Preparation method of P-Fe2O3 / P-CoP heterostructure nanosheet for water treatment
By preparing P-Fe2O3/P-CoP heterostructured nanosheets, the problem of high cost of noble metal catalysts was solved, and efficient electrocatalytic water splitting under low voltage was achieved, which is suitable for freshwater and seawater treatment.
Patent Information
- Application Number
- CN202310952472.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-01
- Publication Date
- 2026-02-06
- Estimated Expiration
- 2043-08-01
AI Technical Summary
The use of precious metal catalysts in existing technologies leads to high costs for hydrogen production through water electrolysis, while non-precious metal catalysts have low efficiency in water splitting reactions, making it difficult to meet the needs of green catalytic water splitting.
By preparing P-Fe2O3/P-CoP heterostructured nanosheets, Co3O4 nanorods were synthesized using a hydrothermal method and calcination process, and then reacted with NaH2PO2·H2O under an argon atmosphere to form P-Fe2O3/P-CoP heterostructured nanosheets, which were then applied to electrocatalytic water splitting.
It achieves efficient catalytic water splitting at low voltage, with a current density of 10 mA/cm2 and a voltage of 1.6-1.7 V. It is suitable for electrocatalytic reactions in both freshwater and seawater and exhibits high catalytic activity.
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Figure CN117244547B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of a P-Fe2O3 / P-CoP heterostructure nanosheet for water treatment, and belongs to the fields of material preparation and application. BACKGROUND
[0002] The increasing consumption of mineral energy has caused serious pollution problems, so solving these problems is still a severe challenge. Developing new energy is considered to be an effective path to alleviate the energy crisis and environmental pollution. Compared with traditional methane reforming and coal gasification, fresh water or seawater desalination provides a green path for catalytic water decomposition to prepare hydrogen. At present, RuO2 is the main catalyst for water oxidation, and Pt / C is the main catalyst for water reduction. For example, the Wang team uses an etching method to obtain Ti3C2T x @Pt; and then compounding the Ti3C2T x @Pt with single-walled carbon nanotubes to form Ti3C2T x @Pt / SWCNT; the material has a water reduction reaction current density of 230 mA / cm x @Pt / SWCNT; the material has a water reduction reaction current density of 230 mA / cm 2 50 mV (Adv Funct Mater 30 (2020) 2000693). The Yang team uses Ni(NO3)2, Co(NO3)2, RuCl3, NaOH and the like to construct a Ni-Co-Ru oxide, which exhibits high water oxidation activity (ACSAppl Energy Mater 2 (2019) 4105-4110). The large use of noble metal materials is the main problem restricting the electrolytic water hydrogen production, and developing non-noble metal catalysts is an important research direction.
[0003] Transition metal oxides, nitrides, carbides, sulfides and the like have been widely studied for catalytic water decomposition to prepare hydrogen. Transition metal phosphides have attracted widespread attention due to their noble metal-like properties. The Chai team uses PTA, FeCl3.6H2O and the like to construct a Fe-MOF, and then obtains FeP nanorods by high-temperature calcination, and obtains N-FeP by high-temperature calcination with NH4CO3; which exhibits high water splitting activity (Appl Surf Sci 507 (2020) 145096). WO3 has high catalytic activity due to its wide band width. The Han team constructs CoO@ZIF-67, which is high-temperature calcined with NaH2PO2 to obtain a N-CoO@CoP electrocatalyst, which has a water hydrolysis voltage of 1.79 V and a current density of 100 mA / cm 2(Electrochim Acta 330 (2020) 135210). Wu team used NCD solution, Co(NO3)2·6H2O, NaH2PO2, etc. to construct CoP-NCDs / NF; it catalyzes water splitting to produce oxygen and hydrogen, and the current density is 10mA / cm 2 (Carbon 182 (2021) 327-334). Therefore, by adjusting the Co-based material to form P-Fe2O3 / P-CoP heterostructure nanosheet, it can effectively catalyze water splitting, which has important theoretical value. SUMMARY:
[0004] The present application aims to provide a preparation method of P-Fe2O3 / P-CoP heterostructure nanosheet for water treatment.
[0005] Based on the above purpose, the technical scheme of the present application is as follows:
[0006] (1) Preparation of P-Fe2O3 / P-CoP heterostructure nanosheet: 8-15mL NH3·H2O, 20-30mL ethylene glycol, 1-2mL 1-2mol / L Na2CO3 solution and 2-10mL 1-2mol / L Co(NO3)2 solution are mixed, and hydrothermal reaction is carried out at 150-200℃ for 8-20h, and the product is calcined in a muffle furnace under air atmosphere at 200-400℃ for 1-3h to obtain Co3O4 nanorods; 40-80mg Co3O4 nanorods and 40-60mg commercial Fe(NO3)3·9H2O obtained above are ground and placed in a porcelain boat in a tube furnace. 0.8-1g NaH2PO2·H2O is placed in another porcelain boat upstream of the tube furnace. Under argon atmosphere, the temperature is raised at a rate of 5℃ / min, and heated at 200-400℃ for 1-2h to obtain P-Fe2O3 / P-CoP heterostructure nanosheet. The preparation method above, the Co3O4 nanorods belong to standard card JCPDS #42-1467, the nanorod width is 25-60nm, and the length is 50-600nm; the CoP belongs to standard card JCPDS #29-0497, and the P-Fe2O3 / P-CoP heterostructure nanosheet has a diameter of 50-300nm.
[0007] (2) Application of P-Fe2O3 / P-CoP heterostructure nanosheet prepared by the above preparation method in water treatment reaction; in electrocatalytic decomposition of water, the reaction current density is 10mA / cm 2 , and the voltage is 1.6-1.65V; in electrocatalytic decomposition of seawater, the reaction current density is 10mA / cm 2 , and the voltage is 1.65-1.7V.
[0008] The present application has the following advantages:
[0009] (1) A new synthesis route of P-Fe2O3 / P-CoP heterostructure nanosheets is provided.
[0010] (2) The P-Fe2O3 / P-CoP heterostructure nanosheets exhibit high catalytic ability in water treatment reactions. BRIEF DESCRIPTION OF DRAWINGS
[0011] Figure 1 is the XRD characterization result of Co3O4 nanorods.
[0012] Figure 2 is the SEM characterization result of Co3O4 nanorods.
[0013] Figure 3 is the XRD (a), SEM / TEM (b-f) and P (g), Co (h), Fe (i), O (j) Mapping characterization results of P-Fe2O3 / P-CoP heterostructure nanosheets. DETAILED DESCRIPTION
[0014] The following examples are used to further illustrate the present application, but do not limit the present application.
[0015] Example 1
[0016] 8 mL of NH3·H2O, 20 mL of ethylene glycol, 1 mL of 1 mol / L Na2CO3 solution and 2 mL of 1 mol / L Co(NO3)2 solution were mixed, and hydrothermal reaction was carried out at 150°C for 8 h. The product was calcined in a muffle furnace under air atmosphere at 200°C for 1 h to obtain Co3O4 nanorods. 40 mg of the obtained Co3O4 nanorods and 40 mg of commercial Fe(NO3)3·9H2O were ground and placed in a porcelain boat in a tube furnace. 0.8 g of NaH2PO2·H2O was placed in another porcelain boat upstream of the tube furnace. Under argon atmosphere, the temperature was raised at a rate of 5°C / min, and heated at 200°C for 1 h to obtain P-Fe2O3 / P-CoP heterostructure nanosheets. In the above preparation method, the Co3O4 nanorods belong to standard card JCPDS #42-1467, the width of the nanorods is 25-50 nm, and the length is 50-500 nm; the CoP belongs to standard card JCPDS #29-0497, and the diameter of the P-Fe2O3 / P-CoP heterostructure nanosheets is 50-200 nm. The prepared P-Fe2O3 / P-CoP heterostructure nanosheets were used for water treatment; in the electrocatalytic decomposition of water, the reaction current density was 10 mA / cm 2 , and the voltage was 1.6-1.65 V; in the electrocatalytic decomposition of seawater, the reaction current density was 10 mA / cm2 at 1.65-1.7 V.
[0017] Example 2
[0018] A mixture of 15 mL NH3H2O, 30 mL ethylene glycol, 2 mL 2 mol / L Na2C03solution and 10 mL 2 mol / L Co(N03)2solution was hydrothermally reacted at 200 °C for 20 h, and the product was calcined in a muffle furnace under air atmosphere at 400 °C for 3 h to obtain Co304nanorods. 80 mg of the obtained Co304nanorods and 60 mg of commercial Fe(N03)3-9H2O were ground and placed in a porcelain boat in a tube furnace. 1 g of NaH2P02H2O was placed in another porcelain boat upstream of the tube furnace. Under argon atmosphere, the temperature was raised at a rate of 5 °C / min, and heated at 400 °C for 2 h to obtain P-Fe203 / P-CoP heterostructure nanosheets. The above preparation method, the Co304nanorods belong to standard card JCPDS #42-1467, the nanorod width is 30-60 nm, and the length is 80-600 nm; the CoP belongs to standard card JCPDS #29-0497, and the P-Fe203 / P-CoP heterostructure nanosheet has a diameter of 80-300 nm. The prepared P-Fe203 / P-CoP heterostructure nanosheets were used for water treatment; in the electrocatalytic decomposition of water, the reaction current density was 10 mA / cm2 2 at 1.6-1.65 V; in the electrocatalytic decomposition of seawater, the reaction current density was 10 mA / cm2 2 at 1.65-1.7 V.
[0019] Example 3
[0020] Co3O4 nanorods were prepared by mixing 10 mL NH3H2O, 25 mL ethylene glycol, 1.5 mL 1 mol / L Na2CO3 solution and 6 mL 1 mol / L Co(NO3)2 solution, and hydrothermal reaction at 190°C for 12 h, and then calcination at 300°C for 2 h in air atmosphere in a muffle furnace; 60 mg of the above prepared Co3O4 nanorods and 50 mg of commercial Fe(NO3)3·9H2O were ground and placed in a porcelain boat in a tube furnace; 1 g of NaH2PO2·H2O was placed in another porcelain boat upstream of the tube furnace; under argon atmosphere, the temperature was raised at a rate of 5°C / min, and heated at 300°C for 1 h to obtain P-Fe2O3 / P-CoP heterostructure nanosheets. In the above preparation method, the Co3O4 nanorods belong to standard card JCPDS #42-1467, the nanorod width is 25-60 nm, and the length is 50-600 nm; the CoP belongs to standard card JCPDS #29-0497, and the P-Fe2O3 / P-CoP heterostructure nanosheet diameter is 50-300 nm. The prepared P-Fe2O3 / P-CoP heterostructure nanosheets were used for water treatment; in the electrocatalytic decomposition of water, the reaction current density was 10 mA / cm 2 , and the voltage was 1.6-1.65 V; in the electrocatalytic decomposition of seawater, the reaction current density was 10 mA / cm 2 , and the voltage was 1.65-1.7 V.
Claims
1. A method for preparing P-Fe2O3 / P-CoP heterostructure nanosheets, characterized in that, Comprising the following steps: Mixing 8-15 mL NH3·H2O, 20-30 mL ethylene glycol, 1-2 mL 1-2 mol / L Na2CO3 solution and 2-10 mL 1-2 mol / L Co(NO3)2 solution, hydrothermal reaction at 150-200 ℃ for 8-20 h, the product is calcined in air atmosphere at 200-400 ℃ for 1-3 h in a muffle furnace, to obtain Co3O4 nanorods; grinding and putting 40-80 mg Co3O4 nanorods and 40-60 mg commercial Fe(NO3)3·9H2O obtained above into a porcelain boat and placing in a tube furnace, putting 0.8-1 g NaH2PO2·H2O in another porcelain boat upstream of the tube furnace, heating at 5 ℃ / min, heating at 200-400 ℃ for 1-2 h under argon atmosphere, to obtain P-Fe2O3 / P-CoP heterostructure nanosheets; the Co3O4 nanorods belong to standard card JCPDS #42-1467, the nanorod width is 25-60 nm, the length is 50-600 nm; the CoP belongs to standard card JCPDS #29-0497, the P-Fe2O3 / P-CoP heterostructure nanosheet diameter is 50-300 nm.
2. The application of P-Fe2O3 / P-CoP heterostructure nanosheets prepared by the preparation method of claim 1 in water treatment reactions; in electrocatalytic decomposition of water, the reaction current density is 10 mA / cm 2 , and the voltage is 1.6-1.65 V; in electrocatalytic decomposition of seawater, the reaction current density is 10 mA / cm 2 , and the voltage is 1.65-1.7 V.