CN115584527A - Preparation method and application of mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction - Google Patents
Preparation method and application of mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000010949 copper Substances 0.000 title claims abstract description 91
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 65
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 59
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 54
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 230000009467 reduction Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
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- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 3
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- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C25B1/27—Ammonia
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction, which comprises the following steps: s1, dissolving dioctadecyl dimethyl ammonium chloride in a cosolvent of water and ethanol; s2, adjusting the pH value of the reaction solution to 7-8 by using sodium hydroxide; s3, sequentially adding the chloropalladium copper nitrate solution into the reaction solution; s4, adding ascorbic acid for reduction; s5, removing the surfactant through centrifugal washing to obtain the mesoporous palladium-copper nano catalyst. The invention provides a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction, which not only improves the utilization rate of noble metals, but also well introduces a mesoporous structure with unique functionality by synthesizing the mesoporous palladium-copper nano catalyst, improves the activity of synthesizing ammonia by electroreduction of nitrate by the mesoporous structure, and particularly obviously improves the selectivity of ammonia. The invention also provides an application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction.
Background
Ammonia (NH) 3 ) As one of the most basic chemical raw materials in the world, the fertilizer is not only a fertilizer, a medicine,Dyes and other indispensable chemical raw materials are also considered as ideal green carbon-free fuels for low-carbon footprint energy technology. Meanwhile, the energy density is high (4.3 kW h kg-1), and the energy is also one of the most promising energy carriers. As a potential hydrogen carrier, NH is different from liquid hydrogen that needs to be stored under more severe conditions 3 Liquefaction can be easily achieved by increasing the pressure to ≈ 10bar at room temperature or cooling to-33 ℃ at atmospheric pressure. In fact, once direct ammonia fuel cells reach greater maturity, it is expected that ammonia will become the primary carbon-free fuel for ships and heavy transportation vehicles. Thus, NH is foreseen 3 Will be increasingly demanded.
Current industrial scale NH 3 Synthesis still relies heavily on the Haber-Bosch process, which requires harsh operating conditions including high temperatures (400-500 ℃), high pressures (150-300 atm), heterogeneous iron-based catalysts, and high purity hydrogen gas from reforming natural gas. Although this conventional process has driven the development of synthetic ammonia, NH is an energy-intensive process due to its enormous annual output and energy-combined emissions 3 The synthetic industry has accounted for 1-2% of the world's energy supply and 1% of the total global energy carbon dioxide emissions. Therefore, in order to meet the two degree celsius (2 DS) target of COP21 for synthetic ammonia, an alternative sustainable strategy compatible with renewable energy sources that can meet the growing demand is urgently needed to replace the traditional Haber-Bosch process.
Electrocatalytic processes have become a clean energy route to decentralized ammonia production at room temperature on a variety of infrastructure scales, and may be driven by locally generated renewable energy sources. Electrochemical Nitrogen Reduction Reactions (NRRs) have recently attracted extensive research interest. Under mild conditions and high compatibility with renewable power, the electrocatalysis of N is realized by respectively using readily available nitrogen and water as a nitrogen source and a proton source 2 To NH 3 The transformation of (3). However, due to the nonpolar nature of nitrogen, the high dissociation energy of N ≡ N bond (945 kJ mol-1), the low water solubility (0.66 mmol L-1at 25 ℃ and 1 bar) and the competitive Hydrogen Evolution Reaction (HER) in the reaction process, the selectivity of NRR synthetic ammonia is obviously insufficient, and the yield of ammonia is (a), (b), (c), (d), (e) and (e)<200 μ g h-1 mgcat-1) is even two times lower than the Haber-Bosch processTo three orders of magnitude. In contrast, NO 3 Exhibit a particular attraction of NO compared with nitrogen 3 Exhibit relatively lower N = O bond dissociation energy (204 kJ mol "1) and higher solubility (3.76 mol L" 1). Theoretically, the reaction energy barrier for the electrocatalytic nitrate reduction reaction (NITRR) occurring at the solid-liquid interface is lower than that of the NRR. Thus, electrocatalytic NITRR is easier to perform from a structural property point of view. At the same time, NO 3 Widely present in surface water, ground water and nuclear waste as one of the most widespread water pollutants in the world, harmful to the environment and human health. Therefore, the conversion of the waste nitric acid aqueous solution into the ammonia value-added product has great significance in the aspects of comprehensive energy and environment.
NO 3 Conversion to NH 3 Is a process involving nine proton and eight electron transfer reactions (NO) 3 -+ 6H2O+8e-→NH 3 +9 OH-), thereby significantly reducing the overall kinetic rate. In addition, the reaction potential (1.20V vs. Reversible Hydrogen Electrode (RHE)) for electrocatalytic nitrate reduction to ammonia compares to NO with a five electron transfer process 3 Conversion to N 2 The reaction (1.25V vs. Reversible Hydrogen Electrode (RHE)) was slightly lower. Make NO 3 Reduction mostly favors five electron processes to reduce to N 2 Rather than the desired NH 3 . More importantly, NO 3 Conversion to NH 3 Typically below the Hydrogen Evolution Reaction (HER) potential (0V vs. Reversible Hydrogen Electrode (RHE)), which also causes hydrogen gas to be generated and electron donors to be consumed, ultimately resulting in low faradaic efficiency. In addition, the complex products of NITRR may include NO 2 -、N 2 And NH 3 This also presents a significant challenge to the goal of highly selective synthesis.
Many transition or noble metals (e.g., pt, pd, ru, rh, ag, and Cu) have been used to design NITRR electrocatalysts. However, the high energy due to the planar resonant D3h configuration and the NO 3-lowest unoccupied orbital results in NO 3 The efficiency of adsorption and electron injection into pi × reverse bond orbitals is low, and therefore their activity is relatively low. Though the NO adsorption and activation are carried out by the traditional alloying strategy by using Sn, cu, ge and other promoters 3 And initiating the reaction, andthe reaction selectivity is controlled with noble metals, but the products generally exhibit a wide distribution and exhibit a lower ammonia selectivity. This is because the strong competition of different nitrogen-containing by-products and the HER complicates the reaction and further reduces the faradaic efficiency of ammonia. Thus, the design can selectively introduce NO 3 Reduction to NH 3 And inhibit N ≡ N bond formation and catalysts of HER are highly desirable.
Disclosure of Invention
The invention aims to provide a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction, which improves the utilization rate of noble metals and well introduces a mesoporous structure with unique functionality by synthesizing the mesoporous palladium-copper nano catalyst, improves the activity of synthesizing ammonia by electroreduction of nitrate by the mesoporous structure, and particularly obviously improves the selectivity of ammonia.
The invention discloses a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction and an application thereof, and adopts the following technical scheme:
a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction comprises the following steps:
s1, dissolving dioctadecyl dimethyl ammonium chloride in a cosolvent of water and ethanol;
s2, adjusting the pH value of the reaction solution in the step S1 to 7-8 by using sodium hydroxide;
s3, sequentially adding chloropalladate and a copper nitrate solution into the reaction solution obtained in the step S2;
s4, adding ascorbic acid into the reaction solution obtained in the step S3 for reduction;
and S5, after the reaction in the step S4 is finished, removing the surfactant through centrifugal washing to obtain the mesoporous palladium-copper nano catalyst.
Preferably, in the step S1, dioctadecyl dimethyl ammonium chloride is dissolved in deionized water at 73-78 ℃, and after complete dissolution, absolute ethyl alcohol is added and mixed uniformly, wherein the volume ratio of the dioctadecyl dimethyl ammonium chloride to the absolute ethyl alcohol to the deionized water is 1.5: 1:4.
Preferably, in the step S2, after the reaction solution is cooled, the concentration of the added sodium hydroxide is 0.1mol/L, and the volume ratio of the dioctadecyldimethylammonium chloride to the sodium hydroxide is 15: 1.
Preferably, in the step S3, the concentrations of the chloropalladate and the copper nitrate solution are both 0.01mol/L, and the volume ratio of the dioctadecyldimethylammonium chloride to the chloropalladate to the copper nitrate solution is 25: 4:3.
Preferably, in the step S4, after the reaction solution is allowed to stand at room temperature for 0.4 to 0.6 hours, 0.3mol/L ascorbic acid is added for reduction, the reaction time is 1 to 2 hours, and the volume ratio of the dioctadecyldimethylammonium chloride to the ascorbic acid is 3: 1.
Preferably, in the step S5, the solvent for centrifugal washing is a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 3:1.
Preferably, the step S5 obtains the component ratio of Pd 63 Cu 37 The mesoporous palladium-copper catalyst.
The application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction comprises the following steps of physically loading the mesoporous palladium-copper nano catalyst and VulcanXC-72 carbon black according to the mass ratio of 1:1, dropwise coating the mesoporous palladium-copper nano catalyst on clean carbon paper as a cathode catalyst, wherein the loading amount of the catalyst is 0.1mg/cm & lt 2 & gt, and drying the catalyst and applying the catalyst to the electroreduction of nitrate to synthesize ammonia.
Preferably, a three-electrode system is adopted, the mesoporous palladium-copper nano catalyst is dripped on carbon paper, a clamping piece electrode is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and a potassium hydroxide and potassium nitrate mixed solution is used as an electrolyte.
According to a preferable scheme, the concentration of potassium hydroxide in the electrolyte is 0.1mol/L, the concentration of potassium nitrate is 0.01mol/L, in the preparation process of the catalyst, ethanol, deionized water and naphthol are used as solvents according to a volume ratio of 15.
The preparation method of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction disclosed by the invention has the beneficial effects that: the advantages of the structure and the components of the prepared mesoporous palladium-copper nano catalyst can greatly improve the utilization rate of noble metals and greatly reduce the cost of raw materials; the one-step synthesis method is simple, easy to operate, capable of being prepared in large quantities and suitable for large-scale industrial production, and favorable adsorption of nitrate can be realized due to the mesoporous characteristics and adjustable components of the mesoporous palladium-copper nano catalyst, so that the invention brings better effects on degradation and utilization of nitrate pollution.
Drawings
FIG. 1 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and comparative catalyst (Pd) 63 Cu 37 X-ray diffraction patterns (XRD) of Nanoparticles (NPs), pd mesoporous nanospheres (MSs), pdNPs).
FIG. 2 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Transmission Electron Microscopy (TEM) of the nanocatalyst.
FIG. 3 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Linear Sweep Voltammetry (LSV) curves (with or without KNO) for nanocatalysts 3 )。
FIG. 4 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and comparative catalyst (Pd) 63 Cu 37 LSV curves of Nanoparticles (NPs), pd mesoporous nanospheres (MSs), pdNPs).
FIG. 5 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and comparative catalyst (Pd) 63 Cu 37 Performance diagram of ammonia synthesis by electrically reducing nitrate of Nanoparticles (NPs), pd mesoporous nanospheres (MSs) and PdNPs (electrolytic solution of 0.1mol/LKOH +0.01mol/LKNO for 2 hours under different voltages) 3 )。
FIG. 6 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and catalyst (Pd) comparative to comparative examples 1-3 63 Cu 37 Energy Efficiency (EE) diagram for synthesizing ammonia by electrically reducing nitrate of nano-particles (NPs), pd mesoporous nanospheres (MSs) and PdNPs).
FIG. 7 is the present inventionMesoporous Pd prepared in inventive example 1 63 Cu 37 Nano-catalyst and comparative catalyst (Pd) 63 Cu 37 The cycle stability performance diagram of Nano Particles (NPs), pd mesoporous nanospheres (MSs) and PdNPs (PdNPs) (the electrolysis time is 2 hours under the optimal voltage of each catalyst, and the electrolyte is 0.1mol/LKOH +0.01mol/LKNO 3 )。
Detailed Description
The invention will be further elucidated and described with reference to the embodiments and drawings of the specification:
the mesoporous noble metal-based nano-particles are novel nano-structure materials, and the solid framework of the mesoporous noble metal-based nano-particles is surrounded by 2-50nm mesopores to form complete and uniform nano-particles. Mesoporous metallic materials have recently been considered as potential selective (electro) catalysts. There are three main structural advantages: (i) The metal mesopores provide a confinement clamping site and change the coordination/chemisorption properties of reactants, selectively promote favorable products and inhibit the competitive reaction thereof; (ii) Mesopores provide a good space for stabilizing unfavorable active sites and retaining reaction intermediates for selectively promoting (electro) catalysis to high-value products; (iii) The long channel mesopores provide a stable and active nanospace to enhance the retention time of deep (electro-) catalyzed multi-step reactions to produce selective products. Therefore, the mesoporous noble metal-based material is an important research direction for promoting the improvement (especially selectivity) of the performance of synthesizing ammonia by electrically reducing nitrate, and the invention is provided in view of the important research direction.
A preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction comprises the following steps:
s1, dissolving dioctadecyl dimethyl ammonium chloride in a cosolvent of water and ethanol, dissolving the dioctadecyl dimethyl ammonium chloride in deionized water at 73-78 ℃, adding absolute ethyl alcohol after complete dissolution, and uniformly mixing, wherein the volume ratio of the dioctadecyl dimethyl ammonium chloride to the absolute ethyl alcohol to the deionized water is 1.5: 1:4;
s2, adjusting the pH value of the reaction solution obtained in the step S1 to 7-8 by using sodium hydroxide, wherein after the reaction solution is cooled, the concentration of the added sodium hydroxide is 0.1mol/L, and the volume ratio of the dioctadecyl dimethyl ammonium chloride to the sodium hydroxide is 15: 1;
s3, sequentially adding a chloropalladic acid solution and a copper nitrate solution into the reaction solution obtained in the step S2, wherein the concentrations of the chloropalladic acid and the copper nitrate solution are both 0.01mol/L, and the volume ratio of the dioctadecyl dimethyl ammonium chloride to the chloropalladic acid to the copper nitrate solution is 25: 4:3;
s4, adding ascorbic acid into the reaction solution obtained in the step S3 for reduction, and after the reaction solution is kept stand at room temperature for 0.4-0.6 h, adding 0.3mol/L ascorbic acid for reduction, wherein the reaction time is 1-2h, and the volume ratio of the dioctadecyldimethylammonium chloride to the ascorbic acid is 3: 1;
s5, after the reaction in the step S4 is finished, removing the surfactant through centrifugal washing to obtain the mesoporous palladium-copper nano catalyst, wherein the solvent for centrifugal washing is a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 3:1, and the component ratio is Pd 63 Cu 37 The mesoporous palladium-copper catalyst.
The application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction comprises the following steps of physically loading the mesoporous palladium-copper nano catalyst and VulcanXC-72 carbon black according to the mass ratio of 1:1, dropwise coating the mesoporous palladium-copper nano catalyst on clean carbon paper as a cathode catalyst, wherein the loading amount of the catalyst is 0.1mg/cm & lt 2 & gt, and drying the catalyst and applying the catalyst to the electroreduction of nitrate to synthesize ammonia.
A three-electrode system is adopted, the mesoporous palladium-copper nano catalyst is dripped on carbon paper, a clamping piece electrode is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum piece electrode is used as a counter electrode, and a potassium hydroxide and potassium nitrate mixed solution is used as an electrolyte.
The concentration of potassium hydroxide in the electrolyte is 0.1mol/L, the concentration of potassium nitrate is 0.01mol/L, in the preparation process of the catalyst, the volume ratio of ethanol to deionized water to naphthol is 15.
Example 1
Preparation of mesoporous Pd63Cu37 nanocatalyst:
3mg dioctadecyldimethylammonium chloride (DODAC) was dissolved in 8mL deionized water at 75 deg.CAfter the materials are completely dissolved, adding 2mL of absolute ethyl alcohol and uniformly mixing; after the reaction solution is cooled, adding 0.2mL of 0.1mol/L sodium hydroxide solution to adjust the pH value of the reaction solution; sequentially adding 0.48mL of chloropalladate with the concentration of 0.01mol/L and 0.36mL of copper nitrate solution with the concentration of 0.01mol/L into the reaction solution obtained in the last step; after the reaction solution is kept stand for 0.5h at room temperature, 1mL of ascorbic acid with the concentration of 0.3mol/L is added for reduction, and the reaction time is 1-2h; after the reaction is finished, the surfactant is removed by centrifugal washing by using a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 3:1, and the mesoporous Pd with the optimal component ratio is obtained 63 Cu 37 A catalyst.
Example 2
Preparation of mesoporous palladium-copper electrode
Weighing 1mg of mesoporous Pd prepared in the example 63 Cu 37 The nano catalyst is mixed with 1mg VulcanXC-72 carbon black solution and stirred (more than 3 h) for physical loading for catalysis. 2mg of carbon black loaded mesoporous Pd 63 Cu 37 Mixing the nano-catalyst with 400 mu L of deionized water, 520 mu L of absolute ethyl alcohol and 80 mu L of naphthol solution, and performing ultrasonic treatment on the mixed solution for 0.5h to obtain 1mg/mL of mesoporous Pd 63 Cu 37 A nano catalyst solution. A pipette gun was used to draw 50. Mu.L of the catalyst solution and uniformly drop-coat it onto a 1cm X2 cm piece of clean carbon paper to a catalyst loading of 0.1mg/cm-2. And drying the electrode to be used as a mesoporous palladium-copper electrode together with the clip electrode.
Example 3
As a comparative example of example 2, a comparative catalyst (Pd) was synthesized 63 Cu 37 Nanoparticles (NPs), pd mesoporous nanospheres (MSs), pdNPs) as a comparison of catalytic properties.
Example 4
Electrocatalytic reduction of nitrate to synthesize ammonia
An electrochemical workstation (Chenhua 660 e) is utilized to carry out the electrocatalytic reduction reaction of nitrate to synthesize ammonia. The test adopts a three-electrode system, a mesoporous palladium copper electrode is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, and a platinum sheet electrode of 1cm multiplied by 2cm is used as a counter electrode. The electrolytic cell adopts an H-type electrolytic cell, and takes a mixed solution of 0.1mol/L potassium hydroxide and 0.01mol/L potassium nitrate as an electrolyte. Argon with a purity of 99.9% or more was required to be passed to saturation both before electrochemical testing and during reduction. The test temperature was 25 ℃.
Example 5
As a comparative example of example 4, in order to qualitatively test the presence or absence of nitrate reduction activity of the catalyst, the procedure of example 4 was repeated except that nitrate (pure KOH) was not added to the electrolyte.
Comparative example 1
Pd 63 Cu 37 Preparation of Nanoparticles (NPs)
Under the condition of room temperature, 0.48m of chloropalladate with the concentration of L0.01mol/L and 0.36mL of copper nitrate solution with the concentration of 0.01mol/L are sequentially added into 10mL of deionized water; adding 0.28mL of 1mg/mLVulcan XC-72 carbon black solution, shaking uniformly, and adding 1mL of 0.3mol/L ascorbic acid for reduction for 1-2h; after the reaction is finished, the Pd with the same component ratio is obtained by using a mixed solution of absolute ethyl alcohol and deionized water with the volume ratio of 3:1 for centrifugal washing 63 Cu 37 NPs。
Comparative example 2
Preparation of Pd mesoporous nanospheres (MSs)
Dissolving 3mgDODAC in 8mL of deionized water at 75 ℃, adding 2mL of absolute ethyl alcohol after complete dissolution, and uniformly mixing; after the reaction solution is cooled, adding 0.2mL of 0.1mol/L sodium hydroxide solution to adjust the pH of the reaction solution; adding 0.48mL of chloropalladic acid with the concentration of 0.01mol/L into the reaction solution obtained in the last step; after the reaction solution is kept stand for 0.5h at room temperature, 1mL of ascorbic acid with the concentration of 0.3mol/L is added for reduction, and the reaction time is 1-2h; after the reaction is finished, a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 3:1 is used for centrifugal washing to remove the surfactant, and PdMSs are obtained.
Comparative example 3
Preparation of Pd Nanoparticles (NPs)
Weighing 1mg of palladium black at room temperature, adding 1mL of 1mg/mLVulcan XC-72 carbon black solution, mixing and stirring (for more than 3 h) for physical loading, and centrifuging by using a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 3:1 to obtain PdNPs.
In the electrocatalytic nitrate reduction ammonia synthesis test, the current density (j) in the implementation voltage range is recorded by utilizing a Linear Sweep Voltammetry (LSV), and the current density can be used for characterizing the electrochemical behavior in the voltage range, wherein the LSV sweep rate is 10mV/s, and the sweep voltage range is-0.6-0.2V relative to a standard hydrogen electrode; the constant voltage method can be used to record the current-time (I-t) curve at an applied potential, to record the amount of charge (Q) to calculate the Faraday Efficiency (FE); the applied voltage range of the embodiment of the application is-0.05 to-0.4V relative to the standard hydrogen electrode; the ammonia yield (NH 3 yieldrate) after the nitrate reduction reaction was tested using the classical indophenol blue chromogenic method and quantified by uv spectrophotometry.
The Faraday efficiency of ammonia was calculated as follows:
FE(NH 3 )＝(8×F×C NH3 ×V10 -6 )/(17×Q)×100％
the ammonia yield was calculated as follows:
Yieldrate(NH 3 )＝(C NH3 ×V)/(t×m)
wherein C is NH3 Is the NH tested 3 Concentration (. Mu.g/mL); v is the volume of electrolyte (30 mL); t is the electrolysis time (2 h); a is the geometric area of the electrode (0.5 cm-2); f is the Faraday efficiency (96485C/mol); q (C) is the total amount of charge passing through the electrode and is the result of the integration of the I-t curve.
The Energy Efficiency (EE) of ammonia was calculated as follows:
Energyefficiency(NH 3 )＝(1.23-E NH30 )×FE(NH 3 )/(1.23-E)×100％
E NH30 equilibrium potential for electroreduction of nitrate to ammonia synthesis in alkaline medium (0.70V): FE (NH) 3 ) Is NH 3 Faradaic efficiency of (a): 1.23V is the water oxidation equilibrium potential (i.e. assuming zero water oxidation overpotential); e is synthetic NH 3 Applied potential (relative to a reversible hydrogen electrode).
Structural characterization of the catalysts of the examples and analysis of the performances of the electroreduction of nitrate synthesis ammonia:
FIG. 1 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and comparative catalysts (Pd) of comparative examples 1-3 63 Cu 37 X-ray diffraction patterns (XRD) of Nanoparticles (NPs), pd mesoporous nanospheres (MSs) and PdNPs) show Pd 63 Cu 37 MSs are face centered cubic (fcc), and the positive shift of all diffraction peaks indicates that Cu atoms with smaller atomic radius are alloyed in a substitutional manner, shortening the lattice spacing of Pd-Pd bonds.
FIG. 2 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Transmission Electron Microscopy (TEM) of the nanocatalyst. The catalyst is shown as highly uniformly dispersed mesoporous nanospheres with an average diameter of 45nm (FIG. 2 a). The whole particle is distributed with three-dimensional radial and cylindrical open mesopores, the average mesopore size is 3.7nm, and the framework thickness is 4.1nm.
FIG. 3 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 LSV profile of nanocatalysts in electrochemical nitrate reduction tests. The graph shows that compared with the electrolyte without nitrate (0.1 mol/LKOH), the nitrate reduction current density is obviously increased under the condition of the electrolyte with the mixed solution of 0.1mol/L potassium hydroxide and 0.01mol/L potassium nitrate, which indicates that the mesoporous Pd is 63 Cu 37 The nano-catalyst has electrocatalytic nitrate reduction activity.
FIG. 4 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and catalyst (Pd) comparative to comparative examples 1-3 63 Cu 37 LSV curves of Nanoparticles (NPs), pd mesoporous nanospheres (MSs), pdNPs). In the figure, mesoporous Pd is shown 63 Cu 37 The maximum nitrate reduction current density of the nano catalyst indicates mesoporous Pd 63 Cu 37 The nano-catalyst has the best electrocatalytic nitrate reduction activity.
FIG. 5 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and catalyst (Pd) comparative to comparative examples 1-3 63 Cu 37 Ammonia yield and Faraday efficiency performance diagrams for ammonia synthesis by electrically reducing nitrate of Nanoparticles (NPs), pd mesoporous nanospheres (MSs) and PdNPs. As shown in the figures, it is shown that,mesoporous Pd 63 Cu 37 The nano catalyst obtains the best Faraday efficiency of 85% under the voltage of-0.25V relative to the standard hydrogen electrode, and the corresponding ammonia yield is 3058 mu gh-1mg-1. Performance superior to comparative catalyst Pd under optimal conditions 63 Cu 37 NPs (58%), pdMSs (72%) and PdNPs (49%).
FIG. 6 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and catalyst (Pd) comparative to comparative examples 1-3 63 Cu 37 Energy Efficiency (EE) diagram for synthesizing ammonia by electrically reducing nitrate of nano-particles (NPs), pd mesoporous nanospheres (MSs) and PdNPs). In the figure, mesoporous Pd is shown 63 Cu 37 The nano catalyst obtains 31% of Faraday efficiency under the corresponding voltage of-0.25V relative to the standard hydrogen electrode, and is greatly superior to a comparative catalyst.
FIG. 7 shows mesoporous Pd prepared in example 1 of the present invention 63 Cu 37 Nano-catalyst and catalyst (Pd) comparative to comparative examples 1-3 63 Cu 37 Cycle stability diagram of the electro-reduction nitrate synthesis ammonia of Nanoparticles (NPs), pd mesoporous nanospheres (MSs), pdNPs). The figure shows that after six cycles, the mesoporous Pd 63 Cu 37 The stability of the nano-catalyst is optimal.
The invention provides a preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction, and the prepared mesoporous palladium-copper nano catalyst has the advantages of greatly improving the utilization rate of noble metals and greatly reducing the cost of raw materials due to the structure and component advantages; the one-step synthesis method is simple, easy to operate, capable of being prepared in large quantities and suitable for large-scale industrial production, and favorable adsorption of nitrate can be realized due to the mesoporous characteristics and adjustable components of the mesoporous palladium-copper nano catalyst, so that the invention brings better effects on degradation and utilization of nitrate pollution.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction is characterized by comprising the following steps:
s1, dissolving dioctadecyl dimethyl ammonium chloride in a cosolvent of water and ethanol;
s2, adjusting the pH value of the reaction solution in the step S1 to 7-8 by using sodium hydroxide;
s3, sequentially adding chloropalladate and a copper nitrate solution into the reaction solution obtained in the step S2;
s4, adding ascorbic acid into the reaction solution obtained in the step S3 for reduction;
and S5, after the reaction in the step S4 is finished, removing the surfactant through centrifugal washing to obtain the mesoporous palladium-copper nano catalyst.
2. The preparation method of the mesoporous palladium-copper nano catalyst for nitrate reduction and ammonia production according to claim 1, wherein in the step S1, dioctadecyl dimethyl ammonium chloride is dissolved in deionized water at 73-78 ℃, and after complete dissolution, absolute ethyl alcohol is added and mixed uniformly, wherein the volume ratio of the dioctadecyl dimethyl ammonium chloride to the absolute ethyl alcohol to the deionized water is 1.5: 1:4.
3. The method of claim 1, wherein in the step S2, after the reaction solution is cooled, the concentration of the added sodium hydroxide is 0.1mol/L, and the volume ratio of the dioctadecyldimethylammonium chloride to the sodium hydroxide is 15: 1.
4. The method for preparing the mesoporous palladium-copper nano catalyst for nitrate reduction to produce ammonia according to claim 1, wherein in the step S3, the concentrations of the chloropalladic acid and the copper nitrate solution are both 0.01mol/L, and the volume ratio of the dioctadecyldimethylammonium chloride to the chloropalladic acid to the copper nitrate solution is 25: 4:3.
5. The method for preparing the mesoporous palladium-copper nano catalyst for ammonia production through nitrate reduction according to claim 1, wherein in the step S4, after the reaction solution is allowed to stand at room temperature for 0.4 to 0.6 hours, 0.3mol/L ascorbic acid is added for reduction, the reaction time is 1 to 2 hours, and the volume ratio of dioctadecyldimethylammonium chloride to ascorbic acid is 3: 1.
6. The method for preparing the mesoporous palladium-copper nano catalyst for nitrate reduction to generate ammonia according to claim 1, wherein in the step S5, the solvent for centrifugal washing is a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 3:1.
7. The method for preparing a mesoporous palladium-copper nanocatalyst for nitrate reduction to ammonia according to claim 6, wherein the component ratio obtained in the step S5 is Pd 63 Cu 37 The mesoporous palladium-copper catalyst.
8. The application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction is characterized in that the mesoporous palladium-copper nano catalyst as claimed in any one of claims 1 to 7 and VulcanXC-72 carbon black are physically loaded according to a mass ratio of 1:1 and are dripped on clean carbon paper as a cathode catalyst, the loading amount of the catalyst is 0.1mg/cm < 2 >, and the catalyst is dried and applied to the electroreduction of nitrate to synthesize ammonia.
9. The application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction is characterized in that a three-electrode system is adopted, the mesoporous palladium-copper nano catalyst is dripped on carbon paper, a clamping piece electrode is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum piece electrode is used as a counter electrode, and a potassium hydroxide and potassium nitrate mixed solution is used as an electrolyte.
10. The application of the mesoporous palladium-copper nano catalyst for producing ammonia by nitrate reduction is characterized in that the concentration of potassium hydroxide in the electrolyte is 0.1mol/L, the concentration of potassium nitrate is 0.01mol/L, in the preparation process of the catalyst, the volume ratio of ethanol to deionized water to naphthol is 15.
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