂。 (4) The Pt/ CeO2 samples in steps (2) and (3) are pressed into tablets at a set pressure on a tablet press, and sieved to obtain a catalyst with a mesh size of 40 to 60.
  4. 按照权利要求3所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，步骤（1）中，所述醋酸铈质量为0.79~2.37 g，所述氢氧化钠的质量为7.7~23.1 g，所述溶液A和溶液B中去离子水的体积分别为10~30 mL和27.5~82.5 mL，悬浮液C中去离子水的体积为37.5~112.5 mL；所述搅拌温度为20~35 ℃；所述搅拌时间为0.5~1 h；所述搅拌速率100~200 r/min；所述反应釜体积规格为60～100 mL；所述水热反应温度为120～140 ℃，反应压力0.1～0.3 MPa，反应时间为3～7 h，离心转速为3500～4000 r/min；所述pH为7～8；所述烘干温度为60~80 ℃，所述烘干时间为8~16 h。 According to claim 3, a method for preparing highly dispersed Pt/CeO2 using monoatomic dispersed platinum as a precursor is characterized in that, in step (1), the mass of cerium acetate is 0.79-2.37 g, the mass of sodium hydroxide is 7.7-23.1 g, the volumes of deionized water in solution A and solution B are 10-30 mL and 27.5-82.5 mL, respectively, and the volume of deionized water in suspension C is 37.5-112.5 mL; the stirring temperature is 20-35 °C; the stirring time is 0.5-1 h; the stirring rate is 100-200 r/min; the reactor volume specification is 60-100 mL; the hydrothermal reaction temperature is 120-140 °C, the reaction pressure is 0.1-0.3 MPa, the reaction time is 3-7 h, and the centrifugal speed is 3500-4000 r/min; the pH is 7-8; the drying temperature is 60-80 ℃, and the drying time is 8~16 h.
  5. 按照权利要求3所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，步骤（2）中，所述CeO 2 的质量为0.75~1.25 g；所述铂盐为四氨合硝酸铂；所述铂盐溶液浓度为4.84~8.06 mmol/mL；所述铂盐溶液体积为1.5~2.5 mL；所述超声时间为0.5~1 h；所述超声频率为20~40 kHz，280~560 W；所述摇床转速120~180 rmp；所述摇床温度60~80 ℃；所述摇床干燥时间为8~16 h；所述管式炉高温焙烧方法为，在干空气氛下，气体流速为80 mL/min，从室温以3~5 ℃/min的速率升温至400~900 ℃，恒温5~10 h，随后降至室温，关闭干空。 According to claim 3, a method for preparing highly dispersed Pt/ CeO2 using monoatomic dispersed platinum as a precursor is characterized in that, in step (2), the mass of CeO2 is 0.75~1.25 g; the platinum salt is tetraammine platinum nitrate; the concentration of the platinum salt solution is 4.84~8.06 mmol/mL; the volume of the platinum salt solution is 1.5~2.5 mL; the ultrasonic time is 0.5~1 h; the ultrasonic frequency is 20~40 kHz, 280~560 W; the shaking table speed is 120~180 rmp; the shaking table temperature is 60~80 °C; the shaking table drying time is 8~16 h; the high temperature roasting method in the tubular furnace is, in a dry air atmosphere, the gas flow rate is 80 mL/min, the temperature is increased from room temperature to 400~900 °C at a rate of 3~5 °C/min, the temperature is kept constant for 5~10 h, then the temperature is reduced to room temperature, and the dry air is turned off.
  6. 按照权利要求3所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，步骤（3）中，所述高温焙烧方法为，在5~15 vol.% H 2 /Ar气氛下，气体流速为60~100mL/min，从室温以3~5 ℃/min的速率升温至250~350 ℃，恒温2~4 h，随后降至室温后，关闭还原气。 According to claim 3, a method for preparing highly dispersed Pt/CeO2 using monoatom dispersed platinum as a precursor is characterized in that in step (3), the high-temperature calcination method is to increase the temperature from room temperature to 250~350°C at a rate of 3~5°C/min under a 5~15 vol.% H2 /Ar atmosphere, with a gas flow rate of 60~100mL/min, and keep the temperature constant for 2~4 hours, then cool to room temperature and turn off the reducing gas.
  7. 按照权利要求3所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法，其特征在于，步骤（4）中，所述压片机压强为12～16 MPa，稳定时间为1～3 min。 According to claim 3, a method for preparing highly dispersed Pt/ CeO2 using monoatomic dispersed platinum as a precursor is characterized in that in step (4), the tablet press pressure is 12 to 16 MPa and the stabilization time is 1 to 3 min.
  8. 由权利要求1～7任一项所述制备方法得到的一种以单原子分散铂为前体物制备高分散Pt/CeO 2 催化剂。 A highly dispersed Pt/ CeO2 catalyst prepared by the preparation method according to any one of claims 1 to 7 using monoatom dispersed platinum as a precursor.
  9. 权利要求8所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 催化剂应用于挥发性有机物的催化净化、一氧化碳完全氧化，对于挥发性有机物的催化净化，选取甲苯为目标污染物，将甲苯/干空通入装有高分散Pt/CeO 2 催化剂的石英管，石英管置于带有热偶的管式炉中加热，甲苯经过催化剂，会完全氧化为二氧化碳和水；对于一氧化碳完全氧化，一氧化碳/干空经过催化剂，会完全氧化为二氧化碳。 The highly dispersed Pt/ CeO2 catalyst prepared with single-atom dispersed platinum as a precursor as described in claim 8 is applied to the catalytic purification of volatile organic compounds and the complete oxidation of carbon monoxide. For the catalytic purification of volatile organic compounds, toluene is selected as the target pollutant, and toluene/dry air is passed into a quartz tube filled with a highly dispersed Pt/ CeO2 catalyst. The quartz tube is placed in a tubular furnace with a thermocouple for heating. Toluene will be completely oxidized into carbon dioxide and water after passing through the catalyst; for the complete oxidation of carbon monoxide, carbon monoxide/dry air will be completely oxidized into carbon dioxide after passing through the catalyst.
  10. 权利要求9所述一种以单原子分散铂为前体物制备高分散Pt/CeO 2 的方法和应用，其特征在于，所述甲苯/干空浓度为200~2000 ppm，所述一氧化碳/干空浓度为1000~10000 ppm；所述加热炉温度30~450 ℃，每个反应温度点保留50 min，以1 ℃/min的速率10min升温至下一个反应温度点；所述甲苯/干空、一氧化碳/干空流速均为50~100 mL；所述甲苯催化净化、一氧化碳完全氧化反应中催化剂的用量均为50~150 mg。 The method and application of preparing highly dispersed Pt/ CeO2 using monoatomically dispersed platinum as a precursor as described in claim 9 is characterized in that the toluene/dry air concentration is 200~2000 ppm, and the carbon monoxide/dry air concentration is 1000~10000 ppm; the heating furnace temperature is 30~450°C, each reaction temperature point is retained for 50 min, and the temperature is increased to the next reaction temperature point at a rate of 1°C/min for 10 min; the toluene/dry air and carbon monoxide/dry air flow rates are both 50~100 mL; the amount of catalyst used in the toluene catalytic purification and carbon monoxide complete oxidation reactions is 50~150 mg.
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