CN117548129A - Preparation method and application of phosphorus-doped biological carbon-based palladium-copper single-atom catalyst - Google Patents
Preparation method and application of phosphorus-doped biological carbon-based palladium-copper single-atom catalyst Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 58
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 23
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000006722 reduction reaction Methods 0.000 claims description 30
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 23
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- 230000032683 aging Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
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- 229910002651 NO3 Inorganic materials 0.000 abstract description 30
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 30
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
- C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a phosphorus-doped biological carbon-based palladium-copper single-atom catalyst, belonging to the technical field of catalysis, and characterized in that: preparing phosphorus doped modified phyllostachys pubescens biochar (P-BC) by taking phyllostachys pubescens waste as a biochar substrate through pretreatment and a phytic acid through a dipping reduction method; then preparing palladium-copper bimetallic precursor solution, and fixing the volume by 3% polyethylene glycol; adding metal precursor solution, and then carrying out ultrasonic treatment and agingThe method comprises the steps of carrying out a first treatment on the surface of the The well dispersed solution was placed on a magnetic stirrer and sodium borohydride (NaBH) was added dropwise while stirring 4 ) A solution; oscillating to make NaBH 4 Fully reducing metal ions in the solution; repeatedly washing deionized water for 3 times, and vacuum-freezing through suction filtration to obtain the phosphorus-doped biological carbon-based palladium-copper monoatomic catalyst (Pd-Cu-P-BC). And constructing a three-dimensional electrocatalytic reduction nitrate reaction system by taking the three-dimensional electrocatalytic reduction nitrate reaction system as a three-dimensional particle electrode. The invention has reference significance for preparing and synthesizing the electrocatalyst with excellent catalytic efficiency and effectively preventing and treating nitrate pollution of underground water.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method and application of a phosphorus-doped biological carbon-based palladium-copper single-atom catalyst.
Background
The Guangxi agricultural and forestry waste moso bamboo is used as a carrier of the catalyst, so that the waste of resources can be greatly reduced, and the solid waste is recycled. There are studies showing that doping of carbon materials with other elements is likely to produce physicochemical properties more suitable for electrocatalytic reduction than ordinary carbon materials. Phosphorus atoms have the advantages of being capable of forming strong covalent bonds with surrounding carbon atoms due to strong electron donating ability, and the like, and are ideal doping atoms. The research shows that the doping of the P atoms can lead the lattice of carbon in the carbon material to be distorted, the defect sites are increased, the increased defect sites often have higher electron cloud density, the conductivity of the carbon material is increased, and the defect sites with high electron cloud density can reduce the catalytic reaction energy barrier and have higher reaction activity, so that the catalytic performance of the catalyst is improved. Meanwhile, the introduction of the hetero atoms can also change the types and the distribution of the surface active groups of the carbon material, so that the acid-base property of the material is regulated. The heteroatom functional group on the modified carbon material can be used for adjusting charge distribution of the loaded metal active component, promoting stability and dispersion of the metal component and inhibiting agglomeration of metal particles, so that the service life and catalytic effect of the catalyst are improved, and the catalyst can be used as an excellent carrier of the loaded catalyst. In the electrocatalytic reduction process, noble metal Pd is used as a main catalyst for catalytic reduction of nitrate. Meanwhile, doping auxiliary metal Cu on the Pd surface can greatly improve the catalytic effect of the catalyst.
Therefore, the method takes moso bamboo as a carrier material, modifies the moso bamboo by phosphorus doping, and obtains the phosphorus doped biological carbon-based palladium-copper single-atom catalyst (Pd-Cu-P-BC) through Pd-Cu metal loading. Currently, three major types of treatment technologies for nitrate in water body comprise a physical treatment technology, a chemical treatment technology and a biological treatment technology, and an electrocatalytic reduction technology is used for constructing a three-dimensional electrocatalytic reduction reaction system suitable for electrocatalytic reduction of nitrate due to the advantages of high efficiency, economy, energy conservation, renewable catalyst and the like, and is applied to treatment of sewage polluted by nitrate. Not only can maximally recycle the agricultural and forestry waste moso bamboo and improve the utilization rate of the moso bamboo, but also can provide a technical reference for the treatment of nitrate-containing wastewater.
Disclosure of Invention
The invention aims to provide a preparation method of a P-doped biological carbon-based palladium-copper single-atom catalyst, which has low cost and high catalytic efficiency and can be used for recycling the catalyst, and the preparation method is applied to nitrate wastewater. The method uses moso bamboo as carrier, 2% NaOH solution as digestion agent, phytic acid as doped phosphorus source, and PdCl 2 Solution and CuCl 2 The solutions were Pd respectively 2+ And Cu 2+ Pd-Cu-P-BC is synthesized by proper surface modification and defect engineering strategies, and Pd-Cu-P-BC is used as a three-dimensional particle electrode, and a three-dimensional electrocatalytic reduction reaction system suitable for electrocatalytic reduction of nitrate is built based on a traditional two-dimensional electrocatalytic reaction system.
The invention provides a preparation method of a phosphorus-doped biological carbon-based palladium-copper monoatomic catalyst, which is characterized by comprising the following steps:
step 1: pretreatment of biochar carrier substrates
Preferably, the specific steps include the following: firstly, the moso bamboo is dried and cut into 10×10×8 (mm) 3 ) The moso bamboo blocks are then soaked in NaOH for 3.5. 3.5 h to eliminate organic matters from the surface of the carrier, washed with ultrapure water to neutrality and dried.
More preferably, the NaOH is at a mass concentration of 2%;
more preferably, the drying temperature is 60 ℃;
more preferably, the drying time is 6 h;
step 2: phosphorus doping of biochar
Preferably, the specific steps include the following: firstly, uniformly mixing 5g of moso bamboo obtained in the step 1 with 15mL phytic acid solution with the mass fraction of 50% according to a certain impregnation ratio, and then transferring to a 100mL hydrothermal reaction kettle for reaction. Then, the cooled hydrothermal carbon is dried in an oven and then moved to a tube muffle furnace for calcination. Finally, the solid obtained after cooling is the P doped modified biochar (P-BC).
More preferably, the impregnation ratio = 3:1 (phytic acid: phyllostachys pubescens pieces);
more preferably, 50% phytic acid is selected as the phosphorus source for the phosphorus doping;
more preferably, the hydrothermal reaction condition is 200 ℃;
more preferably, the hydrothermal reaction time is 2 h;
more preferably, the drying temperature of the hydrothermal carbon in the oven is 105 ℃;
more preferably, the hydrothermal carbon is placed in an oven for a drying time of 24 h;
more preferably, the calcination conditions of the tubular muffle are: n (N) 2 Heating to 800 ℃ at 10 ℃/min under the condition;
more preferably, the calcination time of the tube muffle is 1 h.
Step 3: pd-Cu monoatomic loading of P-doped modified phyllostachys pubescens biochar
Preferably, the specific steps include the following: firstly, weighing PdCl with a certain mass 2 Solution and CuCl 2 The solution is prepared into a metal precursor solution with the required concentration. The two solutions are evenly mixed and then transferred into a 50mL volumetric flask, and polyethylene glycol is used for sizing to obtain the palladium-copper bimetallic mixed solution. Next, a certain mass of the P-BC obtained in step 2 was weighed into a triangle glass bottle with a stopper, and the metal precursor solution 50mL prepared by the above-described process was added thereto. Sonicating and aging the solution so that Pd in the solution 2+ And Cu 2+ Fully dispersed on the surface of the biological carbon and enters the pores of the moso bamboo carbon. Then, the well-dispersed solution was placed on a magnetic stirrer, and sodium borohydride (NaBH 4 ) And (3) the solution is added until no bubbles are generated in the dropwise added solution and the solution is in a transparent and clear state. Then the solution is placed in a constant temperature water bath oscillator to continuously oscillate so as to lead NaBH 4 The metal ions in the solution are fully reduced. Then repeatedly washing with 100mL deionized water for 3 times, vacuum-filtering, and lyophilizing in vacuum freeze-drying agent for 4 hr (preventing NaBH 4 Reduced metal monoatoms are bound by O in air 2 Oxidized into metal oxide to cover the surface of the biochar), and the dried solid is sealed and preserved to obtain the phosphorus doped biochar-based palladium-copper single-atom catalyst (Pd-Cu-P-BC). In the whole process, metal precursor solutions with different combination concentrations can influence the metal loading and the uniformity of dispersion of the biochar carrier.
More preferably, the PdCl 2 Dissolving with a small amount of 1.0 mol/L hydrochloric acid solution;
more preferably, the CuCl 2 Dissolving with ultrapure water;
more preferably, polyethylene glycol is selected to be used as the dispersant at a mass concentration of 3%;
more preferably, the ultrasound time is 30 min;
more preferably, the aging time is 30 minutes;
more preferably, the NaBH 4 The concentration is 0.01 mol/L;
more preferably, the NaBH 4 The dropping speed is 2 mL/min;
more preferably, the selected thermostatic waterbath shaker is rotated at 130 rpm;
more preferably, the selected thermostatic waterbath shaker oscillation time is 30 minutes.
And (3) taking the Pd-Cu-P-BC prepared in the step (3) as a three-dimensional particle electrode, and constructing a three-dimensional electrocatalytic reduction reaction system by combining a traditional two-dimensional electrochemical system. In the electrocatalytic reduction system, different precursor solution concentrations, initial nitrate concentrations, catalyst addition amounts, current densities and initial pH values can directly influence the removal efficiency of nitrate in water.
The phosphorus doped biological carbon-based palladium-copper monoatomic catalyst realizes that metal monoatoms are uniformly dispersed on the surface of biological carbon, and meanwhile, the doping of phosphorus regulates and controls the intrinsic structural property of the Pd-Cu metal supported catalyst. Pd-P or Cu-P is anchored to form a bond, so that the catalyst has stable catalytic activity, the electrocatalytic performance of the catalyst is effectively improved, and the catalyst is suitable for removing nitrate in water through a constructed three-dimensional electrocatalytic reduction system.
Compared with the existing electrocatalytic technology, the technical scheme provided by the invention has the following advantages:
1. the method adopts the cheap and easily obtained moso bamboo as the carrier of the catalyst, realizes the recycling of the solid waste, optimizes the defects of low surface activity, small specific surface area and the like of the traditional catalyst carrier by doping and modifying the heteroatomic catalyst, and promotes the deposition and dispersion of metal atoms on the carrier surface.
2. The metal loaded by the method exists in an atomic form, metal atoms and nonmetal atoms are anchored to form bonds and are uniformly dispersed, so that the catalyst has strong stability, and compared with other catalysts, the Pd-Cu-P-BC single-atom catalyst structure has more active sites, and the structural characteristics are more favorable for hydrogen evolution reaction.
3. The method adopts a three-dimensional electrocatalytic reduction reaction system, and the system has the advantages of high energy conservation, cost saving and the like while high-efficiency electrocatalytic reduction of nitrate, and can provide effective reference for developing an electrocatalytic monoatomic catalyst with high-efficiency catalytic activity and high selectivity.
Drawings
FIG. 1 is a STEM-HAADF morphology map and EDS element mapping map of a P-doped Phyllostachys Pubescens biochar-based palladium-copper monoatomic catalyst calcined at 800 ℃ in a nitrogen atmosphere in example 1;
FIG. 2 is an XRD spectrum of a single-atom catalyst doped with biological carbon-based palladium and copper in example 1P of the invention;
FIG. 3 is a graph showing the effect of impregnating electrocatalytic reduction of nitrate with different precursor concentrations in example 2 of the present invention;
FIG. 4 is a graph showing the electrocatalytic reduction effect of different initial nitrate nitrogen concentrations according to example 3 of the present invention;
FIG. 5 is a graph showing the effect of electrocatalytic reduction of nitrate with different amounts of catalyst according to example 4 of the present invention;
FIG. 6 is a graph showing the electrocatalytic reduction of nitrate at different current density intensities according to example 5 of the present invention;
FIG. 7 is a graph showing the effect of electrocatalytic reduction of nitrate by catalyst at different pH values in example 6 of the present invention;
FIG. 8 is a graph showing the recycling stability of the catalyst of example 7 Pd-Cu-P-BC according to the present invention.
Detailed Description
The invention is further illustrated by the following examples.
The P-doped biological carbon-based palladium-copper monoatomic catalyst is characterized in that: the catalyst consists of a P atom doped modified biochar serving as a matrix and palladium-copper bimetallic monoatoms uniformly dispersed in the matrix; the metal atoms in the catalyst are uniformly dispersed on the surface of the catalyst; the carbon material in the catalyst is selected from moso bamboo of agricultural and forestry waste. And the biological carbon material is pretreated to remove surface organic matters, and P is doped into a moso bamboo carbon lattice network to form a rich defect structure, so that more fixing sites are provided for loading anchoring metal monoatoms. Wherein the metal is selected from Pd, pt, ru, rh, ir, cu, fe, sn.
The invention provides a preparation method of a phosphorus-doped biological carbon-based palladium-copper monoatomic catalyst, which is characterized by comprising the following steps:
step 1: the biological carbon carrier substrate is pretreated by the following specific steps:
firstly, the moso bamboo is dried and cut into 10×10×8 (mm) 3 ) The moso bamboo blocks are then digested in 2% NaOH for 2.5. 2.5h to remove organic matters on the surface of the carrier, washed with ultrapure water to neutrality and dried.
Step 2: the method comprises the following specific steps of:
first, according to phytic acid: moso bamboo (impregnation ratio) =3:1 will 5g byAnd (2) uniformly mixing the moso bamboo obtained in the step (1) with a 15mL phytic acid solution with the mass fraction of 50%, transferring to a 100mL hydrothermal reaction kettle, and reacting at the temperature of 200 ℃ for 2 h. Then, the cooled hydrothermal charcoal is put into an oven at 105 ℃ to be dried for 24h, and then is moved into a tube muffle furnace to be treated with N 2 The temperature was raised to 800℃at a rate of 10℃per minute under an atmosphere, and 1h was calcined under this condition. Finally, the solid obtained after cooling is the P doped modified biochar (P-BC).
Step 3: pd-Cu monoatomic loading is carried out on the P-doped modified biochar, and the specific steps are as follows:
firstly, weighing PdCl with a certain mass 2 Solution and CuCl 2 The solution is prepared into a metal precursor solution with the required concentration. Wherein PdCl 2 Dissolving with small amount of 1.0 mol/L hydrochloric acid solution, cuCl 2 Dissolving with ultrapure water, mixing the two solutions uniformly, transferring into a 50mL volumetric flask, and fixing the volume to 50mL by using 3% polyethylene glycol as a dispersing agent to obtain a palladium-copper mixed solution. Next, a certain mass of the P-BC obtained in step 2 was weighed into a triangle glass bottle with a stopper, and the metal precursor solution 50mL prepared by the above-described process was added thereto. Ultrasonic treating the solution for 30min, and aging for 30min to obtain Pd in the solution 2+ And Cu 2+ Fully dispersed on the surface of the biological carbon and enters the pores of the moso bamboo carbon. Then, the well-dispersed solution was placed on a magnetic stirrer, and sodium borohydride (NaBH 4 ) The solution (the concentration is 0.01 mol/L, the dropping speed is about 2 mL/min) until no bubbles are generated in the dropped solution and the solution is in a transparent and clear state. Then the solution is placed in a constant temperature water bath oscillator and is continuously oscillated at the speed of 130 rpm to lead NaBH 4 The metal ions in the solution are fully reduced. Then repeatedly washing with 100mL deionized water for 3 times, suction filtering, and collecting lyophilized powder 4h (for preventing NaBH) 4 Reduced metal monoatoms are bound by O in air 2 Oxidized into metal oxide to cover the surface of the biochar), and the dried solid is sealed and preserved to obtain the phosphorus doped biochar-based palladium-copper single-atom catalyst (Pd-Cu-P-BC). In the whole process, metal precursor solutions with different combination concentrations can be used forThe metal loading of the biochar carrier and the uniformity of dispersion are affected.
And (3) taking the Pd-Cu-P-BC prepared in the step (3) as a three-dimensional particle electrode, and constructing a three-dimensional electrocatalytic reduction reaction system by combining a traditional two-dimensional electrochemical system. In the electrocatalytic reduction system, different precursor solution concentrations, initial nitrate concentrations, catalyst addition amounts, current densities and initial pH values can directly influence the removal efficiency of nitrate in water.
The phosphorus doped biological carbon-based palladium-copper monoatomic catalyst realizes that metal monoatoms are uniformly dispersed on the surface of biological carbon, and meanwhile, the doping of phosphorus regulates and controls the intrinsic structural property of the Pd-Cu metal supported catalyst. Pd-P or Cu-P is anchored to form a bond, so that the catalyst has stable catalytic activity, the electrocatalytic performance of the catalyst is effectively improved, and the catalyst is suitable for removing nitrate in water through a constructed three-dimensional electrocatalytic reduction system.
Example 1
The preparation method of the phosphorus doped modified biochar by taking moso bamboo as a carbon substrate and phytic acid as a phosphorus source comprises the following steps: drying Phyllostachys Pubescens, and cutting into 10×10×8 (mm) 3 ) The moso bamboo pieces are then boiled in 2% naoh for 2.5. 2.5h, washed with ultrapure water to neutrality and dried. The preparation method comprises the following steps of: moso bamboo (impregnation ratio) =3:1 5g of the treated moso bamboo was mixed with a 50% mass fraction of a 15mL phytic acid solution, and then transferred to a 100mL hydrothermal reaction kettle for reaction at 200 ℃ for 2 h. Then, the cooled hydrothermal charcoal is put into an oven at 105 ℃ to be dried for 24h, and then is moved into a tube muffle furnace to be treated with N 2 The temperature was raised to 800℃at a rate of 10℃per minute under an atmosphere, and 1h was calcined under this condition. Finally, the P doped modified biochar (P-BC) can be obtained after cooling.
Fig. 1 is a STEM-HAADF morphology map and EDS element mapping map of heteroatomic doped moso bamboo biochar after calcination at 800 ℃ in nitrogen atmosphere, from which it can be seen that heteroatomic doping into graphitized moso bamboo carbon lattices forms a rich defect structure, providing more active sites for metal loading. The metal atoms are dispersed more uniformly, the metal species can be better dispersed on the surface of the carrier in a single-atom form, and the metal loading capacity is higher, so that the carrier has better atom utilization rate and electrocatalytic activity. This also demonstrates that the catalyst support preparation method employed in the present invention has more excellent selectivity than the conventional catalyst support.
The P-BC obtained by the process is used for preparing a phosphorus doped modified biological carbon-based palladium-copper single-atom catalyst, and the preparation method comprises the following steps: pdCl is selected for use 2 Solution and CuCl 2 The solution is prepared into two different metal precursor solutions, which are respectively: pd (Pd) 2+ The concentration is 0.3 g/L, cu 2+ The concentration is 0.075 g/L; pd (Pd) 2+ The concentration is 0.6 g/L, cu 2+ The concentration is 0.15 g/L (PdCl) 2 Dissolving with small amount of 1.0 mol/L hydrochloric acid solution, cuCl 2 Dissolved with ultrapure water), the two solutions are evenly mixed and then transferred into a 50mL volumetric flask, 3 percent polyethylene glycol is used as a dispersing agent and the volume is fixed to 50mL, thus obtaining two palladium-copper bimetallic mixed solutions with different concentrations. Next, two parts of P-BC of the same mass were weighed into a triangular glass bottle with a stopper, to which two metal precursor solutions 50, mL of different concentrations prepared by the above procedure were added, respectively. Ultrasonic treating the solution for 30min, and aging for 30min to obtain Pd in the solution 2+ And Cu 2+ Fully dispersed on the surface of the biological carbon and enters the pores of the moso bamboo carbon. Then, the well-dispersed solution was placed on a magnetic stirrer, and sodium borohydride (NaBH 4 ) The solution (the concentration is 0.01 mol/L, the dropping speed is about 2 mL/min) until no bubbles are generated in the dropped solution and the solution is in a transparent and clear state. Then the solution is placed in a constant temperature water bath oscillator and is continuously oscillated at the speed of 130 rpm to lead NaBH 4 The metal ions in the solution are fully reduced. Then repeatedly washing with 100mL deionized water for 3 times, suction filtering, collecting the filtrate, and lyophilizing in vacuum freeze drying agent for 4h to obtain two phosphorus doped biochar based palladium copper monoatomic catalysts (Pd) 0.30 -Cu 0.075 -P-BC and Pd 0.60 -Cu 0.15 -P-BC）。
FIG. 2 shows characterization analysis of three different catalysts, namely BC, P-BC and Pd-Cu-P-BC, and the characterization of the three catalysts is shown by XRD spectra: the successful doping of phosphorus atoms into the biochar lattice proves that Pd and Cu metals of the catalyst prepared by the research are successfully loaded on the surface of the phosphorus doped modified biochar carrier. After phosphorus doping, the biochar lattice has defects with different degrees, which further proves that the defect structure is favorable for loading and dispersing metal atoms on the surface of the moso bamboo biochar.
Example 2
According to the method for preparing the catalyst in example 1, pd was used 2+ PdCl with concentration of 0.30, 0.60 and 0.80 g/L 2 Preparing precursor solutions with different concentrations according to the mass ratio of Pd/Cu of 4:1 based on the solution, carrying out impregnating metal loading on the moso bamboo biochar, and respectively marking the obtained catalysts as Pd 0.30 -Cu 0.075 -P-BC、Pd 0.60 -Cu 0.15 -P-BC、Pd 0.80 -Cu 0.20 -P-BC. The initial concentration of nitrate nitrogen was 50 mg/L and the current density was 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 =1.5 cm, catalyst addition 0.80 g/L, positive and negative electrolyte chamber volume of the reactor 125 mL, supporting electrolyte solution Na 2 SO 4 The solution (the concentration is 0.20. 0.20 g/L) is used for constructing a three-dimensional electrocatalytic reduction reaction system.
As shown in fig. 3, the effect of different precursor concentrations on electrocatalytically reducing nitrate in water was investigated with three catalysts of different precursor concentration values as three-dimensional particles. As can be seen from the figure: the removal rate of nitrate nitrogen increases with increasing reaction time, wherein Pd 0.60 -Cu 0.15 -P-BC and Pd 0.80 -Cu 0.20 P-BC shows similar catalytic reduction effect, and combined with an electron microscope characterization result, the catalyst is shown in Pd 0.60 -Cu 0.15 In the P-BC catalyst, the metal atoms are dispersed more uniformly and the loading is higher, thus more proving Pd 0.60 -Cu 0.15 P-BC is the most suitable precursor solution impregnation concentration for preparing the phosphorus doped Pd-Cu-BC bimetallic monoatomic catalyst.
Example 3
Preparing nitrate nitrogen solutions with different initial concentrations of 50 mg/L, 75 mg/L, 100 mg/L and 125 mg/L as initial pollutant solutions, and Pd 0.60 -Cu 0.15 P-BC catalyst as a three-dimensional particle catalyst with a current density of 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 =1.5 cm, catalyst addition 0.80 g/L, positive and negative electrolyte chamber volume of the reactor 125 mL, supporting electrolyte solution Na 2 SO 4 The solution (the concentration is 0.20. 0.20 g/L) is used for constructing a three-dimensional electrocatalytic reaction system.
FIG. 4 is a graph showing electrocatalytic reduction performance for different initial nitrate nitrogen concentrations, as follows: under different initial nitrate nitrogen concentrations, the nitrate nitrogen can achieve good removal effect, but the final result shows that the catalytic reduction effect is optimal when the initial nitrate nitrogen concentration is 100 mg/L, so that the initial pollutant concentration is selected to be 100 mg/L optimally in the study.
Example 4
To explore the influence of different catalyst addition amounts on electrocatalytic nitrate, pd is used 0.60 -Cu 0.15 P-BC catalyst as a three-dimensional particle catalyst with a current density of 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 =1.5 cm, initial concentration of nitrate nitrogen 100 mg/L, volume of the cathode and anode electrolytic chamber of the reactor 125 mL, and Na as supporting electrolyte solution 2 SO 4 The solution (the concentration is 0.20 g/L), the adding amount of the catalyst is 0.40 g/L, 0.60 g/L, 0.80 g/L and 1.00 g/L respectively, and a three-dimensional electrocatalytic reaction system is built.
FIG. 5 is a graph showing the effectiveness of electrocatalytic reduction of nitrate with four different catalyst loadings, showing: in the three-dimensional particle electrode reaction system, when the adding amount of the catalyst is high, the final removal effect of nitrate nitrogen is not ideal. It is evident that the final removal efficiency for nitrate nitrogen was nearly 100% when the catalyst loading was 0.8 g/L. Therefore, the catalyst addition amount of 0.80 g/L was selected as the optimal addition amount for denitration of the catalyst in this study.
Example 5
In Pd 0.60 -Cu 0.15 P-BC catalyst as a three-dimensional particle catalyst with a current density of 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 The initial concentration of nitrate nitrogen is 100 mg/L, the catalyst addition amount is 0.80 g/L, the volume of a cathode and anode electrolytic chamber of the reactor is 125 mL, and the support electricity is providedThe solution of the electrolyte is Na 2 SO 4 Solutions (concentration 0.20. 0.20 g/L) with current densities of 1.90, 2.54, 3.17, 3.81, 4.44 mA/cm, respectively 2 The effect on electrocatalytic reduction of nitrate at different current densities was investigated.
FIG. 6 is a graph showing the effectiveness of electrocatalytic reduction of nitrate nitrogen at various current density intensities, as follows: the removal rate of nitrate nitrogen is obviously increased along with the increase of the current density, but after the current density reaches a certain value, the influence on the reduction rate of the nitrate nitrogen is reduced, so that the side reaction rate of electrolytic hydrogen evolution in a system is obviously accelerated, and the research considers the consumption of electric energy and the harmless treatment of pollutants, so that the current density is 3.17 mA/cm 2 Is most preferable.
Example 6
In Pd 0.60 -Cu 0.15 P-BC catalyst as a three-dimensional particle catalyst with a current density of 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 =1.5 cm, initial concentration of nitrate nitrogen 100 mg/L, catalyst addition 0.80 g/L, current density 3.17 mA/cm 2 The volume of the cathode and anode electrolytic chamber of the reactor is 125 mL, and the supporting electrolyte solution is Na 2 SO 4 The effect of the catalyst on electrocatalytic reduction of nitrate at different pH values was investigated for the solution (concentration 0.20 g/L).
FIG. 7 is a graph showing the effectiveness of the catalyst in electrocatalytic reduction of nitrate at various pH values, showing: when the pH value is less than 7 and the pH value is more than 7, the removal rate of nitrate nitrogen is obviously lower; when the pH value is equal to 7, the solution is neutral, and the removal rate of nitrate nitrogen in the reaction system is optimal; thus, the catalytic reduction effect of the catalyst is more favorable under neutral conditions.
Example 7
In order to examine the stability of the phosphorus doped biological carbon based palladium copper monoatomic catalyst, the catalyst is researched for recycling. The repeated experiment results of 3 times of circulation under the same conditions show (as shown in fig. 8), after the catalyst is recycled in the reaction system for 3 times, the removal rate of nitrate nitrogen is reduced from 99.46% to 94.75% under the optimal conditions, the generation rate of nitrogen is reduced from 44.51% to 40.52%, and the mass activity of the catalyst is basically unchanged. However, the catalyst can ensure the removal rate of nitrate nitrogen to be more than 95%, the generation rate of nitrogen is basically kept unchanged, and the mass activity of the catalyst is basically unchanged, so that the catalyst prepared by the research has relatively stable catalytic activity, and meanwhile, pd-Cu metal particles loaded on the surface of the moso bamboo biochar carrier are anchored to form bonds mainly in the form of Pd-P or Cu-P bonds, and the metal particles exist in the form of atomic morphology, so that the catalyst has stable catalytic activity and mass activity.
In summary, as described in the examples, different concentrations of precursor solutions, different initial nitrate concentrations, different amounts of catalyst addition, different current densities, and different promotion pH values all have different degrees of influence on the electrocatalytic reduction of nitrate nitrogen by Pd-Cu-P-BC catalysis. As proved by researches, the invention adopts Pd 0.60 -Cu 0.15 P-BC catalyst as a three-dimensional particle catalyst with a current density of 3.17 mA/cm 2 The distance between the polar plates is d 1 =d 2 =1.5 cm, initial concentration of nitrate nitrogen 100 mg/L, catalyst addition 0.80 g/L, current density 3.17 mA/cm 2 The volume of the cathode and anode electrolytic chamber of the reactor is 125 mL, and the supporting electrolyte solution is Na 2 SO 4 The solution (the concentration is 0.20 g/L) is used for constructing a three-dimensional electrocatalytic reduction nitrate reaction system under the condition of an initial pH value of 7, so that the optimal treatment effect on nitrate in water can be achieved.
Claims (8)
1. A preparation method and application of a phosphorus-doped biological carbon-based palladium-copper monoatomic catalyst are characterized by comprising the following specific steps:
(1) Drying Phyllostachys Pubescens, and cutting into 10×10×8 (mm) 3 ) The moso bamboo blocks are soaked in NaOH solution for 2.5 hours, washed to be neutral by ultrapure water and then dried;
(2) Uniformly mixing 5g of moso bamboo obtained in the step (1) with 15ml of phytic acid solution with the mass fraction of 50% according to a certain impregnation ratio (phytic acid: moso bamboo), and then transferring the mixture into a 100ml hydrothermal reaction kettle for hydrothermal reaction;
(3) Placing the cooled hydrothermal carbon in an oven at 105 ℃ for drying for 24 hours, and then transferring the hydrothermal carbon into a tubular muffle furnace for calcination for 1 hour; finally, the solid obtained after cooling is P doped modified biochar (P-BC);
(4) Weighing PdCl with certain mass 2 Solution and CuCl 2 Preparing a metal precursor solution with a required concentration by the solution, weighing a certain mass of P-BC, placing the P-BC into a triangular glass bottle with a plug, and adding 50ml of the metal precursor solution prepared by the process into the triangular glass bottle; ultrasonic treatment and aging of the solution;
(5) The well dispersed solution was placed on a magnetic stirrer and sodium borohydride (NaBH) was added dropwise while stirring 4 ) The solution is added until no bubble is generated in the dropped solution and the solution is transparent and clear; then the solution is placed in a constant temperature water bath oscillator and is continuously oscillated at the speed of 130 rpm to lead NaBH 4 Fully reducing metal ions in the solution; repeatedly washing with 100ml deionized water for 3 times, collecting the solid after freeze drying in vacuum freeze drying agent for 4h, and sealing and preserving to obtain the phosphorus doped biological carbon-based palladium copper single-atom catalyst (Pd-Cu-P-BC).
2. The preparation method of the phosphorus-doped biological carbon-based palladium-copper monoatomic catalyst, which is characterized in that the mass concentration of the NaOH solution in the step (1) is 2%.
3. The method for preparing a phosphorus-doped biochar-based palladium-copper monoatomic catalyst according to claim 1, wherein the impregnation ratio in the step (2) is 3:1 optimally.
4. The method for preparing the phosphorus-doped biochar-based palladium-copper monoatomic catalyst according to claim 1, wherein the hydrothermal reaction condition in the step (2) is 200 ℃ and the optimal reaction time is 2 hours.
5. The method for preparing a phosphorus-doped biochar-based palladium-copper monoatomic catalyst according to claim 1, wherein the tubular muffle of step (3) isThe calcining condition of the furnace is N 2 The atmosphere is optimally heated to 800 ℃ at a heating rate of 10 ℃/min.
6. The method for preparing a phosphorus-doped biochar-based palladium-copper monoatomic catalyst according to claim 1, wherein the ultrasonic treatment and aging time in the step (4) are 30min respectively.
7. The method for preparing a phosphorus-doped biochar-based palladium-copper monoatomic catalyst according to claim 1, wherein the concentration of sodium borohydride added dropwise in the step (5) is 0.01 mol/L, and the dropping speed is about 2 ml/min.
8. The method for preparing the phosphorus-doped biological carbon-based palladium-copper single-atom catalyst prepared by the method in claims 1, 2, 3, 4, 5, 6 and 7 is characterized in that the biological carbon-based palladium-copper single-atom catalyst is applied to electrocatalytic reduction reaction of nitrate nitrogen in water.
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