CN114481212B - Preparation method and application of phosphide/phosphate heterojunction electrocatalytic material - Google Patents

Preparation method and application of phosphide/phosphate heterojunction electrocatalytic material Download PDF

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CN114481212B
CN114481212B CN202210185049.3A CN202210185049A CN114481212B CN 114481212 B CN114481212 B CN 114481212B CN 202210185049 A CN202210185049 A CN 202210185049A CN 114481212 B CN114481212 B CN 114481212B
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phosphide
phosphate
heterojunction
nivmof
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CN114481212A (en
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杜晓航
韩彬彬
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Hebei University of Technology
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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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract

The invention relates to a preparation method and application of a phosphide/phosphate heterojunction electrocatalytic material. The catalyst passes throughFormation of a phosphide/phosphate heterojunction by vapor deposition by electrodeposition of Ni (OH) on self-supporting foam nickel 2 The substrate is then grown with NiVMOF in situ, phosphate formation can be facilitated by optimizing the ratio of nickel to vanadium, and phosphide/phosphate heterostructure materials can be formed by one-step phosphating; the material is used for urea-assisted alkaline electrolysis of water. The method is simple and convenient, is easy to operate, and has a better catalytic effect due to the heterojunction formed by two different crystal forms.

Description

Preparation method and application of phosphide/phosphate heterojunction electrocatalytic material
Technical Field
The technical scheme of the invention relates to a preparation method and application of a phosphide/phosphate heterojunction electrocatalytic material, and belongs to the technical field of water electrolysis hydrogen production.
Background
The ever-increasing consumption of traditional fossil fuels and the consequent environmental pollution are affecting the global society on an unprecedented scale. Therefore, the world energy pattern is fundamentally adjusted, and a clean, low-carbon, safe and efficient modern energy system is established. Hydrogen energy, which is an ideal clean chemical fuel, has extremely high gravimetric energy density and energy conversion efficiency, and is expected to be an excellent candidate for replacing traditional fossil fuels. Electrochemical electrolysis of water is considered as one of the most promising hydrogen production technologies, and can utilize electric energy generated by renewable energy sources such as solar energy, wind energy, geothermal energy, bioenergy and the like to form a closed loop of the renewable energy sources.
Unfortunately, the large-scale commercial application of electrochemical electrolyzed water is limited by (1) the overpotential required to drive the overall electrolyzed water is greater than theoretical (1.23V); (2) poor stability of the electrode material; and (3) noble metal electrocatalysts are rare and have high cost. To date, pt-based and Ru/Ir-based noble metal materials are basic electrocatalysts for Hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER), which have small overpotential and low Tafel slope, but these noble metals have problems of dissolution, agglomeration, poor durability, etc. during water splitting.
In addition, due to the slow kinetics of OER on the anode, the water splitting efficiency is generally low, resulting in the thermodynamic potential required for O-O bond formation>1.23V) is higher. Thus, in most cases, high pressures in excess of 1.8V are required to drive electrolyzed water for hydrogen production. Thus, strategies such as oxidation of hydrazine, methanol, urea, ethanol, and glycerol have been adopted to replace OER with other anodic oxidation reactions in order to reduce the driving voltageIs widely applied. Among the oxidizable molecules that can replace OER, urea (a common sewage waste) is considered a very promising oxidizable molecule because of its non-toxicity and low cost. Notably, in urea-assisted energy-saving integral cracking cells, the anodic urea oxidation reaction (UOR: CO (NH 2 ) 2 +6OH-→N 2 +5H 2 O+CO 2 +6e-) cathodic hydrogen evolution reaction (HER: 6H) 2 O+6e-→3H 2 +6OH-). The potential of a theoretical electrode for urea oxidation is 0.37V, which is greatly lower than the standard level of 1.23V, so that the high-efficiency utilization of energy can be realized. Furthermore, UOR is also a treatment of urea-containing wastewater, which can solve environmental problems, and therefore, from the viewpoint of low energy consumption hydrogen production and wastewater treatment, it is desirable to search for a highly efficient UOR catalyst.
To solve the above problems, an efficient, stable, low-loss electrocatalyst was designed and developed to replace noble metal electrocatalysts (Pt and Ru/IrO 2 ) It is necessary to accelerate the reaction process and reduce the reaction overpotential. For non-noble metal materials, such as transition metal sulfides, metal selenides, metal phosphides, metal nitrides, metal carbides, etc., there is a great deal of attention because of their low cost and abundant reserves. However, the performance of the type cannot meet the requirement of wide application, and at present, the synergistic effect between a heterostructure and an interface is an effective way for improving the catalytic activity and stability, so that a heterojunction catalyst of phosphide/phosphate is designed, and phosphate groups in a transition metal compound can be used as proton acceptors to promote the oxidation of metal species and induce the distortion of the local geometric shape of metal, thereby being beneficial to the adsorption and oxidation of water; phosphide is widely studied as an electrolytic water catalyst, and has good electronic conductivity and excellent chemical stability. The heterogeneous structure of phosphide/phosphate formed by the method can optimize the optimal electronic structure of Ni cations serving as electrocatalytic active centers, can better promote the formation of NiOOH active substances, is favorable for the adsorption of reaction intermediates, and reduces the free energy barrier of reaction, thereby improving the catalytic activity and realizing low-energy consumption hydrogen production and urea-containing wastewater treatment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a phosphide/phosphate heterostructure material for urea-assisted alkaline electrolysis water. The catalyst forms a phosphide/phosphate heterojunction by vapor deposition, by electrodeposition of Ni (OH) on self-supporting foam nickel 2 The substrate and then the NiVMOF are grown in situ, the formation of phosphate can be facilitated by optimizing the proportion of nickel and vanadium, and the phosphide/phosphate heterostructure material is formed by one-step phosphating.
The technical scheme of the invention is as follows:
a method for preparing phosphide/phosphate heterojunction electrocatalytic material, which comprises the following steps:
(1) Placing the flaky foam nickel into hydrochloric acid for ultrasonic treatment, then washing with deionized water and ethanol, and drying;
the concentration of the hydrochloric acid is 1-5M;
(2)Ni(OH) 2 formation of the substrate
Taking the foam nickel treated in the step (1) as a working electrode, a graphite rod as a counter electrode and Ag/AgCl as a reference electrode, depositing for 800-1200 s in electrolyte at a constant potential at 60-90 ℃, washing with water, and drying in a vacuum oven to obtain Ni (OH) 2 A substrate;
wherein the composition of the electrolyte is Ni (NO) with the concentration of 0.03-0.05M 3 ) 2 .6H 2 O, the constant potential is-0.8 to-1V;
(3) Preparation of NiVMOF
Ni (NO) 3 ) 2 .6H 2 O、NH 4 VO 3 And C 8 H 6 O 4 Dissolving in a solvent, stirring for 20-40 minutes, and then dropwise adding absolute ethyl alcohol and deionized water to obtain a reaction solution; then the reaction solution was put into a stainless steel autoclave lined with polytetrafluoroethylene, ni (OH) 2 Immersing the substrate into the reaction liquid, sealing and keeping the temperature at 80-120 ℃ for 6-10 hours; naturally cooling toTaking out the sample after room temperature, washing with distilled water and ethanol, and vacuum drying at 50-80 ℃ for 2-5 hours to obtain NiVMOF;
wherein, 2-3 mmol Ni (NO) is added into each 35mL solvent 3 ) 2 .6H 2 O、0.2～0.3mmol NH 4 VO 3 、1～2mmol C 8 H 6 O 4 2-5 mL absolute ethyl alcohol, 2-5 mL deionized water, ni (NO) 3 ) 2 .6H 2 O：NH 4 VO 3 =10:0.8 to 1.5; absolute ethyl alcohol: deionized water = 1:1; the solvent is N-N, dimethylformamide or methanol;
(4)V-Ni(PO 3 ) 2 /Ni 2 preparation of P
Will be respectively provided with NaH 2 PO 2 Placing the two ceramic boats of the NiVMOF obtained in the step (3) into a tube furnace, introducing carrier gas, heating to 300-400 ℃, and then preserving heat for 80-100 min to obtain a phosphide/phosphate heterojunction electrocatalytic material;
wherein the proportion is 1cm 2 0.5-2 g NaH for NiVMOF 2 PO 2 Phosphating with NaH 2 PO 2 The porcelain boat is close to the carrier gas inlet; the heating rate is 1-5 ℃/min; the carrier gas is argon;
the phosphide/phosphate heterojunction electrocatalytic material prepared by the method is used for urea-assisted alkaline electrolysis of water.
The beneficial effects of the invention are as follows:
(1) The catalyst is a transition metal-based catalyst, does not contain noble metal, can obviously reduce the cost of the catalyst, and is driven by a voltage of 1.62V to 100mA cm -2 Is driven by a voltage of 1.89V higher than that of noble metal by 100mA cm -2 Is set in the above-described range).
(2) The heterostructure of phosphide/phosphate prepared by the invention is reported for the first time, and the heterostructure is also used as urea-assisted alkaline electrolyzed water for the first time. Tests show that the material can be driven at a low voltage of 1.30V for 10mA cm -2 Is driven by a voltage of 1.62V at 100mA cm -2 And at 100mA cm -2 Can keep 130h stable under the condition of large currentQualitative, and only 8% drop.
(3) According to the invention, niVMOF is taken as a substrate, and a phosphide/phosphate heterojunction is formed through one-step phosphating, wherein the introduction of vanadium is beneficial to the formation of phosphate, the forming process is simple to operate and easy to operate, the phosphate can better optimize the optimal electronic structure of Ni cations as electrocatalytic active centers, the formation of NiOOH active substances can be better promoted, the adsorption of reaction intermediates is facilitated, the free energy barrier of reaction is reduced, and the catalytic activity is improved, so that the low-energy hydrogen production and urea-containing wastewater treatment are realized.
Description of the drawings:
FIG. 1 shows Ni (OH) obtained in example 1 2 SEM images of (a).
FIG. 2 is an SEM image of NiVMOF obtained in example 1.
FIG. 3 shows the V-Ni (PO) obtained in example 1 3 ) 2 /Ni 2 SEM image of P.
FIG. 4 shows the V-Ni (PO) obtained in example 1 3 ) 2 /Ni 2 X-ray diffraction pattern of P.
FIG. 5 is Ni obtained in example 2 2 X-ray diffraction pattern of P.
FIG. 6 is a LSV graph of the total electrolyzed water, urea assisted total electrolyzed water obtained in example 1.
FIG. 7 shows the stability of urea-assisted total electrolyzed water obtained in example 1.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto.
The invention will be further described with reference to the drawings and examples.
Example 1:
(1) Treatment of foam nickel
1.2cm of foamed nickel is placed in 3moL/L hydrochloric acid for ultrasonic treatment for 10min, an oxide layer is removed, and then deionized water and ethanol are used for washing and drying in sequence.
(2)Ni(OH) 2 Preparation of the substrate
1.2cm X1.2 cm clean foam nickel is used as a working electrode,graphite rod was used as counter electrode and Ag/AgCl (saturated KCl solution) was used as reference electrode. Then, in 0.04M Ni (NO 3 ) 2 ·6H 2 In O electrolyte, the temperature is 85 ℃, constant potential deposition is carried out for 1000s with Ag/AgCl under the pressure of minus 0.95V, then the solution is washed by water and dried in a vacuum oven to obtain Ni (OH) 2 A substrate.
(3) Preparation of NiVMOF
Will be 1.75mmol C 8 H 6 O 4 、2.5mmol Ni(NO 3 ) 2 6H 2 O and 0.25mmol NH 4 VO 3 Dissolved in 35mL of N, N-dimethylformamide to form a homogeneous solution. Then, 2.5mL of C was stirred for 30 minutes 2 H 5 OH and 2.5mL H 2 O was added dropwise to the solution (during MOF formation, the coordination environment was adjusted). The clear solution was then transferred to a 50mL stainless steel autoclave lined with polytetrafluoroethylene, which contained a piece of Ni (OH) formed in (2) 2 A substrate. The autoclave was sealed and kept in an oven at 120 ℃ for 10 hours. After natural cooling to room temperature, the sample was taken out, washed several times with distilled water and ethanol, and then dried in vacuo at 70 ℃ for 3 hours.
(4)V-Ni(PO 3 ) 2 /Ni 2 Preparation of P
The sample of (3) was placed in a porcelain boat, 1.0g NaH 2 PO 2 In another porcelain boat. Then the porcelain boat is put into a tube furnace, wherein NaH is put in 2 PO 2 Is close to the air inlet to ensure NaH 2 PO 2 Upstream. Preserving heat for 90min at 350 ℃, heating at a rate of 2 ℃/min, introducing argon into the tube furnace, wherein the gas flow is 15mL/min, and driving NaH by the argon 2 PO 2 The heated gas uniformly reacts with the sample in (3) to obtain the phosphide/phosphate heterojunction electrocatalytic material.
Example 2:
the synthesis procedure was the same as in example 1 except that (3) NH was not added in the preparation of NiVMOF 4 VO 3 The other steps are the same as in example 1. The addition of NH is shown by comparison of FIG. 4 and FIG. 5 4 VO 3 Can helpThe formation of metaphosphate yields a phosphide/phosphate heterojunction electrocatalytic material.
The electrolyte is respectively selected from 1M KOH and 0.33M Urea+1M KOH, the temperature of the electrolyte is room temperature, the performance of the electrolyte is tested by using an Shanghai chemical electrochemical workstation, and a three-electrode test is adopted.
Fig. 1 shows that: the smooth foam nickel uniformly supports a layer of substrate, the surface of the substrate is provided with folds, and the conditions for in-situ MOF growth can be better provided than that of the smooth foam nickel.
Fig. 2 shows that: the synthesized NiVMOF is a three-dimensional flower-like structure, and the three-dimensional structure can have more areas to be contacted with electrolyte, so that the NiVMOF has more catalytic sites.
Fig. 3 shows that: synthesis of V-Ni (PO) 3 ) 2 /Ni 2 The P basically maintains a three-dimensional flower-like structure, and the large specific surface area can have more catalytic sites, so that the catalyst has better catalytic performance.
Fig. 4 shows that: it can be seen that V-Ni (PO 3 ) 2 /Ni 2 Characteristic peaks of P material. Illustrating the successful synthesis of phosphide/phosphate heterojunction electrocatalytic materials.
Fig. 5 shows that: it can be seen that the Ni is apparent 2 Characteristic peaks of P material. Indicating that doping without vanadium only forms one phosphide and no phosphate is formed.
Fig. 6 shows that: full electrolysis of water at 10mA cm -2 The potential was 1.48V,100mA cm -2 The potential was 1.79V; full urea electrolysis at 10mA cm -2 The potential was 1.30V,100mA cm -2 The potential was 1.62V, and the commercial electrolyzed water was at 10mA cm -2 The potential was 1.55V,100mA cm -2 The potential was 1.89V, indicating that the phosphide/phosphate heterojunction electrocatalyst had better water electrolysis performance and urea-assisted total electrolysis performance than the commercial catalyst.
Fig. 7 shows: urea-assisted total electrolysis of water at 100mA cm -2 The catalyst can be ensured to be stable for a long time of 130h under the high current.
Example 3:
the other steps are the same as in example 1 except that (3) the oven temperature is 100℃when NiVMOF is formed. The performance of the obtained phosphide/phosphate heterojunction electrocatalytic material is close.
Example 4:
the other steps are the same as in example 1 except that (4) V-Ni (PO) 3 ) 2 /Ni 2 At P, the tube furnace temperature was 300 ℃. The performance of the obtained phosphide/phosphate heterojunction electrocatalytic material is close.
The invention is not a matter of the known technology.

Claims (3)

1. The preparation method of the phosphide/phosphate heterojunction electrocatalytic material is characterized by comprising the following steps of:
(1) Placing the flaky foam nickel in hydrochloric acid for ultrasonic treatment, then washing with deionized water and ethanol respectively, and drying;
(2)Ni(OH) 2 formation of the substrate
Taking the foam nickel treated in the step (1) as a working electrode, a graphite rod as a counter electrode and Ag/AgCl as a reference electrode, depositing for 800-1200 s in electrolyte at a constant potential at 60-90 ℃, washing with water, and drying in a vacuum oven to obtain Ni (OH) 2 A substrate;
wherein the composition of the electrolyte is Ni (NO) with the concentration of 0.03-0.05M 3 ) 2 .6H 2 O, the constant potential is-0.8 to-1V;
(3) Preparation of NiVMOF
Ni (NO) 3 ) 2 .6H 2 O、NH 4 VO 3 And C 8 H 6 O 4 Dissolving in a solvent, stirring for 20-40 minutes, and then dropwise adding absolute ethyl alcohol and deionized water to obtain a reaction solution; then, the reaction solution was charged into a stainless steel autoclave lined with polytetrafluoroethylene, and Ni (OH) 2 Immersing the substrate into the reaction liquid, sealing and keeping the temperature at 80-120 ℃ for 6-10 hours; naturally cooling to room temperature, taking out a sample, washing with distilled water and ethanol, and vacuum drying at 50-80 ℃ for 2-5 hours to obtain NiVMOF;
wherein, 2-3 mmole of Ni (NO) is added into each 35mL of solvent 3 ) 2 .6H 2 O、0.2～0.3mmolNH 4 VO 3 、1～2mmol C 8 H 6 O 4 2-5 mL absolute ethyl alcohol, 2-5 mL deionized water, ni (NO) 3 ) 2 .6H 2 O：NH 4 VO 3 =10:0.8 to 1.5; absolute ethyl alcohol: deionized water = 1:1;
(4)V-Ni(PO 3 ) 2 /Ni 2 preparation of P
Will be respectively provided with NaH 2 PO 2 Placing the two ceramic boats of the NiVMOF obtained in the step (3) into a tube furnace, introducing carrier gas, heating to 300-400 ℃, and then preserving heat for 80-100 min to obtain a phosphide/phosphate heterojunction electrocatalytic material;
wherein the proportion is 1cm 2 For NiVMOF of 0.5-2 gNaH 2 PO 2 Phosphating with NaH 2 PO 2 The porcelain boat is close to the carrier gas inlet;
the concentration of the hydrochloric acid in the step (1) is 1-5M;
the solvent in the step (3) is N-N, dimethylformamide or methanol.
2. The method for preparing a phosphide/phosphate heterojunction electrocatalytic material as set forth in claim 1, wherein the heating rate in the step (4) is 1-5 ℃/min;
the carrier gas is argon.
3. The phosphide/phosphate heterojunction electrocatalytic material prepared by the method as claimed in claim 1, which is characterized by being used for urea-assisted alkaline electrolysis of water.
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