CN111013581A - Electro-catalytic nitrogen reduction palladium-ruthenium nanorod self-assembly and controllable preparation method thereof - Google Patents
Electro-catalytic nitrogen reduction palladium-ruthenium nanorod self-assembly and controllable preparation method thereof Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 32
- 230000009467 reduction Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
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- 239000003054 catalyst Substances 0.000 claims abstract description 27
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- 238000002156 mixing Methods 0.000 claims abstract description 25
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- 239000011734 sodium Substances 0.000 claims abstract description 20
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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Abstract
An electro-catalyst of palladium ruthenium nano rod assembly and a controllable preparation method thereof are disclosed, wherein sodium chloropalladate and ruthenium chloride solution with the concentration of 1-40 mM, hydrochloric acid solution with the concentration of 1-12M and ascorbic acid solution with the concentration of 0.01-0.5M are respectively prepared; respectively mixing sodium chloropalladate and ruthenium chloride solutions with the total volume of 4.5mL, then adding 0.01-0.5 mL of prepared hydrochloric acid solution, then adding 0.01-0.5 g of potassium bromide and F127, and uniformly mixing; and finally, adding 1-10 mL of ascorbic acid solution, and carrying out ultrasonic mixing for 5-20 minutes. And after the solutions are fully mixed, placing the mixture in an oil bath pot, heating the mixture to 60-100 ℃, reacting for 0.1-10 h, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod assembly catalyst. The preparation method is simple in preparation process and short in reaction time, and the prepared material has excellent electrochemical nitrogen reduction performance at low temperature and normal pressure.
Description
(I) technical field
The invention relates to a palladium-ruthenium nanorod self-assembly for electrocatalysis nitrogen reduction and a controllable preparation method thereof.
(II) background of the invention
Ammonia (NH)3) As the most common industrial chemicals in modern society, play a vital role in both human and earth ecosystems. Furthermore, NH3Is considered to be a stable hydrogen energy carrier and ideal transportation fuel, and reduces nitrogen (N) due to the abundance (78%) of the hydrogen energy carrier in the atmosphere2) Is NH with very promising prospect3A production method. However, due to the chemical inertness and high stability of nitrogen, multi-step reduction is a kinetically complex reaction. Until now, the Hubble-Bosch process is still the most important ammonia production method in industrial processes, but this method relies heavily on capital-intensive and energy resources, and the industrial production technology is ultra-large scale production under extreme reaction conditions (350-3Synthetic energy and feedstock (H)2) Most are derived from fossil fuels, which results in over 1% carbon dioxide emissions worldwide. In response to the challenges of reducing and increasing carbon dioxide emissions from fossil fuels, it is highly desirable to develop a more economical and sustainable process for producing NH3Thereby meeting the increasing world demand.
In recent years, under ambient conditions, NH is driven by renewable electrical energy using nitrogen as a raw material3Have attracted a great deal of interest in electrochemical synthesis. Environmentally friendly electrochemical N thanks to high energy conversion efficiency and reduced energy consumption2Reduction Reactions (NRR) have great potential to replace traditional synthetic methods. Electrochemical NRR requires a highly efficient catalyst. Despite the great progress made in the application of NRR to noble metal catalysts, high activity, high selectivity active metal catalysts were designed for NH3Production of (b) is still highly desirable. Alloying noble metals with other metals is an effective way to improve the catalytic performance of materials, and this method has been demonstrated in small molecule redox reactions. Alloy strategies have recently also been successful in NRR applications, which has prompted the search for highly active NRR metal catalysts by controlling the composition and structure of the NRR metal catalyst.
Among the various structures, branched nanostructures are gaining increasing attention. The open porous structure can not only provide enough exposed active sites, but also improve the utilization rate of the catalyst. In addition, the branched nanostructures may effectively reduce the reduction of active sites during the polymerization of the catalyst. Despite the great advances made in bimetallic and multi-metal alloys, the direct process for preparing branched metal catalysts remains a great challenge. Face-centered cubic metals are generally difficult to spontaneously form anisotropic metal nanostructures due to the absence of endogenous driving forces in aqueous solutions. In order to prepare the branched metal nanostructure, a multistep synthesis method such as Gawani displacement method, etching method, seed growth method and the like is generally adopted. These synthetic processes are complex, time consuming and difficult to scale up, and it is therefore essential to develop a direct synthesis of branched metal catalysts.
Disclosure of the invention
The invention aims to provide a palladium-ruthenium nanorod self-assembly and a controllable preparation method thereof, and research on electrocatalytic nitrogen reduction reaction.
The technical scheme adopted by the invention is as follows:
a palladium-ruthenium nanorod self-assembly catalyst for electrocatalysis nitrogen reduction is prepared by the following method:
(1) respectively preparing 1-40 mM sodium chloropalladate and ruthenium chloride solution, 1-12M hydrochloric acid solution and 0.01-0.5M ascorbic acid solution;
(2) respectively mixing sodium chloropalladate and ruthenium chloride solutions with the total volume of 4.5mL, then adding 0.01-0.5 mL of prepared hydrochloric acid solution, then adding 0.01-0.5 g of potassium bromide and F127, and uniformly mixing; finally, adding 1-10 mL of ascorbic acid solution, and ultrasonically mixing for 5-20 minutes;
(3) and after fully mixing the solution, placing the mixture in an oil bath pot, heating the mixture to 60-100 ℃, reacting for 1-10 hours, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod self-assembly catalyst.
The selection of reaction conditions has important influence on the structure of the palladium-ruthenium catalyst, and the potassium bromide is added in the reaction because of Br-Can be adsorbed on the (100) crystal face of the face-centered cubic metal, can selectively prevent the growth of the metal on the (100) crystal face, and is beneficial to the growth of dendritic metal. The Ru ions act as shape directors, eventually leading to the formation of dendritic nanocrystals. In addition, the triblock copolymer F127 is selected as a blocking agent, so that the dispersity of the nucleation center can be effectively improved, and the possibility of agglomeration is reduced, thereby leading to the formation of a three-dimensional palladium-ruthenium nanorod self-assembly with good dispersity. In the preparation process, the morphology and the structure of the palladium ruthenium can be controlled by changing the adding proportion of the precursor.
A controllable preparation method of a palladium-ruthenium nanorod self-assembly catalyst for electrocatalysis nitrogen reduction, which comprises the following steps:
(1) respectively preparing 1-40 mM sodium chloropalladate and ruthenium chloride solution, 1-12M hydrochloric acid solution and 0.01-0.5M ascorbic acid solution;
(2) respectively mixing sodium chloropalladate and ruthenium chloride solutions with the total volume of 4.5mL, then adding 0.01-0.5 mL of prepared hydrochloric acid solution, then adding 0.01-0.5 g of potassium bromide and F127, and uniformly mixing; finally, adding 1-10 mL of ascorbic acid solution, and ultrasonically mixing for 5-20 minutes;
(3) and after fully mixing the solution, placing the mixture in an oil bath pot, heating the mixture to 60-100 ℃, reacting for 1-10 hours, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod self-assembly catalyst.
Further, the concentrations and volumes of sodium chloropalladate, ruthenium chloride and ascorbic acid, the amounts of potassium bromide and F127, and the temperature and time of the reaction are controlled to control the morphology and structure of the palladium-ruthenium.
Carrying out electrochemical catalytic nitrogen reduction reaction at normal temperature and normal pressure, wherein the specific performance test operation process is as follows:
(1) weighing about 2-10 mg of sample, dispersing in ultrapure water, adding 100 mu L of Nafion solution (5 wt%), performing ultrasonic treatment for 30 minutes to obtain uniform dispersion, and coating 10-50 mu L of dispersion on carbon paper (0.5 multiplied by 0.5 cm)2) Drying at 50 ℃;
(2) the carbon paper loaded with the palladium-ruthenium nanorod self-assembly is used as an electrode material to carry out an experiment for preparing ammonia by nitrogen reduction. In an H-cell, carbon paper was used as the working electrode, and a saturated Ag/AgCl electrode and a carbon rod were used as the reference electrode and the counter electrode, respectively. Before testing, nitrogen gas is introduced for 30 minutes to saturate the solution with nitrogen gas, test programs of linear sweep cyclic voltammetry and chronoamperometry are selected, and the current condition of the working electrode under different potentials is monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
The palladium-ruthenium nanorod self-assembly and the preparation method thereof provided by the invention have the beneficial effects that:
(1) the preparation method is simple and mild, the product is directly obtained by a one-step method, and the yield of the nano-rod self-assembly is high.
(2) The morphology and structure of the palladium ruthenium can be controlled by changing the concentration and volume of the precursor, so that the palladium ruthenium has different performances in nitrogen reduction application.
(3) The synthesized palladium-ruthenium nanorod self-assembly body shows outstanding activity and stability in nitrogen reduction reaction, and the palladium-based material has a very high application prospect as an electrocatalyst.
(IV) description of the drawings
FIG. 1 is an SEM image of a palladium ruthenium nanorod self-assembly according to embodiment 1 of the invention.
FIG. 2 is TEM and HRTEM images of palladium-ruthenium nanorod self-assemblies of specific example 1 of the present invention.
FIG. 3 is an XRD pattern of the palladium ruthenium nanorod self-assembly according to embodiment 1 of the present invention.
FIG. 4 is an XPS plot of a palladium ruthenium nanorod self-assembly of example 1 of the present invention.
FIG. 5 is a linear cyclic voltammogram of a palladium-ruthenium nanorod self-assembly of example 1 of the present invention in 0.1M HCl solution.
FIG. 6 is a performance diagram of the Pd-Ru nanorod self-assembly for preparing ammonia by catalytic nitrogen reduction in the embodiment of the invention 1.
FIG. 7 is an SEM image of a palladium ruthenium nano-thorn self-assembly according to embodiment 2 of the invention.
FIG. 8 is a graph of the performance of the Pd-Ru nano-thorn self-assembly for preparing ammonia by nitrogen reduction in accordance with embodiment 2 of the present invention.
FIG. 9 is an SEM image of palladium ruthenium nanoparticles according to embodiment 3 of the present invention.
FIG. 10 is a graph of the performance of palladium ruthenium nanoparticles in catalyzing nitrogen reduction to prepare ammonia according to embodiment 3 of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
referring to fig. 1 to 10, in this example, the performance test of nitrogen reduction on the palladium-ruthenium material is performed on a CHI660E electrochemical workstation, and the operation process is as follows:
in the first step, about 4mg of a sample was weighed and dispersed in 0.9mL of ultrapure water, then 100. mu.L of Nafion solution (5 wt%) was added thereto, and ultrasonic treatment was carried out for 30 minutes to obtain a uniform dispersion, and then 40. mu.L of the dispersion was applied to a carbon paper (0.5X 0.5 cm)2) Drying at 50 ℃;
and secondly, taking the carbon paper loaded with the palladium-ruthenium nanorod self-assembly as an electrode material, and carrying out an experiment for preparing ammonia by nitrogen reduction. Before testing, nitrogen gas is introduced for 30 minutes to saturate the solution with nitrogen gas, test programs of linear sweep cyclic voltammetry and chronoamperometry are selected, and the current condition of the working electrode under different potentials is monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
Example 1
A controllable preparation method of a palladium-ruthenium nanorod self-assembly catalyst for electrocatalysis nitrogen reduction, which comprises the following steps:
1) respectively preparing sodium chloropalladate and ruthenium chloride with the concentration of 20mM, a hydrochloric acid solution with the concentration of 6M and an ascorbic acid solution with the concentration of 0.1M;
2) respectively mixing 3.4mL of sodium chloropalladate and 1.1mL of ruthenium chloride solution, then adding 0.2mL of hydrochloric acid solution, then adding 120mg of potassium bromide and 5mg of F127, and ultrasonically mixing uniformly; finally, adding 2mL of ascorbic acid solution, and carrying out ultrasonic mixing for 10 minutes;
3) and after the solutions are fully mixed, placing the mixture in an oil bath pot to be heated to 95 ℃, reacting for 4 hours, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod self-assembly catalyst.
The SEM image of the obtained palladium ruthenium nanorod self-assembled electrocatalyst is shown in fig. 1. A TEM image of the obtained palladium ruthenium nanorod self-assembly is shown in fig. 2. The XRD pattern of the obtained palladium ruthenium nanorod self-assembly is shown in figure 3. The XPS pattern of the obtained palladium ruthenium nanorod self-assembly is shown in fig. 4. The linear cyclic voltammogram of the obtained palladium-ruthenium nanorod self-assembly in 0.1M HCl solution is shown in FIG. 5. The performance diagram of the obtained palladium ruthenium nano rod self-assembly body for catalyzing nitrogen reduction to prepare ammonia is shown in figure 6.
As seen from the SEM image, the yield of the palladium-ruthenium nanorod self-assembly is close to 100%, each particle is highly branched, a three-dimensional structure is formed by the staggered nanorods, and the nanorods extend to all directions from the center. By HRTEM, XRD and XPS analysis, the material has good alloying degree and palladium-ruthenium alloy is formed. According to the performance graph of the palladium-ruthenium nano rod assembly for preparing ammonia by catalyzing nitrogen reduction in 0.1M HCl, the palladium-ruthenium nano rod self-assembly can be calculated to have very high nitrogen reduction activity and the ammonia production rate of 34.2 mu g h-1mg-1 cat.The Faraday efficiency was 2.4%.
Example 2
A preparation method of a palladium-ruthenium nano thorn self-assembly body comprises the following steps:
1) respectively preparing 1mM sodium chloropalladate solution and 1M ruthenium chloride solution, 1M hydrochloric acid solution and 0.01M ascorbic acid solution;
2) 1.1mL of sodium chloropalladate and 3.4mL of ruthenium chloride solution are respectively mixed, then 0.01mL of hydrochloric acid solution is added, 10mg of potassium bromide and 2mg of F127 are added, and the mixture is uniformly mixed by ultrasound. Finally, adding 1mL of ascorbic acid solution, and carrying out ultrasonic mixing for 5 minutes;
3) and after the solutions are fully mixed, placing the mixture in an oil bath pot to be heated to 60 ℃, reacting for 1 hour, washing, centrifuging and drying to obtain the palladium-ruthenium nano thorn self-assembly nitrogen reduction catalyst.
Obtaining an SEM image of the pd — ru nano-thorn self-assembly, see fig. 7; the performance diagram of the palladium ruthenium nano-thorn self-assembly body for catalyzing the reduction of nitrogen to prepare ammonia is shown in figure 8.
From the SEM images, palladium ruthenium nano-spines self-assemblies have been formed. This is mainly due to the change in the ratio of precursors leading to a change in the palladium ruthenium morphology. The performance diagram of ammonia preparation by nitrogen reduction shows that the ammonia production rate of the palladium-ruthenium nano-thorn self-assembly is 17.1 mu g h-1mg-1 cat.The Faraday efficiency was 0.2%.
Example 3
A method for preparing a palladium ruthenium nanoparticle electrocatalyst, comprising the steps of:
1) respectively preparing sodium chloropalladate and ruthenium chloride with the concentration of 40mM, hydrochloric acid solution with the concentration of 12M and ascorbic acid solution with the concentration of 0.5M;
2) 3.9mL of sodium chloropalladate and 0.6mL of ruthenium chloride solution are respectively mixed, then 0.5mL of hydrochloric acid solution is added, 500mg of potassium bromide and 50mg of F127 are added, and the mixture is uniformly mixed by ultrasound. Finally, 10mL of ascorbic acid solution is added, and ultrasonic mixing is carried out for 20 minutes;
3) and after the solutions are fully mixed, placing the mixture in an oil bath pot, heating the mixture to 100 ℃, reacting the mixture for 10 hours, washing, centrifuging and drying the mixture to obtain the palladium-ruthenium nano small particle nitrogen reduction catalyst.
Obtaining an SEM image of the palladium ruthenium nano-particles, which is shown in figure 9; the performance diagram of palladium ruthenium nanoparticles for catalyzing nitrogen reduction to prepare ammonia is shown in figure 10.
From the SEM images, it can be seen that palladium ruthenium nanoparticles have formed. This is mainly due to the change in the ratio of precursors leading to a change in the palladium ruthenium morphology. The performance chart of ammonia prepared by nitrogen reduction shows that the ammonia generating rate of the palladium-ruthenium nanometer particles is 26.3 mu g h- 1mg-1 cat.The Faraday efficiency was 0.83%.
Example 4
A method for preparing a palladium ruthenium nanoparticle electrocatalyst, comprising the steps of:
1) preparing 10mM sodium chloropalladate solution, 3M hydrochloric acid solution and 0.05M ascorbic acid solution;
2) 3.4mL of sodium chloropalladate and 1.1mL of ruthenium chloride solution are respectively mixed, then 0.5mL of hydrochloric acid solution is added, 50mg of potassium bromide and 3mg of F127 are added, and the mixture is uniformly mixed by ultrasound. Finally, adding 1mL of ascorbic acid solution, and carrying out ultrasonic mixing for 10 minutes;
3) and after the solutions are fully mixed, placing the mixture in an oil bath pot, heating the mixture to 70 ℃, reacting for 2 hours, washing, centrifuging and drying to obtain the palladium-ruthenium small-particle nitrogen reduction catalyst.
In the synthesis process, the use level of hydrochloric acid is excessive, the use level of potassium bromide is excessive, the reaction speed is reduced, the reaction time is too short, palladium and ruthenium can not be well reduced, and the palladium-ruthenium nanorod self-assembly body with uniform appearance can not be obtained; in addition, the concentration of the precursor and the reducing agent is too low to reduce palladium and ruthenium well, the reaction temperature is too low, the reduction rate is slow, and an intended rod-like structure cannot be obtained, so that it is difficult to obtain the palladium-ruthenium nanorod self-assembly catalyst.
Claims (3)
1. A palladium-ruthenium nanorod self-assembly catalyst for electrocatalysis nitrogen reduction is prepared by the following method:
(1) respectively preparing 1-40 mM sodium chloropalladate and ruthenium chloride solution, 1-12M hydrochloric acid solution and 0.01-0.5M ascorbic acid solution;
(2) respectively mixing sodium chloropalladate and ruthenium chloride solutions with the total volume of 4.5mL, then adding 0.01-0.5 mL of prepared hydrochloric acid solution, then adding 0.01-0.5 g of potassium bromide and F127, and uniformly mixing; finally, adding 1-10 mL of ascorbic acid solution, and ultrasonically mixing for 5-20 minutes;
(3) and after fully mixing the solution, placing the mixture in an oil bath pot, heating the mixture to 60-100 ℃, reacting for 0.1-10 h, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod assembly catalyst.
2. A controllable preparation method of the palladium ruthenium nanorod self-assembly catalyst for electrocatalytic nitrogen reduction according to claim 1, comprising the following steps:
(1) respectively preparing 1-40 mM sodium chloropalladate and ruthenium chloride solution, 1-12M hydrochloric acid solution and 0.01-0.5M ascorbic acid solution;
(2) respectively mixing sodium chloropalladate and ruthenium chloride solutions with the total volume of 4.5mL, then adding 0.01-0.5 mL of prepared hydrochloric acid solution, then adding 0.01-0.5 g of potassium bromide and F127, and uniformly mixing; finally, adding 1-10 mL of ascorbic acid solution, and ultrasonically mixing for 5-20 minutes;
(3) and after fully mixing the solution, placing the mixture in an oil bath pot, heating the mixture to 60-100 ℃, reacting for 0.1-10 h, washing, centrifuging and drying to obtain the palladium-ruthenium nanorod assembly catalyst.
3. The method of claim 2, wherein the concentrations and volumes of sodium chloropalladate, ruthenium chloride, ascorbic acid, the amounts of potassium bromide and F127, and the temperature and time of the reaction are controlled to control the morphology and structure of the palladium ruthenium.
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| CN115779897A (en) * | 2022-11-28 | 2023-03-14 | 青岛科技大学 | Preparation and application of bimetallic nano material for degrading organic pollutants in water by electrocatalysis |
| CN115779897B (en) * | 2022-11-28 | 2024-05-24 | 青岛科技大学 | Preparation and application of bimetallic nano material for degrading organic pollutants in water by using electrocatalytic reaction |
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