CN114100660A - Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof - Google Patents
Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a titanium nitride and nitrogen doped composite graphene-black phosphorus based catalyst, and a preparation method and application thereof, and belongs to the technical field of hydrogen energy. The preparation method of the catalyst based on the titanium nitride and the nitrogen-doped composite graphene-black phosphorus comprises the following steps: step 1: preparing composite graphene-black phosphorus powder; step 2: preparing a reducing agent dispersion liquid; and step 3: preparing reducing agent powder; and 4, step 4: preparing a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus. The invention also discloses a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus and application thereof. The catalyst prepared by the method has very high catalytic activity, can catalyze the ORR to be carried out by a route close to four electron transfer, and is a promising fuel cell cathode ORR electro-catalyst.
Description
Technical Field
The invention relates to a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus, a preparation method and application thereof, and belongs to the technical field of hydrogen energy.
Background
The combustion product of the hydrogen is water, so that the environment is not polluted, and the heat generated by combustion is high and the heat value is high; and the like, which are widely noticed by people, scientists have conducted a great deal of research on the advantages. It is mainly applied to the fields of petrochemical industry, fuel cells, solar cells and the like. At present, hydrogen used for industrial production is produced by steam reforming reaction of natural gas or methane, but the natural gas is a non-renewable resource,in addition, when natural gas is used for producing hydrogen, a large amount of CO is released2And causes pollution to the environment. Therefore, methods of hydrogen production by electrolysis, hydrogen production by thermal decomposition, hydrogen production by solar energy, hydrogen production by biomass and the like become research hotspots. However, according to the current research data, the efficiency of hydrogen production by electrolysis can reach 75-85%, and the method is the highest efficiency in the current hydrogen production method. However, during the hydrogen production by electrolysis, the cathode hydrogen evolution overpotential leads to the increase of the cell voltage for hydrogen production by water electrolysis and the increase of the electric energy consumption, which greatly limits the large-scale development and application.
In order to reduce the electrolysis energy consumption and improve the hydrogen evolution efficiency, a high-efficiency cathode hydrogen evolution catalyst material is required to be adopted. At present, in the actual application of Hydrogen Evolution Reaction (HER for short), a noble metal Pt-based catalyst is still required. The precious metal material has limited reserves and high price, and cannot meet the requirements of the energy field on HER, and the development of a high-efficiency non-precious metal HER catalyst becomes an effective way for solving the problem. Similar to other heterogeneous catalysts, the catalytic performance of HER catalysts is influenced by the density of active sites and the reactivity, factors such as low and medium conductivity, low specific surface area and instability at operating voltage are important causes of low catalytic activity. The transition metal element has the advantages of high stability, rich reserves, low cost and the like, and is expected to become a good HER catalyst. The nitride, carbide and phosphide of the transition metal have the advantages of high corrosion resistance, high stability, high melting point, high mechanical property and the like, and become ideal alternative materials for applications such as electro-catalysts, cone ion batteries, solar batteries and the like.
In the field of industrial catalysis, transition metal nitrides, especially titanium nitride (TiN), in the ORR catalyst of non-noble metal fuel cell cathodes have become a promising material due to their high conductivity, chemical stability and simple synthesis conditions, and have been widely used. Titanium nitride has shown excellent performance in many fields including dye-sensitized solar cells, lithium air cells, supercapacitors, biosensors, and the like. In addition, nitrogen-doped graphene (NG) and black phosphorus (P) have attracted much research interest due to their unique atomic structures and electron transport properties. In the two-dimensional framework of nitrogen-doped graphene and black phosphorus, nitrogen atoms can create net positive charges on adjacent carbon atoms, so that electrons are more easily attracted, and the Oxygen absorption and Oxygen Reduction Reaction (ORR) process is facilitated. Moreover, compared with noble metals, titanium nitride, nitrogen-doped graphene and black phosphorus are all wide in storage amount and low in cost, and can resist corrosion of alkaline solution for a long time. In the prior art, no relevant report about the preparation of the catalyst by combining the three is available.
In view of this, there is a need to provide a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus, a preparation method and an application thereof, so as to overcome the defects of the prior art.
Disclosure of Invention
One of the purposes of the invention is to provide a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus.
The technical scheme for solving the technical problems is as follows: a preparation method of a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus comprises the following steps:
step 1: preparation of composite graphene-black phosphorus powder
Uniformly mixing 0.1g-0.2g of graphene oxide and 0.1g-0.2g of black phosphorus, dispersing in 10mL of absolute ethanol, and drying to obtain composite graphene-black phosphorus powder;
step 2: preparation of reducing agent Dispersion
Respectively dispersing the composite graphene-black phosphorus powder obtained in the step 1 and 2.0-3.0 mL of tetrabutyl titanate in 15mL of absolute ethyl alcohol, mixing the two obtained dispersions, and continuously stirring overnight to obtain a reducing agent dispersion;
and step 3: preparation of reducing agent powder
Carrying out suction filtration separation on the reducing agent dispersion liquid obtained in the step 2, cleaning and drying to obtain reducing agent powder;
and 4, step 4: preparation of titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst
And (4) calcining the reducing agent powder obtained in the step (3) by adopting temperature programming under the atmosphere of ammonia gas to obtain the catalyst based on the titanium nitride and the nitrogen-doped composite graphene-black phosphorus.
The principle of the preparation method of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus is as follows:
in step 1, Graphene Oxide (GO for short) and Black Phosphorus (P for short) are uniformly mixed, dispersed in absolute ethyl alcohol and dried to obtain composite Graphene-Black Phosphorus (GP) powder.
In step 2 of the invention, the composite graphene-black phosphorus (GP) powder is dispersed in an absolute ethanol solution of tetrabutyl titanate (TBT for short) to obtain a reducing agent dispersion liquid, wherein the surface of the composite graphene-black phosphorus (GP) can effectively adsorb titanium (Ti) ions.
In the step 4 of the invention, the reducing agent powder is calcined in the ammonia atmosphere, the composite graphene-black phosphorus (GP) is subjected to a reduction reaction, and nitrogen (N) is successfully introduced to dope and generate nitrogen-doped composite graphene-black phosphorus (NGP) and synchronously generate titanium nitride (TiN). Meanwhile, titanium nitride (TiN) nanoparticles are also generated on the nitrogen-doped composite graphene-black phosphorus (NGP) substrate through a nitridation reaction.
In conclusion, the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the invention has good catalytic activity, and can catalyze ORR to be carried out by a path close to four-electron transfer. The nitrogen-doped composite graphene-black phosphorus (NGP) sheet under the titanium nitride (TiN) nanoparticles provides a good conductive carrier, reduces aggregation of catalyst particles, and improves ORR catalytic activity of titanium nitride (TiN) through a synergistic chemical coupling effect. Moreover, the composite shows better methanol tolerance and long-range stability in alkaline medium than commercial lead-carbon catalyst (Pt/C), thereby becoming a promising fuel cell cathode ORR electrocatalyst.
The preparation method of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus has the beneficial effects that:
1. the raw materials used in the invention, such as graphene oxide, black phosphorus and titanium nitride, have wide reserves and low cost, can resist the corrosion of alkaline solution for a long time, and have high product purity, no by-product mixing, simple process flow, low energy consumption of low-temperature calcination, and suitability for industrial large-scale production.
2. The catalyst prepared by the invention has very high catalytic activity, and can catalyze ORR to be carried out by a route close to four electron transfer. The nitrogen-doped composite graphene-black phosphorus (NGP) sheet under the titanium nitride (TiN) nanoparticles provides a good conductive carrier, reduces aggregation of catalyst particles, and improves ORR catalytic activity of titanium nitride (TiN) through a synergistic chemical coupling effect. Moreover, the composite shows better methanol tolerance and long-range stability in alkaline medium than commercial lead-carbon catalyst (Pt/C), thereby becoming a promising fuel cell cathode ORR electrocatalyst.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step 1, the graphene oxide has a sheet diameter of 0.5 to 5 μm and a thickness of 0.8 to 1.2 nm.
The adoption of the further beneficial effects is as follows: by adopting the graphene oxide with the parameters, the performance of the final product obtained subsequently is better.
Further, in the step 1, the purity of the black phosphorus is 99.998%.
The adoption of the further beneficial effects is as follows: by adopting the black phosphorus with the parameters, the performance of the subsequent final product is better.
Further, in the step 1, the drying temperature is 80 ℃ and the drying time is 2 hours.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the composite graphene-black phosphorus powder can be obtained.
Further, in the step 2, the dispersion is that ultrasonic treatment with 16KW-60KW power is carried out for 8min-10min under the condition that the stirring speed is 1mm/min-4 mm/min.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the dispersion effect is better.
Further, in the step 3, a PVDF membrane with the aperture of 200nm is adopted for suction filtration and separation.
The adoption of the further beneficial effects is as follows: PVDF membrane, i.e., Polyvinylidene Fluoride membrane, has a layered porous network fiber structure. The PVDF membrane is hydrophobic, the pore size of the membrane is large or small, and the binding of the membrane to low molecular weight protein is firmer along with the continuous reduction of the pore size of the membrane. The PVDF membrane with the aperture of 200nm is covered on the sand core funnel, so that the suction filtration and separation of the reducing agent dispersion liquid can be realized.
Further, in step 3, the cleaning is to clean 3 times with absolute ethyl alcohol and then clean 3 times with deionized water.
Further, in the step 3, the drying temperature is 100 ℃ and the drying time is 12 hours.
The adoption of the further beneficial effects is as follows: with the above parameters, a third mixture can be obtained which meets the requirements.
Further, in step 4, the temperature programming refers to raising the temperature to 1000 ℃ at a rate of 10 ℃/min and keeping the temperature for 2 hours.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the calcining effect is better.
The second purpose of the invention is to provide a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus.
The technical scheme for solving the technical problems is as follows: the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus has the beneficial effects that:
the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus has very high catalytic activity, excellent methanol tolerance and long-range stability, and is a promising fuel cell cathode ORR electrocatalyst.
The third purpose of the invention is to provide the application of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method.
The technical scheme for solving the technical problems is as follows: the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method is applied to hydrogen production by water electrolysis.
The application of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus has the beneficial effects that:
the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method can be used for hydrogen production by water electrolysis, and has a wide application prospect.
Drawings
Fig. 1 is an infrared spectrum of a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus obtained in example 1 of the present invention.
FIG. 2 TEM images of a catalyst at different calcination temperatures in Experimental example 2 of the present invention, wherein the calcination temperature in A is 900 deg.C, the calcination temperature in B is 1000 deg.C, and the calcination temperature in C is 1100 deg.C.
FIG. 3 is a graph of Koutecky-Levich of different substances at a potential of 0.3V in example 3 of the present invention.
FIG. 4 is a CV diagram of various complexes in Experimental example 4 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus of the embodiment comprises the following steps:
step 1: preparation of composite graphene-black phosphorus powder
Uniformly mixing 0.15g of graphene oxide and 0.15g of black phosphorus, dispersing in 10mL of absolute ethanol, and drying at 80 ℃ for 2h to obtain the composite graphene-black phosphorus powder. Wherein the sheet diameter of the graphene oxide is 0.5-5 μm, and the thickness is 0.8-1.2 nm; the purity of the black phosphorus is 99.998%.
Step 2: preparation of reducing agent Dispersion
And (3) respectively dispersing the composite graphene-black phosphorus powder obtained in the step (1) and 2.5mL of tetrabutyl titanate in 15mL of absolute ethyl alcohol under the condition that the stirring speed is 2.5mm/min, and treating for 8min by using ultrasonic waves with the power of 30 KW. The two dispersions obtained were mixed and stirred continuously overnight to give a reducing agent dispersion.
And step 3: preparation of reducing agent powder
And (3) carrying out suction filtration and separation on the reducing agent dispersion liquid obtained in the step (2) by adopting a PVDF membrane with the aperture of 200nm, washing for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, and drying for 12h at 100 ℃ to obtain reducing agent powder.
And 4, step 4: preparation of titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst
And (3) heating the reducing agent powder obtained in the step (3) to 1000 ℃ at a speed of 10 ℃/min in an ammonia atmosphere, keeping the temperature for 2 hours, and calcining to obtain the titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method is applied to hydrogen production by water electrolysis.
Example 2
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus of the embodiment comprises the following steps:
step 1: preparation of composite graphene-black phosphorus powder
Uniformly mixing 0.1g of graphene oxide and 0.1g of black phosphorus, dispersing in 10mL of absolute ethanol, and drying at 80 ℃ for 2h to obtain the composite graphene-black phosphorus powder. Wherein the sheet diameter of the graphene oxide is 0.5-5 μm, and the thickness is 0.8-1.2 nm; the purity of the black phosphorus is 99.998%.
Step 2: preparation of reducing agent Dispersion
And (3) respectively dispersing the composite graphene-black phosphorus powder obtained in the step (1) and 2.0mL of tetrabutyl titanate in 15mL of absolute ethyl alcohol under the condition that the stirring speed is 1mm/min, and treating for 9min by using ultrasonic waves with the power of 16 KW. The two dispersions obtained were mixed and stirred continuously overnight to give a reducing agent dispersion.
And step 3: preparation of reducing agent powder
And (3) carrying out suction filtration and separation on the reducing agent dispersion liquid obtained in the step (2) by adopting a PVDF membrane with the aperture of 200nm, washing for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, and drying for 12h at 100 ℃ to obtain reducing agent powder.
And 4, step 4: preparation of titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst
And (3) heating the reducing agent powder obtained in the step (3) to 1000 ℃ at a speed of 10 ℃/min in an ammonia atmosphere, keeping the temperature for 2 hours, and calcining to obtain the titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method is applied to hydrogen production by water electrolysis.
Example 3
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus of the embodiment comprises the following steps:
step 1: preparation of composite graphene-black phosphorus powder
00.2g of graphene oxide and 0.2g of black phosphorus are uniformly mixed, dispersed in 10mL of absolute ethanol and dried at 80 ℃ for 2h to obtain composite graphene-black phosphorus powder. Wherein the sheet diameter of the graphene oxide is 0.5-5 μm, and the thickness is 0.8-1.2 nm; the purity of the black phosphorus is 99.998%.
Step 2: preparation of reducing agent Dispersion
And (3) respectively dispersing the composite graphene-black phosphorus powder obtained in the step (1) and 3.0mL of tetrabutyl titanate in 15mL of absolute ethyl alcohol under the condition that the stirring speed is 4mm/min, and treating for 10min by using ultrasonic waves with the power of 60 KW. The two dispersions obtained were mixed and stirred continuously overnight to give a reducing agent dispersion.
And step 3: preparation of reducing agent powder
And (3) carrying out suction filtration and separation on the reducing agent dispersion liquid obtained in the step (2) by adopting a PVDF membrane with the aperture of 200nm, washing for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, and drying for 12h at 100 ℃ to obtain reducing agent powder.
And 4, step 4: preparation of titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst
And (3) heating the reducing agent powder obtained in the step (3) to 1000 ℃ at a speed of 10 ℃/min in an ammonia atmosphere, keeping the temperature for 2 hours, and calcining to obtain the titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method.
The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method is applied to hydrogen production by water electrolysis.
Experimental example 1
An ITO glass working electrode is used for Cyclic Voltammetry (CV), the surface resistivity of the ITO glass working electrode is 7-10 omega, and the area of the working electrode is 1cm multiplied by 1 cm. The method comprises the following steps of firstly ultrasonically cleaning the glass substrate with acetone for 30min, then washing the glass substrate with ethanol and deionized water under the assistance of ultrasound to obtain a mirror-surface smooth surface, and finally blow-drying the glass substrate with nitrogen airflow for later use.
Dissolving 2mg of a sample to be detected in 1mL of Nafion solution with the mass percent of 0.5%, and forming 2mg/mL of electrode solution to be detected through ultrasonic treatment. Subsequently, 6. mu.l (for CV testing, load of 0.17 mg. cm) was added dropwise-2) Or 20. mu.l (for RDE test, load-0.2 mg. cm)-2) The reducing agent dispersion is placed on the surface of the ITO glass, and the ITO glass is placed and aired for 2 hours at room temperature for testing. This reducing agent dispersion liquid was the reducing agent dispersion liquid prepared in step 2 of example 1.
Cyclic Voltammetry (CV) tests were performed on the titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst (denoted as TiN/NGP composite), the pure-phase nitrogen-doped composite graphene-black phosphorus (NGP), and the pure-phase titanium nitride (TiN) prepared in example 1. Phase-pure titanium nitride (TiN) nanoparticles exhibit very weak ORR catalytic activity with an onset potential and a reduction peak potential at about-0.15V and-0.53V, respectively. The cathode peak current of the pure-phase nitrogen-doped composite graphene-black phosphorus (NGP) is similar to that of pure-phase titanium nitride (TiN), but a more positive initial potential is about-0.08V, the peak potential is about-0.31V, and the performance of the pure-phase titanium nitride (TiN) is better. Compared with the former two, the catalytic performance of the catalyst (marked as TiN/NGP compound) based on the titanium nitride and the nitrogen-doped composite graphene-black phosphorus has obvious enhanced initial potential and reduction peak potential which are respectively shifted to about-0.12V and-0.37V in the positive direction, and the cathode peak current is also obviously improved, which indicates that the titanium nitride (TiN) and the nitrogen-doped composite graphene-black phosphorus (NGP) in the catalyst have synergistic ORR catalytic activity. ORR performance tests were also performed on physical mixtures of titanium nitride (TiN) and nitrogen-doped composite graphene-black phosphorus (NGP) (noted TiN + NGP), and the results showed that the initial and reduction peak potentials were at about-0.18V and-0.45V, respectively, which are significantly lower than the performance of the composite, indicating that simply mixing the two is not sufficient to effectively improve the overall catalytic performance.
From fig. 3, it can be observed that a large amount of titanium nitride (TiN) nanoparticles are uniformly distributed on the surface of the nitrogen-doped composite graphene-black phosphorus (NGP) sheet layer, and a series of clear-defined circular rings can be observed. The edges of the nitrogen-doped composite graphene-black phosphorus (NGP) sheets can also be observed, which indicates that the nitrogen-doped composite graphene-black phosphorus (NGP) sheets can promote uniform distribution of nanoparticles of titanium nitride (TiN), and also indicates that the introduction of titanium nitride (TiN) can also reduce agglomeration of the NG sheets.
Experimental example 2
The addition volume of tetrabutyl titanate in step 2 of example 1 was adjusted, and the mass of the composite graphene-black phosphorus powder was kept unchanged. The addition volumes of tetrabutyltitanate were 0.01mL, 0.02mL, 0.03mL, 0.04mL, 0.05mL, 0.5mL, lmL, 1.5mL, 2mL, 2.5mL, 3mL, 4mL and 5mL, respectively, and changes in the loading amount of titanium nitride (TiN) on the nitrogen-doped composite graphene-black phosphorus (NGP) substrate were observed by XRD and TEM. The ORR test demonstrated that the loading of titanium nitride (TiN) did have a significant effect on the electrocatalytic performance of a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus (denoted as TiN/NGP composite).
In addition, the electrocatalytic performance of the titanium nitride and nitrogen doped composite graphene-black phosphorus based catalyst (denoted as TiN/NGP composite) prepared in example 1 is also affected by the calcination temperature. The calcination temperatures were set at 900 deg.C, 1000 deg.C, and 1100 deg.C, respectively. TEM images of the catalyst at different calcination temperatures are shown in fig. 3. In the composite calcined at 1000 ℃, the distribution of titanium nitride (TiN) nanoparticles on the nitrogen-doped composite graphene-black phosphorus (NGP) sheet is very uniform, and the performance thereof is also significantly better than that of the sample calcined at 1100 ℃ and 900 ℃.
Therefore, the optimum amount of tetrabutyl titanate to be added was 2.5mL, and the optimum calcination temperature was 1000 ℃.
Experimental example 3
The electron transfer number (n) is calculated based on a Koutecky-Levich formula, and through an RDE test at different rotating speeds, the ORR catalytic performance of a catalyst (marked as a TiN/NGP compound) based on titanium nitride and nitrogen-doped composite graphene-black phosphorus can be further recognized. The Koutecky-Levich diagram of the different substances at a potential of 0.3V is shown in FIG. 3.
It can be observed that the nitrogen-doped composite graphene-black phosphorus catalyst (noted as TiN/NGP composite) prepared in example 1 has higher current density at the same rotation speed. NG and black phosphorus (P) show good ORR catalytic performance, the electron transfer number n is 3.25 and 3.45 respectively, and the electron transfer number n is close to the four-electron transfer process. For titanium nitride (TiN), n is 2.55, which is between the two and four electron paths, indicating that the ORR process at the electrode may proceed in a co-existing path, with both two and four electron paths. The n value of titanium nitride (TiN) + NG + black phosphorus (P) is only 3.16, which is a little lower than that of pure-phase NG and black phosphorus (P), indicating that the chemical coupling effect between the two components is very small and the effect of improving the overall performance is limited. Compared with the above materials, the n value of the nitrogen-doped composite graphene-black phosphorus catalyst prepared in example 1 is significantly increased to 3.99, which indicates that the common ORR catalyst is performed in a highly efficient four-electron transfer path, close to the commercial Pt/C catalyst.
Experimental example 4
In order to verify the function of the nitrogen-doped composite graphene-black phosphorus (NGP) substrate in the composite, the experimental example synthesizes a composite of titanium nitride (TiN) nanoparticles and multi-walled carbon nanotubes (denoted as TiN/MWCNT) and a composite of carbon black (denoted as TiN/CB) according to the same method, and the corresponding CV test curve is shown in fig. 4.
It can be observed that although TiN/MWCNT exhibit current density comparable to TiN/NGP, they are much worse than the latter in terms of initial and peak potentials. In contrast, the peak potential of TiN/CB composites is close to that of TiN/NGP, but the current density is much smaller. Therefore, it can be concluded that the nitrogen-doped composite graphene-black phosphorus (NGP) substrate plays an important role in the performance enhancement of the titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst (denoted as TiN/NGP composite).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus is characterized by comprising the following steps:
step 1: preparation of composite graphene-black phosphorus powder
Uniformly mixing 0.1g-0.2g of graphene oxide and 0.1g-0.2g of black phosphorus, dispersing in 10mL of absolute ethanol, and drying to obtain composite graphene-black phosphorus powder;
step 2: preparation of reducing agent Dispersion
Respectively dispersing the composite graphene-black phosphorus powder obtained in the step 1 and 2.0-3.0 mL of tetrabutyl titanate in 15mL of absolute ethyl alcohol, mixing the two obtained dispersions, and continuously stirring overnight to obtain a reducing agent dispersion;
and step 3: preparation of reducing agent powder
Carrying out suction filtration separation on the reducing agent dispersion liquid obtained in the step 2, cleaning and drying to obtain reducing agent powder;
and 4, step 4: preparation of titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst
And (4) calcining the reducing agent powder obtained in the step (3) by adopting temperature programming under the atmosphere of ammonia gas to obtain the catalyst based on the titanium nitride and the nitrogen-doped composite graphene-black phosphorus.
2. The method for preparing the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 1, the graphene oxide has a sheet diameter of 0.5 μm to 5 μm and a thickness of 0.8nm to 1.2 nm.
3. The method for preparing the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 1, the purity of the black phosphorus is 99.998%.
4. The preparation method of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 1, the drying temperature is 80 ℃ and the drying time is 2 h.
5. The method for preparing the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 2, the dispersion is carried out by ultrasonic treatment with power of 16KW-60KW for 8min-10min under the condition that the stirring speed is 1mm/min-4 mm/min.
6. The preparation method of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 3, a PVDF membrane with a pore diameter of 200nm is adopted for the suction filtration and separation; the cleaning is to clean for 3 times by using absolute ethyl alcohol and then clean for 3 times by using deionized water.
7. The preparation method of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 3, the drying temperature is 100 ℃ and the drying time is 12 h.
8. The method for preparing the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus according to claim 1, wherein in the step 4, the temperature programming is that the temperature is raised to 1000 ℃ at a rate of 10 ℃/min and is kept for 2 h.
9. The catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method of any one of claims 1 to 8.
10. The application of the catalyst based on titanium nitride and nitrogen-doped composite graphene-black phosphorus prepared by the preparation method of any one of claims 1 to 8 in hydrogen production by electrolyzing water.
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| CN115011972A (en) * | 2022-07-13 | 2022-09-06 | 云南大学 | Non-metal electrocatalytic material and preparation method and application thereof |
| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
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| MENGJIA LIU等: "Titanium Nitride Nanocrystals on Nitrogen-Doped Graphene as an Efficient Electrocatalyst for Oxygen Reduction Reaction", 《CHEM. EUR. J.》, vol. 19, pages 14781 * |
| ZHONGKE YUAN等: "Ultrathin Black Phosphorus-on-Nitrogen Doped Graphene for Efficient Overall Water Splitting: Dual Modulation Roles of Directional Interfacial Charge Transfer", 《J. AM. CHEM. SOC.》, vol. 141, pages 4972 * |
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| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
| CN115011972A (en) * | 2022-07-13 | 2022-09-06 | 云南大学 | Non-metal electrocatalytic material and preparation method and application thereof |
| CN115011972B (en) * | 2022-07-13 | 2023-08-18 | 云南大学 | Nonmetal electrocatalytic material and preparation method and application thereof |
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