WO2022083793A1 - 三维 / 二维 Ni-Co 双金属氧化物 /g-C3N4 纳米复合材料及其制备方法与应用 - Google Patents

三维 / 二维 Ni-Co 双金属氧化物 /g-C3N4 纳米复合材料及其制备方法与应用 Download PDF

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WO2022083793A1
WO2022083793A1 PCT/CN2021/139029 CN2021139029W WO2022083793A1 WO 2022083793 A1 WO2022083793 A1 WO 2022083793A1 CN 2021139029 W CN2021139029 W CN 2021139029W WO 2022083793 A1 WO2022083793 A1 WO 2022083793A1
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dimensional
calcination
exhaust gas
nanocomposite material
metal oxide
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French (fr)
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路建美
陈冬赟
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苏州大学
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    • 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
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • the invention belongs to the technical field of inorganic functional materials, and particularly relates to a preparation method of a two-dimensional gC 3 N 4 nanosheet-wrapped three-dimensional hollow Ni-Co bimetallic oxide composite catalyst and its application in waste gas treatment.
  • gC 3 N 4 has been widely studied due to its unique planar structure, suitable band gap (2.7 eV), and metal-free catalysts; however, due to its low specific surface area, poor conductivity, and narrow visible light response range , the extremely fast photogenerated carrier recombination greatly limits its photocatalytic performance as a pure catalyst.
  • the purpose of the present invention is to introduce and provide a preparation method of a two-dimensional gC 3 N 4 nanosheet encapsulated three-dimensional hollow Ni-Co double metal oxide composite catalyst capable of responding to visible light and the visible light catalytic degradation of exhaust gas.
  • the Ni-Co Prussian blue precursor was loaded onto two-dimensional gC 3 N 4 nanosheets by self-assembly, and then calcined at low temperature to obtain three-dimensional/two-dimensional Ni-Co bimetallic oxide/gC 3 N 4 Nanocomposite materials and photocatalytic degradation of exhaust gas.
  • a three-dimensional/two-dimensional Ni-Co double metal oxide/gC 3 N 4 nanocomposite material the preparation method thereof includes the following steps: (1) Using urea as a raw material, calcining gC3N4 nanosheets were fabricated.
  • the invention also discloses a method for photocatalytic treatment of waste gas, comprising the following steps: (1) using urea as a raw material, and calcining the gC 3 N 4 nanosheets.
  • Three-dimensional/two-dimensional Ni-Co bimetallic oxide/gC 3 N 4 nanocomposites were obtained by low-temperature calcination using nickel salt, cobalt salt and gC 3 N 4 nanosheets as raw materials.
  • the exhaust gas is passed through the three-dimensional/two-dimensional Ni-Co bimetallic oxide/gC 3 N 4 nanocomposite material to realize the photocatalytic treatment of the exhaust gas.
  • the nickel salt is nickel nitrate hexahydrate (Ni(NO 3 ) 3 ⁇ 6H 2 O)
  • the cobalt precursor is cobalt potassium cyanide (K 3 [Co(CN) 6 ])
  • the sodium salt is sodium citrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O).
  • the calcination temperature is 300-600 °C
  • the time is 2-8 h
  • the heating rate is 2-5 °C ⁇ min -1 .
  • the calcination consists of the first calcination and the second calcination, the temperature of the first calcination is higher than the temperature of the second calcination, and the heating rate of the first calcination is lower than that of the second calcination.
  • step (2) the mass ratio of nickel salt, cobalt salt, sodium salt, and gC 3 N 4 nanosheets is (1-6): (3-8): (3-8): 3, Preferably (1-3): (3-6): (3-6): 3; the aging time is 12-48 h; the low-temperature calcination temperature is 150-450 °C, the time is 1-4 h, and the heating rate is 2 ⁇ 5°C ⁇ min -1 .
  • the illumination is visible light illumination;
  • the exhaust gas is nitrogen oxides, preferably nitrogen monoxide.
  • the invention further improves its photocatalytic activity by treating gC 3 N 4 ; the invention also discloses the application of the above-mentioned Ni-Co double metal oxide/gC 3 N 4 nanocomposite catalyst in waste gas treatment.
  • the present invention adopts a simple and easy-to-operate self-assembly and low-temperature calcination method to prepare a three-dimensional/two-dimensional Ni-Co bimetallic oxide/gC 3 N 4 composite photocatalyst, the preparation process is simple, and the cost of raw materials is low , which is conducive to reducing the preparation cost and is easy to achieve large-scale production.
  • the three-dimensional/two-dimensional Ni-Co double metal oxide/gC 3 N 4 composite photocatalyst of the present invention promotes the separation efficiency of photo-generated carriers in gC 3 N, effectively increases the survival life of photo-generated charges, and promotes its photocatalysis active; at the same time, the hollow Ni-Co bimetallic oxide can provide a larger specific surface area and more active sites to participate in the reaction.
  • the three-dimensional/two-dimensional Ni-Co double metal oxide/gC 3 N 4 composite photocatalyst obtained by the present invention can improve the absorption and utilization of visible light, and can effectively carry out photocatalytic degradation of exhaust gas.
  • Figure 1 shows the scanning electron microscope (SEM) and transmission electron microscope (TEM) images of gC 3 N 4 , Ni 3 [Co(CN) 6 ]/gC 3 N 4 and NiCoO x /gC 3 N 4 .
  • Figure 2 shows the scanning electron microscope (SEM) and transmission electron microscope (TEM) images of Ni 3 [Co(CN) 6 ] and NiCoO x .
  • Fig. 3 is the effect diagram of NiCoO x , gC 3 N 4 and different ratios of NiCoO x /gC 3 N 4 for the treatment of exhaust gas.
  • Figure 4 shows the effect of NICO/CN-100 composite on the recycling of degraded waste gas.
  • the preparation method of the visible light-responsive three-dimensional/two-dimensional Ni-Co bimetal oxide/gC 3 N 4 nanocomposite material in the present invention can be carried out as follows: Preparation of two-dimensional gC 3 N 4 nanosheets: First, in an aluminum crucible with a lid A certain amount of urea was added into the muffle furnace, covered with a lid, and calcined for the first time; then the product was collected, and the calcination temperature and heating rate were adjusted for the second calcination, and the obtained pale yellow product was gC 3 N 4 nanosheets .
  • Ni-Co bimetallic oxide/gC 3 N 4 nanocomposites First, nickel nitrate hexahydrate (Ni(NO 3 ) 3 ⁇ 6H 2 O), sodium citrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) and gC 3 N 4 nanosheets were mixed uniformly in water to obtain solution A, and potassium cobalt cyanide (K 3 [Co(CN) 6 ]) was dissolved in water to obtain colorless and transparent Solution B, solution A and solution B were mixed, centrifuged and washed after aging to obtain a light blue Ni - Co Prussian blue/ gC3N4 precursor, and then the precursor was transferred to a muffle furnace for calcination to obtain Ni-Co Bimetallic oxide/ gC3N4 nanocomposites .
  • Ni(NO 3 ) 3 ⁇ 6H 2 O nickel nitrate hexahydrate
  • sodium citrate Na 3 C 6 H 5 O 7 ⁇ 2H 2 O
  • Ni-Co bimetallic oxides First, nickel nitrate hexahydrate (Ni(NO 3 ) 3 ⁇ 6H 2 O) and sodium citrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) were dissolved in water to obtain colorless and transparent solution A, dissolve potassium cobalt cyanide (K 3 [Co(CN) 6 ]) in water to obtain colorless and transparent solution B, mix solution A and solution B and stir evenly, after aging
  • K 3 [Co(CN) 6 ] potassium cobalt cyanide
  • the blue Ni-Co Prussian blue precursor is obtained by centrifugal washing; the Ni-Co Prussian blue precursor is calcined in a muffle furnace to obtain a black Ni-Co bimetallic oxide.
  • Photocatalytic degradation of waste gas The operation of photocatalytic degradation of waste gas is as follows.
  • the three-dimensional/two-dimensional Ni-Co bimetallic oxide/ gC3N4 nanocomposite is flattened on a wooden board in a closed cylindrical detection chamber, and then tested in a closed cylindrical detection chamber.
  • a 300 W xenon lamp was placed vertically above to simulate visible light; the nitric oxide concentration was controlled to 600 ppb by mixing air and nitric oxide in a compressed bottle and passed through the reaction chamber at a flow rate of 1.2 L/min.
  • the catalyst reached adsorption-desorption equilibrium (0.5 h), the xenon lamp was turned on, and the photocatalytic measurements were started on the NOx analyzer.
  • Ni-Co bimetallic oxide, gC3N4 and a series of Ni - Co bimetallic oxide/ gC3N4 nanocomposite catalysts on exhaust gas were investigated at the same concentration.
  • the raw materials involved in the present invention are all commercially available conventional compounds, and the specific operations and testing methods are conventional techniques.
  • Example 1 Preparation of two-dimensional gC 3 N 4 nanosheets: First, add 10 g of urea to an aluminum crucible with a lid, put it into a muffle furnace, cover the lid, and calcine at 550 °C for 4 h at a heating rate of 2.5 °C min - 1 (room temperature to 550 °C), after the muffle furnace was cooled to room temperature, a yellow solid was obtained; then the obtained yellow solid was spread in a rectangular crucible, and then calcined at 500 °C for 2 h, and the heating rate was 5 °C min -1 (room temperature to 500 °C), the light yellow product, namely two - dimensional gC3N4 nanosheets, was collected.
  • Figure 1 is the SEM and TEM images of the two-dimensional gC 3 N 4 nanosheets prepared in this example, (a ) and (b) are the gC3N4 nanosheets prepared in this example, respectively, called CN.
  • Example 2 Preparation of Ni-Co double metal oxide/gC 3 N 4 nanocomposite: First, 100 mg of nickel nitrate hexahydrate (Ni(NO 3 ) 3 ⁇ 6H 2 O), 162.5 mg of sodium citrate ( Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) and 150 mg gC 3 N 4 nanosheets were dispersed in 20 ml of deionized water, and the solution A was formed by conventional stirring; 200 mg of cobalt potassium cyanide (K 3 [Co(CN) 6 ]) Routine stirring in 20 ml of deionized water to form solution B; after mixing solutions A and B, they were left for aging at room temperature for 24 h, the obtained product was washed by conventional centrifugal washing with water and ethanol, and the precipitate was dried in an oven at 60 °C for 24 h.
  • Ni(NO 3 ) 3 ⁇ 6H 2 O nickel nitrate hexahydrate
  • the obtained light blue sample is Ni 3 [Co(CN) 6 ]/gC 3 N 4 nanocomposite; then the obtained Ni 3 [Co(CN) 6 ]/gC 3 N 4 nanocomposite was prepared in a muffle
  • the NiCoO x /gC 3 N 4 nanocomposite was prepared by calcining in a furnace at 350 °C for 2 h, and the heating rate was 2 °C min -1 (room temperature to 350 °C). For NICO/CN-100.
  • Figure 1 shows the Ni 3 [Co(CN) 6 ]/gC 3 N 4 nanocomposite prepared in this example and the SEM images and TEM images of NiCoO x /gC 3 N 4 nanocomposites, (c) and (d) Ni 3 [Co(CN) 6 ]/gC 3 N 4 nanocomposites prepared in this example, ( e) and (f) represent the three-dimensional/two-dimensional NiCoO x /gC 3 N 4 nanocomposites prepared in this example.
  • NiCoOx / gC3N4 nanocomposites were prepared with 50 mg, 75 mg, and 125 mg of nickel nitrate hexahydrate, respectively, with gC3N4 nanosheets kept at 150 mg .
  • the materials (the mass of cobalt salt and sodium salt are unchanged) are marked as NICO/CN-50, NICO/CN-75 and NICO/CN-125, respectively.
  • Comparative Example 1 Preparation of Ni-Co Double Metal Oxides: First, 0.8 g of nickel nitrate hexahydrate (Ni(NO 3 ) 3 ⁇ 6H 2 O) and 1.3 g of sodium citrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) in 20 ml of deionized water to form clear solution A; 1.6 g of potassium cobalt cyanide (K 3 [Co(CN) 6 ]) in 20 ml of deionized water to form solution B; A and B The solution was mixed and aged at room temperature for 24 h (standing), the obtained product was washed by conventional centrifugation with water and ethanol, and the precipitate was dried in an oven at 60 °C for 24 h.
  • Ni(NO 3 ) 3 ⁇ 6H 2 O nickel nitrate hexahydrate
  • sodium citrate Na 3 C 6 H 5 O 7 ⁇ 2H 2 O
  • K 3 [Co(CN) 6 ] potassium cobalt cyanide
  • Ni-Co Prussian blue precursor Ni-Co Prussian blue precursor (Ni 3 [Co(CN) 6 ] 2 ). Then the obtained Ni-Co Prussian blue precursor was calcined in a muffle furnace at 350 °C for 2 h, and the heating rate was 2 °C min -1 (room temperature to 350 °C). After the muffle furnace was naturally cooled to room temperature, the obtained black The product is a Ni-Co bimetallic oxide known as NiCoOx .
  • Figure 2 is the scanning and transmission of the Ni 3 [Co(CN) 6 ] 2 and Ni-Co bimetallic oxides prepared above. Electron micrograph. (a) and (b) are Ni 3 [Co(CN) 6 ] 2 solid hexahedrons, respectively, and (c) and (d) represent hollow NiCoO x .
  • photocatalytic treatment of exhaust gas the specific steps are as follows: at room temperature, 100 mg of the catalyst to be tested is spread on a wooden board in a closed cylindrical detection chamber with a volume of 2.26 L, and a 300 W xenon lamp is placed vertically above it.
  • the nitric oxide concentration was controlled to 600 ppb by mixing air and nitric oxide in a compressed bottle and passed through the reaction chamber at a flow rate of 1.2 L/min.
  • the catalyst reached adsorption-desorption equilibrium (0.5 h)
  • the xenon lamp was turned on, and the photocatalytic measurements were started on the NOx analyzer.
  • the measurement time was 30 min, and the sampling interval was 1 min, and a total of 30 sets of data were obtained.
  • NiCoO x , gC 3 N 4 and NiCoO x /gC 3 N 4 composite materials in different proportions in the treatment of exhaust gas, and it is found that the catalytic efficiency of NiCoO x /gC 3 N 4 to exhaust gas is obviously better than that of NiCoO through the effect of Fig. 3 x (20%), and gC 3 N 4 (37%); and NICO/CN-100 can achieve the highest degradation effect of 59.1%. It shows that NiCoO x /gC 3 N 4 composite has good catalytic degradation activity for nitric oxide.
  • Example 2 100 mg of the Ni 3 [Co(CN) 6 ]/gC 3 N 4 nanocomposite of Example 2 is subjected to the same test as above, and a degradation effect of up to 40% can be achieved.
  • Example 2 The calcination temperature of Example 2 was adjusted to 550° C., and the rest remained unchanged to obtain high-temperature NICO/CN-100. The same test as above was carried out, and a degradation effect of up to 43.2% could be achieved.
  • Example 2 The cobalt potassium cyanide in Example 2 was replaced with cobalt nitrate hexahydrate with an equal cobalt molar amount, and the rest remained unchanged to obtain a comparative NICO/CN-100, and the above-mentioned same test was carried out to achieve a maximum degradation effect of 49.6%.
  • Figure 4 is a cycle effect diagram of NICO/CN-100 on waste gas degradation. It can be seen from the figure that after 5 cycles, it still shows a good degradation effect. Therefore, the catalyst can be reused and has good stability.
  • the present invention successfully prepared three-dimensional/two-dimensional NiCoO x /gC 3 N 4 nanocomposite materials through a simple and easy-to-operate self-assembly and low-temperature calcination method.
  • the composite material disclosed in the present invention has strong visible light catalytic degradation for exhaust gas.
  • the present invention has the advantages of simple production process, economical and environmental protection, and low production cost, so it will have a good application prospect in waste gas treatment.

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Abstract

本发明公开了三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料及其制备方法与应用。以尿素为原料，煅烧制成g-C 3N 4纳米片；以镍盐、钴盐和g-C 3N 4纳米片为原料，通过低温煅烧得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料；光照下，将废气通过三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，实现废气的光催化处理。本发明NiCoO x/g-C 3N 4对废气的催化效率明显优于NiCoO x（20%），和g-C 3N 4（37%）；并且NICO/CN-100可以达到最高59.1%的降解效果；说明NiCoO x/g-C 3N 4复合物对一氧化氮有良好的催化降解活性。

Description

三维/二维Ni-Co双金属氧化物/g-C3N4纳米复合材料及其制备方法与应用 技术领域
本发明属于无机功能材料技术领域，具体涉及二维g-C 3N 4纳米片包裹三维中空Ni-Co双金属氧化物复合催化剂的制备方法及其对废气处理方面的应用。
背景技术
随着世界各地工业的迅速发展，空气污染已成为当今最严重的问题之一。废气会导致光化学污染、酸雨、雾霾、等，都会对人体、土地、水源造成极大的危害。所以，寻找廉价、高效、节能的方法降解处理废气，已成为环境研究的热点问题。目前来说，半导体光催化技术具有无毒，降解效率高，氧化还原能力强等优点，被认为是处理废气污染的最经济有效的方法之一。在现行的多种光催化剂中，g-C 3N 4因其独特的平面结构、合适的带隙(2.7eV)、无金属催化剂被广泛研究；但由于其比表面积低、导电性差、可见光响应范围窄，极快的光生载流子复合大大限制了其作为纯催化剂的光催化性能。
技术问题
本发明目的是介绍提供一种能够对可见光响应的二维g-C 3N 4纳米片包裹三维中空Ni-Co双金属氧化物复合催化剂的制备方法以及对废气的可见光催化降解。将Ni-Co普鲁士蓝前驱体，通过自组装的方式将其负载到二维的g-C 3N 4纳米片上，而后通过低温煅烧从而得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，并对废气进行光催化降解。
技术解决方案
为了达到上述目的，本发明具体技术方案如下：一种三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其制备方法包括以下步骤：（1）以尿素为原料，煅烧制成g-C 3N 4纳米片。
（2）以镍盐、钴盐、钠盐和g-C 3N 4纳米片为原料，通过老化、低温煅烧得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料。
本发明还公开了一种光催化处理废气的方法，包括以下步骤：（1）以尿素为原料，煅烧制成g-C 3N 4纳米片。
（2）以镍盐、钴盐和g-C 3N 4纳米片为原料，通过低温煅烧得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料。
（3）光照下，将废气通过三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，实现废气的光催化处理。
本发明中，镍盐为六水合硝酸镍（Ni(NO 3) 3·6H 2O），钴前驱体为钴氰化钾(K 3[Co(CN) 6])，钠盐为柠檬酸钠（Na 3C 6H 5O 7·2H 2O）。
上述技术方案中，步骤（1）中，煅烧的温度为300～600℃，时间为2～8 h，升温速率为2～5℃·min -1。优选的，煅烧由第一次煅烧与第二次煅烧组成，第一次煅烧的温度高于第二次煅烧的温度，第一次煅烧的升温速率小于第二次煅烧的升温速率。
上述技术方案中，步骤（2）中，镍盐、钴盐、钠盐、g-C 3N 4纳米片的质量比为（1～6）∶（3～8）∶（3～8）∶3，优选（1～3）∶（3～6）∶（3～6）∶3；老化时间为12～48 h；低温煅烧的温度为150～450℃，时间为1～4 h，升温速率为2～5℃·min -1。
上述技术方案中，步骤（3）中，光照为可见光照射；废气为氮氧化物，优选一氧化氮。
本发明对g-C 3N 4进行处理进一步提高其光催化活性；本发明还公开了上述Ni-Co双金属氧化物/g-C 3N 4纳米复合催化剂在废气处理中的应用。
有益效果
本方案的优点：1、本发明采用简单易操作的自组装和低温煅烧法，制得三维/二维Ni-Co双金属氧化物/g-C 3N 4复合光催化剂，制备工艺简单，原材料成本低廉，有利于实现制备成本的降低，易实现大规模生产。
2、本发明三维/二维Ni-Co双金属氧化物/g-C 3N 4复合光催化剂促进了g-C 3N中光生载流子的分离效率，有效地增加光生电荷的存活寿命，促进其光催化活性；同时中空的Ni-Co双金属氧化物可以提供更大的比表面积和更多的活性位点参与反应。
3、本发明得到的三维/二维Ni-Co双金属氧化物/g-C 3N 4复合光催化剂能提高对可见光的吸收和利用，能够有效地对废气进行光催化降解。
附图说明
图1 为g-C 3N 4，Ni 3[Co(CN) 6]/g-C 3N 4和NiCoO x/g-C 3N 4的扫描电镜图（SEM）和透射电镜图（TEM）。
图2 为Ni 3[Co(CN) 6]、NiCoO x的扫描电镜图（SEM）和透射电镜图（TEM）。
图3 为NiCoO x、g-C 3N 4和不同比例NiCoO x/g-C 3N 4处理废气的效果图。
图4 为NICO/CN-100复合材料对降解废气的循环效果图。
 本发明的实施方式
本发明中可见光响应的三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料的制备方法可如下进行：二维g-C 3N 4纳米片的制备：首先，在带盖铝坩埚中加入一定量尿素，放入马弗炉，盖上盖子，进行第一次煅烧；而后收集产物，调整煅烧温度和升温速率进行第二次煅烧，得到的浅黄色产物为g-C­ 3N 4纳米片。
三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料的制备：首先，将六水合硝酸镍（Ni(NO 3) 3·6H 2O）、柠檬酸钠（Na 3C 6H 5O 7·2H 2O）和g-C 3N 4纳米片在水中混合均匀，得到溶液A，将钴氰化钾(K 3[Co(CN) 6]) 溶于水中，得到无色透明的溶液B，将溶液A和溶液B混合，老化后离心洗涤得到淡蓝色的Ni-Co普鲁士蓝/ g-C 3N 4前驱体，然后将前驱体转移到马弗炉中进行煅烧，得到Ni-Co双金属氧化物/g-C 3N 4纳米复合材料。
三维Ni-Co双金属氧化物的制备：首先，将六水合硝酸镍（Ni(NO 3) 3·6H 2O）和柠檬酸钠（Na 3C 6H 5O 7·2H 2O）溶于水中，得到无色透明的溶液A，将钴氰化钾(K 3[Co(CN) 6]) 溶于水中，得到无色透明的溶液B，将溶液A和溶液B混合搅拌均匀，老化后离心洗涤得到蓝色的Ni-Co普鲁士蓝前驱体；将Ni-Co普鲁士蓝前驱体放入马弗炉中煅烧得到黑色的Ni-Co双金属氧化物。
光催化降解废气：光催化降解废气的操作具体如下，将三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料平铺在密闭圆柱形检测室中的木板上，并在其上方垂直放置300 W氙灯模拟可见光；通过将压缩瓶中的空气和一氧化氮混合来控制一氧化氮浓度为600 ppb，并以1.2 L/min的流速通过反应室。当催化剂达到吸附-解吸平衡时（0.5 h），打开氙灯，并在NO x分析仪上开始光催化测量。
在相同浓度下探究Ni-Co双金属氧化物、g-C 3N 4和一系列的Ni-Co双金属氧化物/g-C 3N 4纳米复合催化剂对废气的降解效果。
本发明涉及的原料都是市售常规化合物，具体操作以及测试方法为常规技术。
下面结合实施例对本发明作进一步描述。
实施例一：二维g-C 3N 4纳米片的制备：首先，在带盖铝坩埚中加入10g尿素，放入马夫炉中，盖上盖子，550℃煅烧4h，升温速度为2.5℃·min -1（室温至550℃），待马弗炉冷却至室温后，得到了黄色固体；然后将得到的黄色固体平铺在长方形坩埚中，再以500℃煅烧2 h，升温速率为5℃·min -1（室温至500℃），收集得到浅黄色产物，即二维g-C 3N 4纳米片。
为了观察材料的形貌，采用扫描电镜和透射电镜对本实施例制备的产品进行表征，附图1是本实施例制备的二维g-C 3N 4纳米片的扫描电镜图和透射电镜图，（a）和（b）分别是本实施例制备的g-C 3N 4纳米片，称为CN。
实施例二：Ni-Co双金属氧化物/g-C 3N 4纳米复合材料的制备：首先，将100 mg六水合硝酸镍（Ni(NO 3) 3·6H 2O），162.5 mg柠檬酸钠（Na 3C 6H 5O 7·2H 2O）和150 mg g-C 3N 4纳米片分散在20 ml去离子水中，常规搅拌形成溶液A；200 mg钴氰化钾(K 3[Co(CN) 6])在20 ml去离子水中常规搅拌形成溶液B；将A和B溶液混合后在室温下静置老化24 h，所得产物经水、乙醇常规离心洗涤后，沉淀在60℃烘箱下干燥24 h，得到的淡蓝色样品为Ni 3[Co(CN) 6]/g-C 3N 4纳米复合材料；然后将所得Ni 3[Co(CN) 6]/g-C 3N 4纳米复合材料在马弗炉中以350℃煅烧2 h，升温速率为2℃min -1（室温至350℃），待马弗炉自然冷却至室温后，制备出了NiCoO x/g-C 3N 4纳米复合材料，简单标记为NICO/CN-100。
为了观察材料复合后的形貌，采用扫描电镜和透射电镜对本实施例制备的产品进行表征，附图1是本实施例制备Ni 3[Co(CN) 6]/g-C 3N 4纳米复合材料和NiCoO x/g-C 3N 4纳米复合材料的扫描电镜图和透射电镜图，（c）和（d）本实施例制备的Ni 3[Co(CN) 6]/g-C 3N 4纳米复合材料，（e）和（f）表示本实施例制备的三维/二维NiCoO x/g-C 3N 4纳米复合材料。
根据上述相同的制备方法，在g-C 3N 4纳米片保持为150 mg的情况下，分别以50 mg、75 mg和125 mg六水合硝酸镍制备了不同比例的NiCoO x/g-C 3N 4纳米复合材料（钴盐、钠盐的质量不变），分别标记为NICO/CN-50、NICO/CN-75和NICO/CN-125。
对比例一：Ni-Co双金属氧化物的制备：首先，0.8 g六水合硝酸镍（Ni(NO 3) 3·6H 2O）和1.3 g柠檬酸钠（Na 3C 6H 5O 7·2H 2O）在20 ml去离子水中常规搅拌形成透明溶液A；1.6 g钴氰化钾(K 3[Co(CN) 6])在20 ml去离子水中常规搅拌形成溶液B；将A和B溶液混合后在室温下老化24 h（静置），所得产物经水、乙醇常规离心洗涤后，沉淀在60℃烘箱下干燥24 h，得到的蓝色样品为Ni-Co普鲁士蓝前驱体(Ni 3[Co(CN) 6] 2)。而后将获得的Ni-Co普鲁士蓝前驱体在马弗炉中以350℃煅烧2 h，升温速率为2℃min -1（室温至350℃），待马弗炉自然冷却至室温后，所得黑色产物是Ni-Co双金属氧化物，称为NiCoO x。
为了观察材料的形貌，采用扫描电镜和透射电镜对上述制备的产品进行表征，附图2是上述制备的Ni 3[Co(CN) 6] 2和Ni-Co双金属氧化物的扫描和透射电镜图。（a）和（b）分别是Ni 3[Co(CN) 6] 2实心六面体，（c）和（d）表示空心的NiCoO x。
应用实施例：光催化处理废气，具体步骤如下：室温下，将100 mg待测催化剂平铺在体积为2.26 L的密闭圆柱形检测室中的木板上，并在其上方垂直放置300 W氙灯。通过将压缩瓶中的空气和一氧化氮混合来控制一氧化氮浓度为600 ppb，并以1.2 L/min的流速通过反应室。当催化剂达到吸附-解吸平衡时（0.5 h），打开氙灯，并在NO x分析仪上开始光催化测量。测量时间为30 min，采样时间间隔为1 min，一共得到30组数据。
附图3为NiCoO x、g-C 3N 4和不同比例NiCoO x/g-C 3N 4复合材料处理废气的效果图，通过效果图3发现NiCoO x/g-C 3N 4对废气的催化效率明显优于NiCoO x（20%），和g-C 3N 4（37%）；并且NICO/CN-100可以达到最高59.1%的降解效果。说明NiCoO x/g-C 3N 4复合物对一氧化氮有良好的催化降解活性。
将100mg实施例二的Ni 3[Co(CN) 6]/g-C 3N 4纳米复合材料进行上述同样的测试，可以达到最高40%的降解效果。
将实施例二的煅烧温度调至为550℃，其余不变，得到高温NICO/CN-100，进行上述同样的测试，可以达到最高43.2%的降解效果。
将实施例二的钴氰化钾更换为等钴摩尔量的六水合硝酸钴，其余不变，得到对比NICO/CN-100，进行上述同样的测试，可以达到最高49.6%的降解效果。
附图4为NICO/CN-100对废气降解的循环效果图，从图中可以看出经5次循环后，仍然表现出良好的降解效果。因此，该催化剂可以重复使用，具有良好的稳定性。
总结：通过以上分析，本发明通过简单易操作的自组装和低温煅烧法成功制备了三维/二维NiCoO x/g-C 3N 4纳米复合材料。而且本发明公开的复合材料对于废气具有较强的可见光催化降解。除此之外，本发明的制作过程简单，经济环保等优点，制备成本低，因此在废气处理中将有着良好的应用前景。

Claims (10)

  1. 一种三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料的制备方法包括以下步骤：
    （1）以尿素为原料，煅烧制成g-C 3N 4纳米片；
    （2）以镍盐、钴盐、钠盐和g-C 3N 4纳米片为原料，通过老化、低温煅烧得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料。
  2. 根据权利要求1所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，镍盐为六水合硝酸镍，钴盐为钴氰化钾，钠盐为柠檬酸钠。
  3. 根据权利要求1所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，步骤（1）中，煅烧的温度为300～600℃，时间为2～8 h，升温速率为2～5℃·min -1。
  4. 根据权利要求3所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，步骤（1）中，煅烧由第一次煅烧与第二次煅烧组成，第一次煅烧的温度高于第二次煅烧的温度，第一次煅烧的升温速率小于第二次煅烧的升温速率。
  5. 根据权利要求1所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，步骤（2）中，镍盐、钴盐、钠盐、g-C 3N 4纳米片的质量比为（1～6）∶（3～8）∶（3～8）∶3。
  6. 根据权利要求1所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，其特征在于，步骤（2）中，老化时间为12～48 h；低温煅烧的温度为150～450℃，时间为1～4 h，升温速率为2～5℃·min -1。
  7. 一种光催化处理废气的方法，其特征在于，包括以下步骤：
    （1）以尿素为原料，煅烧制成g-C 3N 4纳米片；
    （2）以镍盐、钴盐和g-C 3N 4纳米片为原料，通过低温煅烧得到三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料；
    （3）光照下，将废气通过三维/二维Ni-Co双金属氧化物/g-C 3N 4纳米复合材料，实现废气的光催化处理。
  8. 根据权利要求7所述光催化处理废气的方法，其特征在于，，步骤（3）中，光照为可见光照射。
  9. 根据权利要求7所述光催化处理废气的方法，其特征在于，废气为氮氧化物。
  10. 权利要求1所述三维/二维 Ni-Co双金属氧化物/g-C 3N 4纳米复合材料在催化处理废气中的应用。
PCT/CN2021/139029 2020-10-20 2021-12-17 三维 / 二维 Ni-Co 双金属氧化物 /g-C3N4 纳米复合材料及其制备方法与应用 WO2022083793A1 (zh)

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CN116351471A (zh) * 2023-03-13 2023-06-30 南方医科大学 一种普鲁士蓝/g-C3N4复合光催化剂及其制备方法和应用
CN116351471B (zh) * 2023-03-13 2024-04-26 南方医科大学 一种普鲁士蓝/g-C3N4复合光催化剂及其制备方法和应用
CN117427661A (zh) * 2023-10-19 2024-01-23 海南师范大学 一种硫化钴镍/薄层石墨相氮化碳复合材料及其制备方法和应用

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