CN115055200B - Cu (copper) alloy 2 Preparation method of O/HBN composite material and nitrogen fixation application - Google Patents
Cu (copper) alloy 2 Preparation method of O/HBN composite material and nitrogen fixation application Download PDFInfo
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- CN115055200B CN115055200B CN202210846996.2A CN202210846996A CN115055200B CN 115055200 B CN115055200 B CN 115055200B CN 202210846996 A CN202210846996 A CN 202210846996A CN 115055200 B CN115055200 B CN 115055200B
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
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- C01C1/04—Preparation of ammonia by synthesis in the gas phase
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Abstract
The invention discloses a Cu 2 Preparation method of O/HBN composite material and nitrogen fixation application. The method of the invention comprises the steps of firstly adding waterAdding hexagonal boron nitride HBN and CuSO 4 A solution; dropwise adding NaOH solution after ultrasonic treatment for minutes, and then adding ascorbic acid; stirring, standing for precipitation, centrifuging, washing, and drying to obtain Cu 2 O/HBN composite material. The invention disperses Cu by a simple strategy 2 The O load forms a heterojunction at the HBN to enhance the photocatalytic nitrogen fixation capacity. The photocatalysis composite material prepared by the invention does not harm the environment, and the prepared Cu 2 The O/HBN composite material has better photocatalysis nitrogen fixation effect.
Description
Technical Field
The invention belongs to the field of semiconductor materials, and relates to a Cu 2 Preparation method of O/HBN composite material and nitrogen fixation application.
Background
Various organic substances containing amino groups, which are indispensable in the natural world to constitute biomacromolecule proteins and genetic material DNA. Ammonia is used as a basic substance constituting amino acids and various base pairs, and the production mode in nature mainly depends on the transformation of nitrogen-fixing bacteria. With the progress of human development, the yield of ammonia cannot meet people's lives. The Haber-Bosch process became the primary source of ammonia production in the beginning of the 20 th century. The Haber-Bosch process is today anyway the main production form of ammonia. The technology requires high temperature (300 ℃) and high pressure (10 MPa) to consume a large amount of fossil fuel, and does not accord with the current green chemical concept. In order to pursue reduction of nitrogen gas to ammonia at normal temperature and pressure, research on photocatalytic nitrogen fixation has been a popular research topic.
Cuprous oxide is a low-cost semiconductor material responding to visible light, and has been widely focused in the fields of photoelectrocatalysis and the like. The proper conduction band potential and forbidden band width of the cuprous oxide meet the reduction potential of the visible light absorption of photocatalysis and the conversion of nitrogen into ammonia. However, the cuprous oxide is located on the valence band and the oxidation potential cannot oxidize the water into oxygen, so that the reaction process needs the participation of a sacrificial agent. Boron nitride HBN is a two-dimensional material with excellent mechanical strength and chemical stability, and the hexagonal boron nitride HBN has a structure similar to graphite. But is often considered an insulator due to the wide forbidden bandwidth of BN. Recent studies have shown that HBN is excited to yield at about 254nm in UV lightHigh energy electrons and holes are generated. Luo et al reduce band gap formation of porous Boron Carbon Nitride (BCN) nanoplatelets for photocatalytic reduction of CO by doping with C 2 . By loading TiO on HBN 2 Formation of BN/TiO 2 The heterojunction is used to degrade RhB. As the research goes deep, HBN may become a new material in photocatalysis research.
Disclosure of Invention
An object of the present invention is to provide a Cu 2 A preparation method of an O/HBN composite material.
The method of the invention is as follows:
step (1) adding hexagonal boron nitride HBN into water to form aqueous HBN solution with the concentration of 0.3-30 g/L, and then adding CuSO with the concentration of 0.5-1.5 mol/L 4 A solution; added CuSO 4 The volume ratio of the solution to the HBN aqueous solution is 0.005-0.01:1;
step (2), dropwise adding NaOH solution with the concentration of 0.5-1.5 mol/L after ultrasonic treatment for 20-60 minutes, and then adding ascorbic acid with the concentration of 0.1-0.3 mol/L; the volume ratio of the added NaOH solution to the HBN aqueous solution is 0.05-0.1:1, and the volume ratio of the added ascorbic acid to the HBN aqueous solution is 0.05-0.1:1;
stirring for 20-60 min, standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
The invention further aims to provide an application of the prepared Cu2O/HBN composite material in photocatalytic nitrogen fixation.
The invention disperses Cu by a simple strategy 2 The O load forms a heterojunction at the HBN to enhance the photocatalytic nitrogen fixation capacity. The beneficial effects of the invention include:
1. the invention does not involve the use of a sacrificial agent in the photocatalysis nitrogen fixation process, and prepares Cu by an ultrasonic coprecipitation method 2 The O/HBN composite material can be prepared into the required photocatalysis composite material without causing harm to the environment.
2. Cu prepared by the invention 2 The O/HBN composite material has better photocatalysis nitrogen fixation effect.
Drawings
FIG. 1 is Cu 2 O-scanning electron microscopeA mirror image;
FIG. 2 is Cu 2 Scanning electron microscope pictures of the O/BN composite material;
FIG. 3 is Cu 2 XRD characterization of the O/BN composite material.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are in no way limiting.
Example 1.
Step (1) adding 0.3g of hexagonal boron nitride HBN to 1L of water, and then adding 0.01L of CuSO with the concentration of 0.5mol/L 4 A solution;
step (2), dropwise adding 0.1L of NaOH solution with the concentration of 0.5mol/L after ultrasonic treatment for 20 minutes, and then adding 0.1L of ascorbic acid with the concentration of 0.1 mol/L;
stirring for 20 minutes in the step (3), standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
Example 2.
Step (1) 1g of hexagonal boron nitride HBN was added to 1L of water, followed by 0.008L of CuSO with a concentration of 0.8mol/L 4 A solution;
step (2) is carried out ultrasonic treatment for 30 minutes, then 0.08L of NaOH solution with the concentration of 0.8mol/L is added dropwise, and then 0.09L of ascorbic acid with the concentration of 0.15mol/L is added;
stirring for 60 minutes in the step (3), standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
Example 3.
Step (1) 8g of hexagonal boron nitride HBN was added to 1L of water, followed by 0.007L of CuSO at a concentration of 1.0mol/L 4 A solution;
step (2), dropwise adding 0.07L of NaOH solution with the concentration of 1.0mol/L after ultrasonic treatment for 40 minutes, and adding 0.08L of ascorbic acid with the concentration of 0.2 mol/L;
stirring for 50 minutes in the step (3), standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
Example 4.
Step (1) 15g of hexagonal boron nitride HBN was added to 1L of water, followed by 0.006L of C at a concentration of 1.2mol/LuSO 4 A solution;
step (2), dropwise adding 0.06L of NaOH solution with the concentration of 1.2mol/L after ultrasonic treatment for 50 minutes, and then adding 0.06L of ascorbic acid with the concentration of 0.25 mol/L;
stirring for 30 minutes in the step (3), standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
Example 5.
Step (1) 30g of hexagonal boron nitride HBN was added to 1L of water, followed by 0.005L of CuSO having a concentration of 1.5mol/L 4 A solution;
step (2), dropwise adding 0.05L of NaOH solution with the concentration of 1.5mol/L after ultrasonic treatment for 60 minutes, and adding 0.05L of ascorbic acid with the concentration of 0.3 mol/L;
stirring for 40 minutes in the step (3), standing for precipitation, centrifuging, washing and drying to obtain Cu 2 O/HBN composite material.
Example 6.
HBN with a mass of 1.4157g is added into 30mL of aqueous solution, and 0.2mL of CuSO with a concentration of 1mol/L is added dropwise 4 After the solution is sonicated for 30min, 2mL of NaOH solution with the concentration of 1mol/L is added dropwise, 2mL of ascorbic acid with the concentration of 0.2mol/L is added, stirring is carried out for 30min, and standing, precipitation, centrifugal washing and drying are carried out.
Example 7.
HBN with a mass of 0.2717g is added into 30mL of aqueous solution, and 0.2mL of CuSO with a concentration of 1mol/L is added dropwise 4 After the solution is sonicated for 30min, 2mL of NaOH solution with the concentration of 1mol/L is added dropwise, 2mL of ascorbic acid with the concentration of 0.2mol/L is added, stirring is carried out for 30min, and standing, precipitation, centrifugal washing and drying are carried out.
Example 8.
HBN with a mass of 0.1287g is added into 30mL of aqueous solution, and 0.2mL of CuSO with a concentration of 1mol/L is added dropwise 4 After the solution is sonicated for 30min, 2mL of NaOH solution with the concentration of 1mol/L is added dropwise, 2mL of ascorbic acid with the concentration of 0.2mol/L is added, stirring is carried out for 30min, and standing, precipitation, centrifugal washing and drying are carried out.
Example 9.
HBN with mass of 0.0572g is added into 30mL of aqueous solution, and 0.2mL of CuSO with concentration of 1mol/L is added dropwise 4 Stirring the solution after ultrasonic treatment for 30min2mL of NaOH solution with the concentration of 1mol/L is added dropwise, 2mL of ascorbic acid with the concentration of 0.2mol/L is added, stirring is carried out for 30min, standing, precipitation, centrifugal washing and drying are carried out.
EXAMPLE 10 Cu prepared by the method of any one of examples 1-9 2 The O/HBN composite material is applied to photocatalytic nitrogen fixation.
Comparative example 1.
Pure Cu 2 O, HBN was not added, and the other conditions were the same as in examples 6 to 9.
To evaluate Cu 2 Feasibility, morphology and distribution of O/HBN composite material preparation, cu was determined by scanning microscope 2 The O/HBN composite material is characterized. As seen by a scanning electron microscope, as shown in FIG. 1, cu is shown 2 O shows a cubic structure. As shown in FIG. 2, cu 2 O/BN composite material, ultra-fine Cu can be seen 2 O is attached to HBN, facilitating photoelectron transfer. Characterization of different mass fractions of Cu by XRD 2 O/BN composite materials (comparative example 1, examples 6-9). As shown in FIG. 3, cu can be seen 2 O/HBN is located at 36.4 degrees, 61.3 degrees and Cu 2 O (PDF#05-0667) corresponds to, and wide diffraction peaks at 26.7 DEG, 41.6 DEG correspond to BN (PDF#34-0421). Not and with Cu 2 The increase in the amount of O is at 36.4 Cu 2 The characteristic peak of O is more obvious, and the characteristic peak of HBN is weakened. XRD shows Cu 2 Cu is effectively obtained by compositing O and HBN through an ultrasonic coprecipitation method 2 O/HBN photocatalyst. By different loading mass percentages of Cu 2 O/HBN,20% Cu loading 2 O/HBN has a higher purity than pure HBN and pure Cu 2 The nitrogen fixation effect of O is higher.
Claims (1)
1. Cu (copper) alloy 2 The application of the O/HBN composite material in the photocatalysis nitrogen fixation is characterized in that the Cu 2 The preparation method of the O/HBN composite material comprises the following steps:
step (1), adding hexagonal boron nitride HBN into water to form aqueous HBN solution with the concentration of 0.3-30 g/L, and then adding CuSO with the concentration of 0.5-1.5 mol/L 4 A solution; added CuSO 4 The volume ratio of the solution to the HBN aqueous solution is (0.005-0.01): 1;
step (2), dropwise adding NaOH solution with the concentration of 0.5-1.5 mol/L after ultrasonic treatment for 20-60 minutes, and then adding ascorbic acid with the concentration of 0.1-0.3 mol/L; the volume ratio of the added NaOH solution to the HBN aqueous solution is (0.05-0.1): 1, and the volume ratio of the added ascorbic acid to the HBN aqueous solution is (0.05-0.1): 1;
step (3), stirring for 20-60 minutes, standing for precipitation, centrifuging, washing and drying to obtain the Cu 2 O/HBN composite material.
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