CN111185220A - Carbon nitride supported Pd-based catalyst, and preparation method and application thereof - Google Patents
Carbon nitride supported Pd-based catalyst, and preparation method and application thereof Download PDFInfo
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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Abstract
The invention provides a preparation method of a carbon nitride supported Pd-based catalyst, which comprises the following steps of A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride; B) dispersing the thin-layer carbon nitride in water to obtain a first suspension; C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension; D) adding sodium hydroxide into the second suspension, and stirring to obtain a third suspension; E) and adding sodium borohydride into the third suspension, stirring to obtain a fourth suspension, and carrying out solid-liquid separation on the fourth suspension to obtain the carbon nitride supported Pd-based catalyst. The nano metal particles in the catalyst prepared by the invention are uniformly distributed on the carrier, have good interaction stability, and show excellent activity and selectivity for hydrogen production by formic acid decomposition. The invention also provides a carbon nitride supported Pd-based catalyst and application thereof as a catalyst in hydrogen production by formic acid decomposition.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a carbon nitride supported Pd-based catalyst, and a preparation method and application thereof.
Background
Since the first industrial revolution, fossil energy has become the main source of energy for the development of our society. The increasing demand for energy in developed and developing countries has led to a rapid depletion of energy resources, consistent with a critical raw material shortage for many important artificial chemicals, such as pesticides, pharmaceuticals, solvents, fertilizers and plastics. Meanwhile, a large amount of carbon dioxide is released into the atmosphere by the combustion of fossil fuel, changing the combination of natural carbon cycles, thereby causing another serious environmental problem of global warming. To alleviate the energy crisis, alleviate climate change, reduce the utilization and dependence on fossil fuels, the development of renewable energy is inevitable. Researchers have conducted extensive research on renewable energy sources such as solar energy, wind energy, tidal energy, and the like, which substitute fossil fuels. But typically these renewable energy sources are not directly available, mostly converted to electricity and connected to a smart grid. However, the electricity generated by renewable energy is transmitted through natural processes, and the instability of the electricity is large, so that the electricity grid is impacted greatly. At the same time, the distribution of renewable energy sources on the earth is also not equal. For example, solar energy is concentrated primarily in the equatorial region, and offshore shore lines have abundant tidal energy. Therefore, the rational and intelligent utilization of renewable energy necessitates energy conversion, storage and transportation systems.
Hydrogen energy is one of the most promising renewable and clean energy sources, obtainable by electrochemical water splitting driven by renewable energy sources. Hydrogen has a relatively high specific energy of 120kJ/kg, but its volumetric energy density is very low (10kJ/L, 1atm and 298K). Compressed hydrogen can provide higher volumetric energy density, but leakage problems and additional energy consumption during compression and cryogenic storage limit practical applications due to transport difficulties.
In recent years, extensive research has been conducted on solid and liquid hydrogen storage materials to develop an effective system to address the problems associated with compression and transportation. Formic acid is an effective liquid hydrogen storage material as an organic liquid micromolecule, and has the advantages of capability of decomposing at normal temperature to prepare hydrogen, no toxicity, wide source and low cost. However, the current formic acid decomposition hydrogen production catalyst faces the problems of complex preparation method, low yield and the like, so the design and development of the formic acid decomposition hydrogen production catalyst with high activity, simple preparation method and high yield becomes a great problem to push the development of formic acid as a commercial liquid hydrogen storage material to be solved urgently.
Palladium (Pd) -based materials have been known for a Long time as effective catalysts for Formic Acid decomposition Hydrogen production reactions, such as Citric Acid-assisted Pd/C (Zhi-Li Wang, Jun-Min Yan, Hong-Li Wang, Yun Ping, Qi junction; Pd/CSynthed with circulation Acid: An Efficient Catalyst for hydrogenetic formation from formation Acid/Sodium Formate; SCIENTIFIC REPORTS, 20122598), alkalized Graphene-loaded Pd (Fu-Zhan Song, Qi-Long Zhu, Nobuko Tsuori, and Qiang Xu; Diamine-Alkalized reduced Graphene Oxide: catalysis of Sub-2nm Palladium Nanoparticles and catalysis of activation 5144), and numerous catalysts for synthesis of Pd 5141. On the one hand, however, the Pd-based catalyst is extremely easy to be poisoned by a side reaction product CO generated by formic acid decomposition, so that the catalytic activity of the Pd-based catalyst is greatly reduced; on the other hand, the current carrier preparation process is complex, and the doping amount of the heteroatom is unstable. Therefore, the design and development of a carrier capable of effectively loading and dispersing metal nanoparticles in a loaded metal Pd-based catalyst becomes a focus of research. However, the preparation process of the carriers of the Pd-based nanocatalysts is cumbersome, and generally requires the use of, for example, polyhydric alcohol, citric acid, etc. as a dispersant and a stabilizer, resulting in easy generation of deposits on the product surface, and the yield of the catalyst during the preparation process is extremely limited, which greatly affects the preparation process of the catalyst that is mass-produced while taking into account high activity.
Disclosure of Invention
The invention aims to provide a carbon nitride supported Pd-based catalyst, and a preparation method and application thereof. The Pd in the catalyst is uniformly distributed on the carrier, the interaction stability is good, and the catalyst shows excellent activity and selectivity on hydrogen production by formic acid decomposition.
The invention provides a preparation method of a carbon nitride supported Pd-based catalyst, which comprises the following steps:
A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride;
the pyrolysis temperature is 500-650 ℃; the pyrolysis time is 60-120 min;
B) dispersing the thin-layer carbon nitride in water to obtain a first suspension;
C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension;
D) adding sodium hydroxide into the second suspension, adjusting the pH to 10-12, and stirring for 10-40 min to obtain a third suspension;
E) and adding sodium borohydride into the third suspension, stirring to obtain a fourth suspension, continuing stirring for 4-8 hours, carrying out solid-liquid separation on the fourth suspension, and drying the obtained solid to obtain the carbon nitride supported Pd-based catalyst.
Preferably, the mass ratio of the thin-layer carbon nitride to the water in the first suspension is (92-97) mg to (85-100) mL.
Preferably, the Pd precursor is H2PdCl4、Pd(NO3)2、K2PdCl4And Na2PdCl4One or more of them.
Preferably, in the second suspension, the mass ratio of the Pd in the Pd precursor to the thin-layer carbon nitride is (0.03-0.08) mg to (0.92-0.97) mg.
Preferably, the stirring time in the step C) is 3-5 hours;
and C), stirring speed in the step C) is 300-600 rpm.
Preferably, the stirring time in the step E) is 5-8 hours;
and E) stirring speed in the step E) is 300-600 rpm.
Preferably, the molar ratio of the sodium borohydride to the Pd precursor is 8: 1-15: 1.
Preferably, the drying temperature in the step E) is 50-65 ℃;
and D), drying for 8-12 h in the step E).
The invention provides a carbon nitride supported Pd-based catalyst prepared by the preparation method,
the particle size of Pd in the carbon nitride supported Pd-based catalyst is 2-4 nm.
The present invention provides the use of a carbon nitride supported Pd-based catalyst as described above as a catalyst for the decomposition of formic acid to produce hydrogen.
The invention provides a preparation method of a carbon nitride supported Pd-based catalyst, which comprises the following steps: A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride; the pyrolysis temperature is 500-650 ℃; the pyrolysis time is 60-120 min; B) dispersing the thin-layer carbon nitride in water to obtain a first suspension; C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension; D) adding sodium hydroxide into the second suspension, adjusting the pH to 10-12, and stirring for 10-40 min to obtain a third suspension; E) and adding sodium borohydride into the third suspension, stirring to obtain a fourth suspension, carrying out solid-liquid separation on the fourth suspension, and drying the obtained solid to obtain the carbon nitride supported Pd-based catalyst. The invention utilizes the trithiocyanuric acid in the pyrolysisThe method comprises the steps of obtaining thin-layer carbon nitride with high specific surface area and pore volume and numerous defects and empty pores by stripping action generated by in-situ escape of sulfur element in the process, and successfully reducing Pd (II) in a precursor solution into simple substance Pd (0) by using the thin-layer carbon nitride as a carrier under the action of a strong reducing agent by utilizing a surface adsorption strategy to obtain the carbon nitride supported Pd-based catalyst. The preparation method is simple, economical and environment-friendly, and is suitable for large-scale production, and the supported metal in the prepared catalyst is nano particles, is uniformly distributed on the carrier, has good interaction stability, and shows excellent activity and selectivity for formic acid decomposition hydrogen production reaction. Experimental results show that the Pd nanoparticles loaded on the surface of the catalyst prepared by the preparation method have the particle size of 2-4 nm, uniform particle size and selectivity (H)2+CO2) Up to 94.55%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a transmission electron microscope image of Pd nano-catalyst on a 20nm scale in example 1 of the present invention;
FIG. 2 is a particle size distribution diagram of Pd nano-catalyst in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern (XRD) of the Pd nanocatalyst in example 1 of the present invention;
FIG. 4 is a graph of the hydrogen production performance of catalysts prepared in examples 1 and 6 of the present invention by catalyzing the decomposition of formic acid;
FIG. 5 is a graph showing the performance of catalysts prepared in examples 1, 2 and 4 of the present invention in catalyzing the decomposition of formic acid to produce hydrogen.
Detailed Description
The invention provides a preparation method of a carbon nitride supported Pd-based catalyst, which comprises the following steps:
A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride;
the pyrolysis temperature is 500-650 ℃; the pyrolysis time is 60-120 min;
B) dispersing the thin-layer carbon nitride in water to obtain a first suspension;
C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension;
D) adding sodium hydroxide into the second suspension, adjusting the pH to 10-12, and stirring for 10-40 min to obtain a third suspension;
E) and adding sodium borohydride into the third suspension, stirring to obtain a fourth suspension, continuing stirring for 4-8 hours, performing solid-liquid separation on the fourth suspension, and drying the obtained solid to obtain the carbon nitride supported Pd-based catalyst.
In the invention, preferably, cyanuric acid is pyrolyzed at high temperature in a protective gas atmosphere to obtain thin-layer carbon nitride. In the pyrolysis process of the trithiocyanuric acid, the sulfur element can form gases such as hydrogen sulfide and the like, agglomeration in the process of forming carbon nitride by pyrolysis is prevented to a certain extent, a similar stripping effect is formed, and finally thin-layer carbon nitride with a plurality of defects and pores and higher specific surface area and pore volume is obtained. The thin-layer carbon nitride can effectively disperse and anchor metal nano particles, reduce the particle size of the nano particles and expose more active sites, thereby improving the catalytic activity of the Pd-based catalyst.
In the invention, the pyrolysis temperature is preferably 500-650 ℃, more preferably 550-600 ℃, and specifically, in the embodiment of the invention, the pyrolysis temperature can be 550 ℃, 600 ℃ or 650 ℃; the pyrolysis time is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and most preferably 2 to 3 hours, and specifically, in an embodiment of the present invention, the pyrolysis time may be 1 hour or 2 hours. The protective gas is preferably nitrogen or argon. The device for the pyrolysis reaction is not particularly limited, and in the embodiment of the invention, trithiocyanuric acid can be placed in a corundum boat with a cover, and then the corundum boat is placed in a muffle furnace for high-temperature pyrolysis.
After the thin-layer carbon nitride is obtained, the thin-layer carbon nitride is dispersed in deionized water to obtain a first suspension. The dispersion mode is preferably ultrasonic dispersion, the ratio of the mass of the thin-layer carbon nitride to the volume of water is preferably (92-97) mg to (85-100) mL, more preferably (93-96) mg to (90-95) mL, and specifically, in the embodiment of the invention, the mass ratio may be 95 mg: 90 mL. The method preferably performs the dispersion of the thin-layer carbon nitride at room temperature, wherein the room temperature is 20-28 ℃.
After the first suspension is obtained, the pd (ii) precursor solution is preferably added to the first suspension and stirred to obtain a second suspension.
In the present invention, the Pd (II) precursor solution is preferably H2PdCl4Solution, Pd (NO)3)2Solution, K2PdCl4Solution and Na2PdCl4One or more of the solutions; the mass concentration of the Pd (II) precursor solution is preferably 3-10 mg/mL, more preferably 4-8 mg/mL, and most preferably 5-6 mg/mL, and specifically, in the embodiment of the present invention, the mass concentration may be 5.9 mg/mL.
The mass ratio of Pd to thin-layer carbon nitride in the Pd precursor is preferably (0.03-0.08) mg to (0.92-0.97) mg, more preferably (0.04-0.07) mg to (0.93-0.96) mg, most preferably (0.05-0.06) mg to (0.94-0.95) mg, and specifically may be 0.05mg to 0.95mg in the embodiment of the present invention.
In the invention, the stirring time is preferably 1-5 hours, and more preferably 2-4 hours; the stirring speed is preferably 300 to 600rpm, and more preferably 400 to 500 rpm.
After the second suspension is obtained, adding a sodium hydroxide solution with a certain concentration into the second suspension, adjusting the pH of the solution to 9-11, preferably 10-10.8, and stirring for 10-40 min to obtain a third suspension.
In the invention, the concentration of the sodium hydroxide solution is preferably 0.5-1.5 mol/L, more preferably 1mol/L, and specifically, in the embodiment of the invention, the concentration may be 1 mol/L; the volume ratio of the sodium hydroxide solution to the Pd (II) precursor solution is preferably (0.1-1.5 ml) to (0.5-1 ml). The stirring time is preferably 10-40 min, more preferably 20-30 min, and specifically, in the embodiment of the present invention, may be 30 min.
After the third suspension is obtained, adding a sodium borohydride solution with a certain concentration into the third suspension, stirring to obtain a fourth suspension, and performing suction filtration, washing and drying on the fourth suspension to obtain the thin-layer carbon nitride supported Pd-based catalyst.
In the invention, the mass concentration of the sodium borohydride solution is preferably 0.5-3 mg/mL, more preferably 1-2.5 mg/mL, and most preferably 1-2 mg/mL, and specifically, in the embodiment of the invention, the mass concentration may be 1 mg/mL; the molar ratio of the sodium borohydride to the Pd precursor is preferably (8-15) to 1, more preferably (9-14) to 1, and most preferably (10-13) to 1.
The stirring time is preferably 5-8 hours, and more preferably 6-7 hours; the stirring speed is preferably 300 to 600rpm, and more preferably 400 to 500 rpm.
The first suspension, the second suspension, the third suspension and the fourth suspension are obtained by stirring at room temperature.
After the fourth suspension is obtained, the Pd nano-catalyst with uniform particle size can be obtained by carrying out suction filtration on the fourth suspension, washing the obtained solid and then drying the washed solid.
In the invention, the suction filtration and the washing are common operation means of technicians in the field, and the drying temperature is preferably 50-65 ℃, more preferably 55-60 ℃; the drying time is preferably 8-12 hours, and more preferably 9-10 hours.
The invention also provides a carbon nitride supported Pd-based catalyst prepared by the preparation method. The carbon nitride supported Pd-based catalyst consists of thin-layer carbon nitride and Pd nanoparticles supported on the surface of the thin-layer carbon nitride, wherein the supported amount of Pd is less than or equal to 5 wt%, and preferably 3-4 wt%; the particle size of the Pd nanoparticles is preferably 2-4 nm.
The invention also provides the application of the carbon nitride supported Pd-based catalyst as the formic acid decomposition hydrogen production catalyst, and in the formic acid decomposition hydrogen production reaction, the ratio of the mass of the carbon nitride supported Pd-based catalyst to the mass of formic acid is preferably 10g to (1-1.5) mol, more preferably 10g to (1.1-1.3) mol, and most preferably 10g to 1.1 mol.
More preferably, the formic acid decomposition hydrogen production method uses sodium formate as an additive, and the molar ratio of the formic acid to the sodium formate is preferably (1.0-1.5): (0.5-1.0), more preferably (1.1-1.3): (0.7-0.8), and specifically may be 1.1: 0.8.
The carbon nitride supported Pd-based catalyst is used for catalyzing the formic acid decomposition hydrogen production reaction, the specific application method is the same as that of the formic acid decomposition hydrogen production catalyst in the prior art, and the detailed description is omitted here.
The invention also provides a method for detecting the catalytic activity of the catalyst for hydrogen production by formic acid decomposition, which comprises the following steps: the performance test of hydrogen production by formic acid decomposition is carried out on a gas mass flowmeter capable of analyzing data on a computer in real time. Weighing a certain mass of the prepared catalyst, placing the catalyst and the formic acid solution containing the additive to be tested in a constant-temperature water bath, introducing nitrogen into a container containing the catalyst to remove air, and keeping for 10 min. The formic acid solution was then quickly added to the round bottom flask containing the catalyst and the mouth of the flask was closed tightly with a plug connected to a mass flow gas meter to prevent gas leakage. The catalytic activity of the catalyst for hydrogen production by formic acid decomposition is analyzed by analyzing the amount of generated gas recorded instantaneously by the gas mass flow meter.
The invention provides a preparation method of a carbon nitride supported Pd-based catalyst, which comprises the following steps: A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride; the pyrolysis temperature is 500-650 ℃; the pyrolysis time is 60-120 min; B) dispersing the thin-layer carbon nitride in water to obtain a first suspension; C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension; D) adding sodium hydroxide into the second suspension, adjusting the pH to 10-12, and stirring for 10-40 min to obtain a third suspension; E) adding sodium borohydride into the third suspension, and stirringAnd (3) obtaining a fourth suspension, carrying out solid-liquid separation on the fourth suspension, and drying the obtained solid to obtain the carbon nitride supported Pd-based catalyst. According to the method, a thin-layer carbon nitride with multiple defects and empty pores and higher specific surface area and pore volume is obtained by utilizing the stripping effect generated by in-situ escape of sulfur element in the pyrolysis process of the trithiocyanic acid, and then the thin-layer carbon nitride is used as a carrier, and Pd (II) in a precursor solution is successfully reduced into elemental Pd (0) under the action of a strong reducing agent by utilizing a surface adsorption strategy, so that the carbon nitride supported Pd-based catalyst is obtained. The preparation method is simple, economical and environment-friendly, and is suitable for large-scale production, and the supported metal in the prepared catalyst is nano particles, is uniformly distributed on the carrier, has good interaction stability, and shows excellent activity and selectivity for formic acid decomposition hydrogen production reaction. Experimental results show that the Pd nanoparticles loaded on the surface of the catalyst prepared by the preparation method have the particle size of 2-4 nm, uniform particle size and selectivity (H)2+CO2) Up to 94.55%.
Compared with the reported preparation method of the Pd nano-catalyst, the method has the advantages of low energy consumption, simpler operation steps, high yield, more uniform dispersion of the Pd nano-particles on the carrier and smaller particle size. The preparation method of the Pd nano-catalyst with the thin-layer carbon nitride as the carrier is simple, economic and environment-friendly, is suitable for industrial large-scale production and can reach hundreds of grams.
In order to further illustrate the present invention, the following examples are provided to describe in detail a carbon nitride supported Pd-based catalyst, its preparation method and application, but should not be construed as limiting the scope of the present invention.
Example 1
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 1h at 600 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding the solution (5.9mg/ml) into the suspension 1 to obtain a suspension 2, and stirring for 2 hours;
adjusting the pH of the solution to 10.8 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
adding 5ml sodium borohydride solution (1mg/ml) into the suspension 3, keeping at room temperature for more than 4h to obtain suspension 4, filtering, washing with water, and drying to obtain Pd nano catalyst (denoted as Pd/C) with uniform particle size3N4-S-10.8)。
The Pd nano-catalyst and the carrier of example 1 were observed by transmission electron micrograph, and the particle size distribution thereof was analyzed, and as shown in fig. 1, it can be seen from fig. 1 that the nanoparticles in the Pd nano-catalyst of example 1 were uniformly dispersed and uniform in size, and consisted of Pd nanoparticles having a particle size of 2 to 4 nm.
The Pd nanocatalyst of example 1 was analyzed by X-ray diffraction, and as a result, as shown in fig. 2, the diffraction peak obtained from the XRD spectrum corresponded to the standard diffraction peak of elemental Pd.
Example 2
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 2 hours at 550 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 11 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 2 was observed by transmission electron microscopy and analyzed for particle size distribution, similar to example 1. The Pd nanocatalyst of example 2 was subjected to X-ray analysis and the results were similar to example 1.
Example 3
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 2 hours at 600 ℃ in a nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 11 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 3 was observed by transmission electron microscopy and analyzed for particle size distribution, similar to example 1. The Pd nanocatalyst of example 3 was subjected to X-ray analysis and the results were similar to example 1.
Example 4
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 1h at 650 ℃ in a nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding the solution (5.9mg/ml) into the suspension 1 to obtain a suspension 2, and stirring for 2 hours;
adjusting the pH of the solution to 11 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 4 was observed in a transmission electron micrograph and analyzed for particle size distribution, resulting in similarity to example 1. The Pd nanocatalyst of example 4 was subjected to X-ray analysis and the results were similar to example 1.
Example 5
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 2 hours at 650 ℃ in a nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 11 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 5 was observed in a transmission electron micrograph and analyzed for particle size distribution, resulting in similarity to example 1. The Pd nanocatalyst of example 5 was subjected to X-ray analysis and the results were similar to example 1.
Example 6
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 1h at 600 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 10 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
adding 5ml sodium borohydride solution (1mg/ml) into the suspension 3, keeping at room temperature for more than 4h to obtain suspension 4, filtering, washing with water, and drying to obtain P with uniform particle sized Nano catalyst (noted as Pd/C3N4-S-10)。
The Pd nanocatalyst of example 6 was observed in a transmission electron micrograph and analyzed for particle size distribution, resulting in similarity to example 1. The Pd nanocrystalline catalyst of example 6 was subjected to X-ray analysis, and the result was similar to example 1.
Example 7
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 1h at 600 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml H2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 9 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 7 was observed in a transmission electron micrograph and analyzed for particle size distribution, resulting in similarity to example 1. The Pd nanocatalyst of example 7 was subjected to X-ray analysis and the results were similar to example 1.
Example 8
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 2 hours at 550 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
adding 0.85ml of Na2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 9 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 8 was observed in a transmission electron micrograph and analyzed for particle size distribution, and the results were similar to those of example 1. The Pd nanocatalyst of example 8 was subjected to X-ray analysis and the results were similar to example 1.
Example 9
Putting 2g of trithiocyanuric acid into a corundum boat with a cover, putting the corundum boat into a muffle furnace, and pyrolyzing for 2 hours at 550 ℃ under the nitrogen atmosphere to obtain a thin-layer carbon nitride carrier;
adding 95mg of thin-layer carbon nitride carrier into 90ml of deionized water, and uniformly dispersing by ultrasonic to obtain uniform suspension 1;
0.85ml K2PdCl4Adding solution (5.9mg/ml) into suspension 1 to obtain suspension 2, stirring for 2 hr,
adjusting the pH of the solution to 10.8 by using a newly prepared 1mol/L NaOH solution to obtain a uniform suspension 3;
and adding 5ml of sodium borohydride solution (1mg/ml) into the suspension 3, keeping the suspension at room temperature for more than 4 hours to obtain a suspension 4, and performing suction filtration, washing and drying on the suspension to obtain the Pd nano catalyst with uniform particle size.
The Pd nanocatalyst of example 9 was observed in a transmission electron micrograph and analyzed for particle size distribution, resulting in similarity to example 1. The Pd nanocatalyst of example 9 was subjected to X-ray analysis and the results were similar to example 1.
Example 10
The catalyst of example 1 was Pd/C3N4-S-10.8 for catalytic formic acid decomposition to produce hydrogen:
the performance test of hydrogen production by formic acid decomposition is carried out on a gas mass flowmeter capable of analyzing data on a computer in real time. 20mg of the prepared catalyst is weighed, placed in a thermostatic water bath at 30 ℃ together with the formic acid solution containing the additive (sodium formate, noted as SF) to be tested, and nitrogen is introduced into the container containing the catalyst to remove air and kept for 10 min. The formic acid solution was then quickly added to the round bottom flask containing the catalyst and the mouth of the flask was closed tightly with a plug connected to a mass flow gas meter to prevent gas leakage. The catalytic activity of the catalyst for hydrogen production by formic acid decomposition is analyzed by analyzing the amount of generated gas recorded instantaneously by the gas mass flow meter. The Pd/C catalyst (the carrier is active carbon XC-72, the Pd loading is less than 5 percent, and the particle size of the Pd nano-particles is more than 3 nm) is used as a comparison sample and is tested under the same condition, and the results are shown in Table 1,
table 1 data of catalytic activity of Pd nanocatalyst in example 1 of the present invention
| Catalyst and process for preparing same | Additive agent | H2/％ | CO2/％ | O2/％ | N2/％ | H2∶CO2 | N2∶O2 |
| Pd/C | SF | 46.38 | 44.60 | 1.81 | 7.21 | 1.04∶1 | 3.98∶1 |
| Pd/C3N4-S | SF | 47.51 | 47.04 | 1.10 | 4.44 | 1.01∶1 | 3.94∶1 |
Note: since the method for detecting the gas components generated by the reaction according to the present invention is to collect and then detect the gas components, rather than to measure the gas components in situ, the gas components inevitably remain in the collecting device, and thus the measurement result may be affected by the air remaining in the collecting device, resulting in selectivity (H)2+CO2) The measurement result of (2) is low, and the actual selectivity can basically achieve 100%.
Comparative example 1
The Pd catalyst was prepared by following the procedure in example 1 except that this comparative example uses melamine as a precursor instead of cyanuric acid as a precursor in example 1. The prepared Pd catalyst is recorded as Pd/C3N4-10.8。
Comparative example 2
The Pd catalyst was prepared by following the procedure in example 6, except that this comparative example uses melamine as a precursor instead of cyanuric acid as a precursor in example 6. The prepared Pd catalyst is recorded as Pd/C3N4-10。
The Pd/C catalysts used in example 1, example 6, comparative example 1, comparative example 2 and example 10 were used to catalyze the reaction for producing hydrogen by decomposing formic acid according to the method of example 10, respectively, and the respective catalytic efficiencies are shown in fig. 4.
As can be seen from FIG. 4, the Pd nano-catalyst prepared by the invention has better performance for catalyzing the decomposition of formic acid to prepare hydrogen than the Pd/C catalyst.
The Pd nanocatalysts of example 1, example 2 and example 4 were used in the hydrogen production reaction from formic acid according to the method of example 10, and the results are shown in fig. 5, where fig. 5 is the performance of the Pd nanocatalysts prepared at different pyrolysis temperatures according to the present invention in catalyzing the decomposition of formic acid to produce hydrogen. As can be seen from fig. 5, the Pd nanocatalyst prepared at the pyrolysis temperature of 600 ℃ has the highest catalytic activity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing a carbon nitride supported Pd-based catalyst, comprising the steps of:
A) pyrolyzing trithiocyanuric acid in a protective gas atmosphere to obtain thin-layer carbon nitride;
the pyrolysis temperature is 500-650 ℃; the pyrolysis time is 60-120 min;
B) dispersing the thin-layer carbon nitride in water to obtain a first suspension;
C) adding a Pd precursor into the first suspension, and stirring to obtain a second suspension;
D) adding sodium hydroxide into the second suspension, adjusting the pH to 10-12, and stirring for 10-40 min to obtain a third suspension;
E) and adding sodium borohydride into the third suspension, stirring to obtain a fourth suspension, continuing stirring for 4-8 hours, carrying out solid-liquid separation on the fourth suspension, and drying the obtained solid to obtain the carbon nitride supported Pd-based catalyst.
2. The method according to claim 1, wherein the first suspension contains the thin layer of carbon nitride in a mass to water volume ratio of (92 to 97) mg to (85 to 100) mL.
3. The preparation method of claim 1, wherein the Pd precursor is one or more of H2PdCl4, Pd (NO3)2, K2PdCl4 and Na2PdCl 4.
4. The method according to claim 1, wherein the ratio of the mass of Pd in the Pd precursor to the mass of the thin-layer carbon nitride in the second suspension is (0.03-0.08) mg to (0.92-0.97) mg.
5. The preparation method according to claim 1, wherein the stirring time in the step C) is 3 to 5 hours;
and C), stirring speed in the step C) is 300-600 rpm.
6. The preparation method according to claim 1, wherein the stirring time in the step E) is 5 to 8 hours;
and E) stirring speed in the step E) is 300-600 rpm.
7. The preparation method according to claim 1, wherein the molar ratio of the sodium borohydride to the Pd precursor is 8: 1-15: 1.
8. The preparation method according to claim 1, wherein the temperature for drying in the step E) is 50-65 ℃;
and D), drying for 8-12 h in the step E).
9. A carbon nitride supported Pd-based catalyst prepared by the preparation method of any one of claims 1 to 8,
the particle size of Pd in the carbon nitride supported Pd-based catalyst is 2-4 nm.
10. Use of a carbon nitride supported Pd-based catalyst according to claim 9 as a catalyst for hydrogen production by formic acid decomposition.
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