CN113697786B - Preparation method of needle-shaped cobalt phosphide with phosphorus vacancies and application of needle-shaped cobalt phosphide in seawater electrolysis hydrogen production - Google Patents
Preparation method of needle-shaped cobalt phosphide with phosphorus vacancies and application of needle-shaped cobalt phosphide in seawater electrolysis hydrogen production Download PDFInfo
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Abstract
The invention belongs to the technical field of seawater electrolytic hydrogen production, and particularly relates to a preparation method of needle-shaped cobalt phosphide with phosphorus vacancies and application thereof in seawater electrolytic hydrogen production 3 O 4 And v-CoP x The catalyst is prepared by twice calcination. The needle-shaped cobalt phosphide catalyst with phosphorus vacancies prepared by the invention can not only carry out hydrogen evolution reaction under seawater electrolyte, solve part of the problems of seawater hydrogen evolution, but also meet the requirement of replacing noble metals, is economical and environment-friendly, and has the advantages of simple operation, high activity, high stability, self-support and the like.
Description
Technical Field
The invention belongs to the technical field of seawater electrolytic hydrogen production, and particularly relates to a preparation method of needle-shaped cobalt phosphide with phosphorus vacancies and application of the needle-shaped cobalt phosphide in seawater electrolytic hydrogen production.
Background
In response to environmental problems such as climate change and ecological badness caused by overuse of global fossil energy, sustainable, clean and efficient energy development is an effective response mode. The electrochemical water cracking is a promising technology for converting electric energy into hydrogen fuel, has the characteristics of high energy density, high output energy, zero carbon emission and the like, and is simple, environment-friendly, high in yield and high in product purity. Electrochemical water splitting therefore has great potential in developing and utilizing renewable energy sources to address the growing energy needs and significant problems with the depletion of fossil fuels (e.g., petroleum, coal, and natural gas). On the other hand, abundant seawater resources on the earth are used as the electrolyte for hydrogen production by electrochemical water splitting, so that the consumption speed of global fresh water resources can be effectively reduced, and the method is particularly important for high-demand fresh water areas such as arid areas, coastal countries, islands and the like.
The noble metal Pt is commonly used as a commercial catalytic water-splitting hydrogen production, but it is expensive, scarce in quantity and poor in durability, resulting in a limitation in its large-scale application. Therefore, it is necessary to develop a Hydrogen Evolution Reaction (HER) catalyst with abundant earth resources, high cost performance and strong performance to realize efficient seawater cracking. The transition metal has unique electronic structure and chemical characteristics, and has the advantages of high activity, low overpotential, long-term stability, rich content, easy acquisition and the like. Therefore, it is necessary to regulate the structure of the transition metal catalytic material to improve HER performance, so that it can be applied to hydrogen evolution reaction. However, most of these electrocatalytic systems operate in pure water electrolytes including acids, bases or buffers, and there are few reports of electrocatalytic water splitting using seawater, and about 97% of the water resources available on earth are seawater. Since natural seawater contains hundreds of different impurities, it may cause catalyst poisoning and the generation of unknown side reactions. Therefore, electro-catalytic seawater hydrogen evolution has become a hot spot and a difficulty in recent research.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of needle-shaped cobalt phosphide with phosphorus vacancies, and the prepared cobalt phosphide has the potential of being used as a catalyst for electrolyzing seawater to prepare hydrogen.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of needle-shaped cobalt phosphide with phosphorus vacancies, which comprises the following steps:
s1, placing foamed nickel in Co (NO) 3 ) 2 ·6H 2 O, urea and NH 4 In the aqueous solution of F, after hydrothermal reaction, washing and drying to prepare a precursor product Co (CO) 3 )0.5(OH)·0.11H 2 O；
S2, p-Co (CO) 3 )0.5(OH)·0.11H 2 Calcining O in inert atmosphere to obtain Co 3 O 4 ；
S3, mixing Co 3 O 4 Transferring to porcelain boat at downstream of tube furnace, and adding NaH into porcelain boat at upstream 2 PO 2 ·H 2 O, calcining under Ar, and finally washing and drying to obtain the catalystTo acicular cobalt phosphide having phosphorus vacancies.
The needle-shaped cobalt phosphide catalyst with phosphorus vacancies, which is prepared by a simple and easy-to-operate method, is used as a self-supporting electrode for simulating seawater electrolysis hydrogen evolution, can effectively overcome the defect that nano particles are used as an electrode material, and compared with needle-shaped cobalt phosphide without phosphorus vacancies, the needle-shaped cobalt phosphide with phosphorus vacancies has the advantages of obviously improved performance, higher stability and no obvious reduction of current density after 25h test. The needle structure has many advantages of enlarging electrochemical surface area, facilitating air bubble migration from the surface of the catalyst, and the like, thereby further improving the performance of the electrocatalyst. In addition, phosphorus vacancy can effectively improve electronic conversion, and researches show that the needle-shaped cobalt phosphide catalyst with phosphorus vacancy has good hydrogen evolution performance in simulated seawater, and is expected to be applied to the seawater electrolysis hydrogen production industry.
Preferably, both the calcinations of step S3 are carried out at 2 ℃ min under Ar atmosphere -1 The temperature is increased to 250-350 ℃ at the temperature rising rate, and the calcination is carried out for 1.5-2.5h. Specifically, the two times of calcination are performed at 2 ℃ and min in Ar atmosphere -1 The temperature rise rate of (2) is increased to 300 ℃ and the calcination is carried out for 2.0h.
Preferably, the calcination of step S2 is in N 2 At 3 ℃ min under atmosphere -1 The temperature is increased to 300-400 ℃ at the temperature increasing rate, and the calcination is carried out for 1.5-2.5h. Specifically, the calcination is in N 2 At 3 ℃ min under atmosphere -1 The temperature is raised to 350 ℃ at the temperature raising rate, and the calcination is carried out for 2.0h.
Preferably, the temperature of the hydrothermal reaction is 100-140 ℃ and the time is 10-14 h. Specifically, the temperature of the hydrothermal reaction is 120 ℃, and the time is 12h.
Preferably, said Co (NO) 3 ) 2 ·6H 2 The molar concentration of O is 0.02M-0.06M, the molar concentration of urea is 0.1M-0.3M 4 The molar concentration of F is 0.14M-0.18M. In particular, the Co (NO) 3 ) 2 ·6H 2 The molar concentration of O is 0.04M, the molar concentration of urea is 0.2M 4 The molar concentration of F was 0.16M.
Preferably, the foamed nickel is subjected to ultrasonic cleaning with hydrochloric acid, acetone, ethanol and water respectively before use.
Furthermore, the power of the ultrasonic cleaning is 300-400W, and the time is 20-40min. Specifically, the power of the ultrasonic cleaning is 360W, and the time is 30min.
The invention also provides the acicular cobalt phosphide with phosphorus vacancies, which is prepared by the preparation method of the acicular cobalt phosphide with phosphorus vacancies.
The invention also provides the application of the needle-shaped cobalt phosphide with phosphorus vacancy as a catalyst in the preparation of hydrogen by electrolyzing seawater.
Compared with the needle-shaped cobalt phosphide catalyst without phosphorus vacancies, the needle-shaped cobalt phosphide catalyst with phosphorus vacancies has the advantages that the hydrogen evolution activity of the cobalt phosphide with phosphorus vacancies in simulated seawater is obviously improved, the stability is higher, and the current density is not obviously reduced after a constant-voltage stability test for 25 hours. The needle-shaped cobalt phosphide catalyst with phosphorus vacancies can not only overcome the problem of chloride ion corrosion in seawater electrolyte and solve the important problem of seawater hydrogen evolution, but also meet the requirement of replacing noble metals, is economical and environment-friendly, and has the advantages of simple preparation, high porosity (namely, the substrate is foamed nickel, so the porosity is high) and high stability.
Compared with the prior art, the invention has the beneficial effects that:
the needle-shaped cobalt phosphide catalyst with phosphorus vacancies is prepared by simple methods such as a hydrothermal method, a calcination method and the like, namely, the cleaned nickel foam is firstly subjected to hydrothermal reaction, taken out, cleaned, dried and calcined to obtain Co 3 O 4 ，Co 3 O 4 And calcining again to obtain the catalyst. The needle-shaped cobalt phosphide catalyst with phosphorus vacancies prepared by the invention can not only carry out hydrogen evolution reaction under seawater electrolyte, solve part of the problems of seawater hydrogen evolution, but also meet the requirement of replacing noble metals, is economical and environment-friendly, and has the advantages of simple operation, high catalytic activity, high stability, self-support (namely prepared by taking foamed nickel as a substrate) and the like.
Drawings
FIG. 1 is a drawing ofNF(Ni foam)，Co(CO 3 ) 0.5 (OH)·0.11H 2 O and Co 3 O 4 An X-ray electron diffraction image of the catalyst;
FIG. 2 is a scanning electron microscope image of various catalysts (A picture is Co (CO) 3 ) 0.5 (OH)·0.11H 2 O precursor; b is Co 3 O 4 An intermediate; graph C is g-CoP x (ii) a Graph D is v-CoP x )；
FIG. 3 is g-CoP x And v-CoP x An X-ray electron diffraction image (A) of (1); g-CoP x And v-CoP x The X-ray photoelectron energy spectrum (B, C); g-CoP x And v-CoP x Electron paramagnetic resonance spectrum (D);
FIG. 4 is a graph of HER performance of various catalysts in simulated seawater 1M KOH +0.5M NaCl electrolyte (graph A is the polarization curve; graph B is the durability test).
In fig. 4, the abscissa is the potential: E/V, ordinate current density: j/mAcm -2 。
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
EXAMPLE 1 preparation of acicular cobalt phosphide catalyst having phosphorus vacancies
(1) Ultrasonically cleaning foamed nickel (Ni foam, NF) with the size of 1cm multiplied by 2mm with 6M hydrochloric acid, acetone, absolute ethyl alcohol and water respectively for 30min under the power of 360W, and drying at the temperature of 60 ℃ in vacuum;
(2) 50mL of H was placed in a 100mL stainless steel autoclave 2 O, then Co (NO) with a concentration of 0.04M is added 3 ) 2 ·6H 2 O, urea at a concentration of 0.2M, NH at a concentration of 0.16M 4 And F, adding the treated foam nickel into the high-pressure autoclave, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and naturally cooling the high-pressure autoclave to room temperature after the reaction is finished. Then repeatedly and alternately washing the foamed nickel for three times by using absolute ethyl alcohol and water, and finally drying in vacuum at 60 ℃ to obtain a precursor product Co (CO) 3 ) 0.5 (OH)·0.11H 2 O。
(3) Mixing the Co (CO) prepared in the step (2) 3 ) 0.5 (OH)·0.11H 2 O is transferred to a tube furnace at 3 ℃ min -1 At a rate of N 2 Heating to 350 ℃ in the atmosphere, calcining for 2 hours, cooling to room temperature, taking out, washing with ultrapure water, and drying in vacuum at 60 ℃ to obtain Co 3 O 4 ；
(4) Mixing Co 3 O 4 (in foamed nickel unit, two pieces of the mixture are added) is transferred to a porcelain boat at the downstream of the tube furnace, and 1g of NaH is added to the porcelain boat at the upstream 2 PO 2 ·H 2 O, under Ar atmosphere at 2 ℃ min -1 The temperature is increased to 300 ℃ at the speed of (1), and the cobalt phosphide (marked as v-CoP) containing vacancy is obtained after washing and vacuum drying x )。
Comparative example 1 cobalt phosphide free of vacancies (noted as g-CoP) x ) Preparation of
The steps (1) and (2) are the same as the steps (1) and (2) of the embodiment 1, and the step (3) is specifically as follows:
mixing Co (CO) 3 ) 0.5 (OH)·0.11H 2 O (two pieces in total, in terms of nickel foam) was transferred to a porcelain boat downstream of the tube furnace, and 1g of NaH was added to the porcelain boat upstream 2 PO 2 ·H 2 O, under Ar atmosphere at 2 ℃ min -1 The temperature is increased to 300 ℃ and calcined for 2h, and the cobalt phosphide (marked as g-CoP) without vacancy is obtained after washing and vacuum drying x )。
v-CoP prepared in example 1 x And g-CoP prepared in comparative example 1 x An X-ray diffraction scan was performed using the instrument model Ultima IV. X-ray diffraction analysis chart as shown in FIG. 1, by comparing standard cards [ Ni (ICCD No: 04-0850), co (CO) 3 ) 0.5 (OH)·0.11H 2 O(ICCD No:48-0083),Co 3 O 4 (ICCD No: 42-1467), it is apparent that Co has been successfully prepared by the above method 3 O 4 Intermediate and Co (CO) 3 ) 0.5 (OH)·0.11H 2 And (4) O precursor. At the same time, for v-CoP x And observing by a scanning electron microscope, wherein the model of the used instrument is JEOL JSM-IT200A. As shown in FIG. 2, co (CO) was observed separately 3 ) 0.5 (OH)·0.11H 2 O catalyst, co 3 O 4 Catalyst, g-CoP x Catalyst and v-CoP x The catalyst is in a needle structure.
In addition, for g-CoP respectively x Catalyst and v-CoP x The catalyst is subjected to X-ray diffraction analysis, X-ray photoelectron spectroscopy analysis and electron paramagnetic resonance spectroscopy analysis. g-CoP as shown in FIG. 3A x Catalyst and v-CoP x X-ray diffraction pattern of the catalyst showing g-CoP x And v-CoP x Are similar in peak position and are all composed of CoP and Co 2 P composition, the peaks at 31.6 degrees, 36.3 degrees and 48.1 degrees are respectively the (011), (111) and (211) crystal planes of the CoP crystal, and the peak at 40.7 degrees is Co 2 The (121) plane of P; FIGS. 3B and C are g-CoP x And v-CoP x According to high resolution Co 2p 3/2 (B) And P2P (C) spectrum, and calculating v-CoP by integration method x The percentage of P in (in the form of Co-P bonds) is 15.76%, much lower than g-CoP x 17.52% in (1), and thus, v-CoP was confirmed x In the presence of P v And the content thereof was 1.76%. FIG. 3D is g-CoP x And v-CoP x Further confirmed the v-CoP x The existence of phosphorus vacancies.
EXAMPLE 2 preparation of acicular cobalt phosphide catalyst having phosphorus vacancies
(1) Ultrasonically cleaning foamed nickel (Ni foam, NF) with the size of 1cm multiplied by 2mm under the power of 300W for 40min by respectively using 6M hydrochloric acid, acetone, absolute ethyl alcohol and water, and drying at the temperature of 60 ℃ in vacuum;
(2) 50mL of H was placed in a 100mL stainless steel autoclave 2 O, then Co (NO) with a concentration of 0.02M is added 3 ) 2 ·6H 2 O, urea at a concentration of 0.1M, NH at a concentration of 0.14M 4 And F, adding the treated foam nickel into the high-pressure autoclave, carrying out hydrothermal reaction at 100 ℃ for 14h, and naturally cooling the high-pressure autoclave to room temperature after the reaction is finished. Then repeatedly and alternately washing the foamed nickel for three times by using absolute ethyl alcohol and water, and finally drying in vacuum at 60 ℃ to obtain a precursor product Co (CO) 3 ) 0.5 (OH)·0.11H 2 O。
(3) Mixing the Co (CO) prepared in the step (2) 3 ) 0.5 (OH)·0.11H 2 O is transferred to a tube furnace at 3 ℃ min -1 Heating to 300 ℃ in Ar atmosphere, calcining for 2.5 hours, cooling to room temperature, taking out, washing with ultrapure water, and vacuum drying at 60 ℃ to obtain Co 3 O 4 ；
(4) Mixing Co 3 O 4 (two pieces are added in total in terms of nickel foam unit) is transferred to a porcelain boat at the downstream of the tube furnace, and 1g NaH is added to the porcelain boat at the upstream 2 PO 2 ·H 2 O, in N 2 At 2 ℃ min under an atmosphere -1 The temperature is increased to 250 ℃ at the speed, the mixture is calcined for 2.5h, and cobalt phosphide (marked as v-CoP) containing vacancy is obtained after washing and vacuum drying x )。
EXAMPLE 3 preparation of acicular cobalt phosphide catalyst having phosphorus vacancies
(1) Ultrasonic cleaning 1cm × 2cm × 2mm foam nickel (Ni foam, NF) with 6M hydrochloric acid, acetone, anhydrous ethanol and water under 300W power for 40min, and vacuum drying at 60 deg.C;
(2) 50mL of H was placed in a 100mL stainless steel autoclave 2 O, then adding Co (NO) with concentration of 0.06M 3 ) 2 ·6H 2 O, urea at a concentration of 0.3M, NH at a concentration of 0.18M 4 And F, adding the treated foam nickel into the high-pressure autoclave, carrying out hydrothermal reaction at 140 ℃ for 10 hours, and naturally cooling the high-pressure autoclave to room temperature after the reaction is finished. Then repeatedly and alternately washing the foamed nickel for three times by using absolute ethyl alcohol and water, and finally drying in vacuum at 60 ℃ to obtain a precursor product Co (CO) 3 ) 0.5 (OH)·0.11H 2 O；
(3) Mixing the Co (CO) prepared in the step (2) 3 ) 0.5 (OH)·0.11H 2 Transferring O into a tube furnace at 3 deg.C/min -1 Heating to 400 ℃ in Ar atmosphere, calcining for 3.5 hours, cooling to room temperature, taking out, washing with ultrapure water, and vacuum drying at 60 ℃ to obtain Co 3 O 4 ；
(4) Mixing Co 3 O 4 (in foamed nickel unit, two pieces of the mixture are added) is transferred to a porcelain boat at the downstream of the tube furnace, and 1g of NaH is added to the porcelain boat at the upstream 2 PO 2 ·H 2 O, in N 2 At 2 ℃ min under an atmosphere -1 Heating to 350 ℃ at the rate of (1.5) and calcining for 1.5h, washing and vacuum drying to obtain the cobalt phosphide (noted as v-CoP) containing vacancy x )。
Experimental example 1 electrochemical test
The electrochemical test was performed using a three-electrode system, the test instrument was AUTOLAB (model AUT 88171), the electrolyte was simulated seawater (1M KOH +0.5M NaCl), the reference electrode was Hg/HgO, the counter electrode was a graphite rod electrode, and the working electrode was the v-CoP prepared in example 1 x After the circuit connection is checked to be correct, a program is set, a Linear sweep volt-metric (LSV) program is selected to carry out a hydrogen evolution test, the scanning speed is 1mV/s, and a LSV (LSV) curve graph is drawn.
As shown in the HER diagram of FIG. 4, as can be seen from FIG. 4A, v-CoP x Only 75mV (vs RHE) overpotential is needed in 1M KOH +0.5M NaCl electrolyte to reach 10mAcm -2 The current density of (1) is 93mV, co are required for g-CoPx at the same current density 3 O 4 Catalyst v-CoP requiring 137mV, NF 200mV, and therefore P vacancies x The performance is obviously improved, and the catalytic activity is high. As can be seen from FIG. 4B, at constant voltage, v-CoP x The current density of the alloy can be kept stable within 25h, and the HER current density after 25h is from 10mAcm -2 Only reduced by 0.7mAcm -2 . Visible, v-CoP x Has good hydrogen evolution performance and stability in simulated seawater.
Furthermore, the v-CoP prepared in examples 2 and 3 x The electrochemical test results of (a) are the same as or similar to those of example 1.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles and spirit of the invention, and these embodiments are still within the scope of the invention.
Claims (4)
1. The application of needle-shaped cobalt phosphide with phosphorus vacancies as a catalyst in the electrolysis of seawater for hydrogen production is characterized in that the preparation method of the needle-shaped cobalt phosphide with phosphorus vacancies comprises the following steps:
s1, placing foamed nickel in Co (NO) 3 ) 2 ·6H 2 O, urea and NH 4 Performing hydrothermal reaction for 10 to 14 hours at the temperature of between 100 and 140 ℃ in an aqueous solution of F, washing and drying to obtain a precursor product Co (CO) 3 )0.5(OH)·0.11H 2 O；
S2, p-Co (CO) 3 )0.5(OH)·0.11H 2 O is in N 2 At 3 ℃ min under atmosphere -1 The temperature rising rate is increased to 300-400 ℃ and the Co is obtained after calcining for 1.5-2.5h 3 O 4 ；
S3, mixing Co 3 O 4 Transferring to porcelain boat at downstream of tube furnace, and adding NaH to porcelain boat at upstream 2 PO 2 ·H 2 O, under Ar atmosphere at 2 ℃ min -1 The temperature is raised to 250 to 350 ℃ at the temperature raising rate, the calcination is carried out for 1.5 to 2.5 hours, and finally the needle-shaped cobalt phosphide with phosphorus vacancy is obtained through washing and drying.
2. The use of the acicular cobalt phosphide with phosphorus vacancies as catalyst in the electrolysis of seawater for hydrogen production as claimed in claim 1, wherein the Co (NO) is 3 ) 2 ·6H 2 The molar concentration of O is 0.02M-0.06M, the molar concentration of urea is 0.1M-0.3M 4 The molar concentration of F is 0.14M-0.18M.
3. The application of the needle-shaped cobalt phosphide with phosphorus vacancies as the catalyst in the hydrogen production by electrolyzing seawater as claimed in claim 1, wherein the foamed nickel is cleaned by ultrasonic wave with hydrochloric acid, acetone, ethanol and water respectively before use.
4. The application of the needle-shaped cobalt phosphide with phosphorus vacancies as the catalyst in the hydrogen production by electrolyzing seawater as claimed in claim 1, characterized in that the power of the ultrasonic cleaning is 300-400W, and the time is 20-40min.
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| CN105107536B (en) * | 2015-10-09 | 2017-11-21 | 清华大学 | A kind of preparation method of polyhedron shape phosphatization cobalt water electrolysis hydrogen production catalyst |
| CN109746007A (en) * | 2018-12-25 | 2019-05-14 | 中山大学 | A kind of functionalization transition metal phosphide-oxide composite nano materials and the preparation method and application thereof |
| CN109841422B (en) * | 2019-03-20 | 2020-12-22 | 武汉理工大学 | Co3O4/Co2P coaxial heterostructure material and preparation method and application thereof |
| KR102251358B1 (en) * | 2019-10-02 | 2021-05-12 | 전북대학교산학협력단 | Transition metal phosphide-based electrocatalyst for water splitting and manufacturing method thereof |
| CN111437853B (en) * | 2020-04-28 | 2021-08-13 | 南昌航空大学 | Preparation method and application of CoP microsphere three-functional catalytic material loaded with vanadium carbide |
| CN112108163A (en) * | 2020-07-10 | 2020-12-22 | 四川大学 | Preparation of CoFe-LDH nanosheet coated CoP nanowire core-shell nano array water oxidation electrocatalyst |
| CN111957327A (en) * | 2020-07-29 | 2020-11-20 | 国网浙江省电力有限公司电力科学研究院 | Cobalt phosphide nanowire array material and application thereof |
| CN113061908A (en) * | 2021-04-08 | 2021-07-02 | 浙江工业大学 | Fe-CoP composite electrode based on foamed nickel and preparation method and application thereof |
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