CN115475648B - Ni is simultaneously loaded on inner and outer surfaces 2 Preparation method of mesoporous P-doped carbon nitride hollow sphere catalyst - Google Patents

Ni is simultaneously loaded on inner and outer surfaces 2 Preparation method of mesoporous P-doped carbon nitride hollow sphere catalyst Download PDF

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CN115475648B
CN115475648B CN202211230707.2A CN202211230707A CN115475648B CN 115475648 B CN115475648 B CN 115475648B CN 202211230707 A CN202211230707 A CN 202211230707A CN 115475648 B CN115475648 B CN 115475648B
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顾泉
吕昱静
高子伟
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Abstract

The invention discloses a method for simultaneously loading Ni on the inner surface and the outer surface 2 Preparation method of mesoporous P-doped carbon nitride hollow sphere catalyst of P, wherein the catalyst takes carbon nitride hollow sphere as carrier and Ni 2 P is taken as a cocatalyst, a simple dipping-phosphating method is adopted, and during the synthesis of the carbon nitride hollow sphere, the template SiO of the carbon nitride hollow sphere is synthesized by adjusting 2 With Ni 2 P synthesis sequence, while Ni 2 The P is loaded on the inner surface and the outer surface of the mesoporous P-doped carbon nitride hollow nanospheres, enough active sites are provided on the inner surface and the outer surface, and the heterojunction formed by the two surfaces simultaneously promotes the migration and separation of photo-generated charges on the inner surface and the outer surface. The catalyst improves the utilization rate of atoms, realizes the internal and external synergistic effect, and thereby remarkably improves the water photocatalytic decomposition performance. The method is generally applicable to other hollow structure semiconductors, and provides guidance for better utilizing hollow structure semiconductor photocatalysis.

Description

Ni is simultaneously loaded on inner and outer surfaces 2 Preparation method of mesoporous P-doped carbon nitride hollow sphere catalyst
Technical Field
The invention belongs to the technical field of preparation of photocatalysts for solar-driven water splitting, and particularly relates to a preparation method of a photocatalyst for simultaneously loading nano particles on the inner surface and the outer surface of a nano hollow sphere.
Background
Hydrogen energy is one of the most desirable alternative energy sources for fossil fuels. The photocatalytic water splitting technology is considered to be one of ideal methods for producing hydrogen because of low cost, no pollution, mild reaction conditions and high stability. The hollow nano-structure photocatalytic material has special physical and chemical properties and has great application potential in the field of photocatalysis. Such as: light scattering inside the hollow nanomaterial is beneficial to light capturing, light absorption and utilization; the interior space may also serve as a microreactor to facilitate the conversion of reactants; the hollow nanostructure provides a high specific surface area for surface reactions; the nanoscale thin shell layer can reduce the migration distance of the photon-generated carriers to the surface, thereby reducing the probability of recombination. Among the numerous photocatalytic semiconductor materials, graphite-like phase carbon nitride (g-C 3 N 4 ) Has the advantages of absorption in visible light region, acid and alkali resistance, low cost, easy availability, etcThe advantage is that the design and synthesis of hollow nanostructured carbon nitride (such as hollow carbon nitride nanospheres) has the potential to improve the photocatalytic efficiency. However, g-C 3 N 4 The inherent characteristics still cause the problems of low photogenerated charge separation efficiency, lack of surface active sites and the like, which affect the photocatalytic water splitting efficiency.
In general, to increase the photocatalytic activity, supported promoters and element doping are good modification modes. P, C, S, B, and the like, can change the electronic structure and promote light absorption and charge separation. The supported catalyst promoter can promote the transfer of photo-generated carriers and reduce the overpotential of the water decomposition of the photocatalyst, so that the activity of the water decomposition is obviously improved. However, the prior studies have generally involved loading a promoter on the outer surface of hollow nanospheres, such as Cui et al (ACS appl. Mater. Interfaces 2022,14,12551-12561) by thermal annealing and heteroatom doping strategies 2 In situ assembly of nanoplates to N, P co-doped hollow carbon nanospheres (MoSe 2 The nano engineering material obtained on the outer surface of the NP-HCNSs) can be well used as an anode of the KIBs; sun et al (International journal of hydrogen energy 2020,45,2840-2851) prepared hollow g-C 3 N 4 @α-Fe 2 O 3 Co-Pi composite heterojunction sphere photocatalyst, wherein alpha-Fe 2 O 3 And spherical g-C 3 N 4 The contact of the outer surface of the sphere forms a z-type heterojunction, and the Co-Pi serving as a hole storage agent can further reduce the recombination of photo-generated electrons and holes. Metal phosphides such as Ni 2 P has been shown to be a good photocatalytic hydrogen-generating promoter due to its low overpotential and stability. Load Ni 2 After the P promoter, the carbon nitride absorbs sunlight to generate photogenerated carriers. Electron transfer to Ni 2 On the P nano particles, the charge separation efficiency is improved, and H is promoted + At Ni 2 Reduction of P. But this fails to fully utilize the advantages of the hollow structure, resulting in that the inner surface and the inner space are not effectively utilized. Due to the lack of cocatalysts inside, there is still a high frequency recombination of electron holes at the inner surface and close to the inner surface, and the photocatalytic activity is not ideal.
Disclosure of Invention
The invention aims to provide a Ni-loaded alloy with inner and outer surfaces simultaneously 2 A preparation method of a mesoporous P-doped carbon nitride hollow sphere catalyst.
In view of the above, the preparation method adopted by the invention comprises the following steps:
1. SiO is made of 2 Refluxing microsphere, gamma-aminopropyl triethoxysilane and isopropanol at 70-80 deg.c for 2-3 hr, centrifuging, drying, mixing the dried product with nickel chloride water solution, stirring for 6-10 hr, centrifuging, drying, grinding and mixing with excessive sodium phosphite, calcining at 350-400 deg.c for 1.5-2.5 hr under flowing argon to obtain supported Ni 2 Non-porous SiO of P 2 A microsphere;
2. adding ammonia water into the mixed solution of ethanol and deionized water, stirring uniformly, adding Ni-loaded solution 2 Non-porous SiO of P 2 Microspheres, after being evenly stirred, tetraethyl orthosilicate and octadecyl trimethoxy silane are added dropwise under the stirring condition, the obtained mixed solution is stood for reaction for 2 to 4 hours at room temperature, after the reaction is finished, the mixture is centrifuged and dried, and calcined for 5 to 6 hours at 500 to 600 ℃ in the air, and then Ni is obtained through hydrochloric acid soaking, deionized washing and drying 2 P-SiO 2 A template;
3. ni is added with 2 P-SiO 2 Adding a template into a cyanamide aqueous solution, rotationally mixing for 2-4 hours under vacuum, sequentially carrying out ultrasonic treatment at 50-60 ℃ for 2-3 hours and stirring at 50-60 ℃ for 6-10 hours, centrifugally separating, drying, transferring the obtained mixture into a porcelain boat, and calcining for 3-5 hours at 500-600 ℃ under flowing argon to obtain the Ni-coated ceramic 2 P is unetched carbon nitride nanospheres;
4. wrapping Ni inside 2 Dispersing P unetched carbon nitride nanospheres into deionized water, adding nickel chloride under stirring, stirring for 8-10 h, drying at 80-100 ℃, mixing the dried product with excessive sodium phosphite, transferring into a magnetic boat, calcining for 2-3 h at 350-400 ℃ under flowing argon, naturally cooling to room temperature, and using 4mol/LNH 4 HF 2 Aqueous etching to remove SiO 2 Centrifuging to collect powdery product, washing with deionized water, and dryingDrying to obtain Ni-loaded inner and outer surfaces simultaneously 2 And the mesoporous P of P is doped with carbon nitride hollow nanospheres.
In the above step 1, the SiO is preferably used 2 The mixing ratio of the microballoons and gamma-aminopropyl triethoxysilane and isopropanol is 1 g:2-3 mL:50-60 mL, and the SiO is prepared by mixing the microballoons with the raw materials 2 The mass ratio of the microspheres to the nickel chloride and the sodium phosphite is 1:0.015-0.030:0.025-0.06.
In the above step 1, the SiO is further preferable 2 The particle size of the microsphere is 300-500 nm.
In the step 2, the volume ratio of the ammonia water to the ethanol, the deionized water tetraethyl orthosilicate and the octadecyl trimethoxy silane is preferably 1:15-20:2-2.5:1-1.1:0.4-0.6, and the Ni is loaded 2 Non-porous SiO of P 2 The charging proportion of the microsphere and the tetraethyl orthosilicate is 1 g:3-4 mL.
In the above step 3, the Ni is preferable 2 P-SiO 2 The mass ratio of the template to the cyanamide is 1:2-4.
In the step 3, the vacuum degree of the vacuum is preferably 10 to 80Pa, and the rotation speed of the rotation is preferably 30 to 100rpm.
In the above step 4, it is preferable that the inside coating Ni 2 The mass ratio of the unetched carbon nitride nanospheres to the nickel chloride and the sodium phosphite is 1:0.1-0.3:0.4-0.5.
The beneficial effects of the invention are as follows:
1. the invention successfully synthesizes the mesoporous P-doped carbon nitride hollow nanospheres (PCNHS) by a dipping-phosphating method and loads Ni on the inner surface and the outer surface of the mesoporous P-doped carbon nitride hollow nanospheres simultaneously 2 And (3) a P cocatalyst. The method has important significance for carrying out photocatalysis reaction by utilizing the semiconductor with the hollow nano structure better.
2. The invention uses triethanolamine as a hole sacrificial agent, and uses Ni under the irradiation of visible light 2 P@PCNHS@Ni 2 P is a photocatalyst, and the performance test of photocatalytic hydrogen production is carried out. Ni (Ni) 2 P@PCNHS@Ni 2 P provides enough active sites for proton reduction on the inner surface and the outer surface, and promotes the migration and separation of photogenerated carriers on the inner surface and the outer surfaceThe atomic utilization rate is high, the inside and outside synergistic photocatalytic decomposition of water is realized, and the efficiency is remarkably improved.
Drawings
FIG. 1 is Ni in example 1 2 P@PCNHS@Ni 2 P (Ni content 3.80 wt.%) CNHS in comparative example 1, ni in comparative example 2 2 P/CNHS, PCNHS in comparative example 3, PCNHS@Ni in comparative example 5 2 P (Ni content 0.05 wt.%) Ni in comparative example 6 2 XRD pattern of p@pcnhs (Ni content 3.19 wt.%).
FIG. 2 is Ni in example 1 2 P@PCNHS@Ni 2 SEM pictures of P (Ni content 3.80 wt.%).
FIG. 3 is Ni in example 1 2 P@PCNHS@Ni 2 TEM image of P (Ni content 3.80 wt.%).
FIG. 4 is Ni in example 1 2 P@PCNHS@Ni 2 External Ni of P (Ni content 3.80 wt.%) 2 Lattice fringe HRTEM diagram for P.
FIG. 5 is Ni in example 1 2 P@PCNHS@Ni 2 Internal Ni of P (Ni content 3.80 wt.%) 2 Lattice fringe HRTEM diagram for P.
FIG. 6 is Ni in example 1 2 P@PCNHS@Ni 2 Dark field STEM and C, N, ni, P element map of P (Ni content 3.80 wt.%).
FIG. 7 is Ni in example 1 2 P@PCNHS@Ni 2 P (Ni content 3.80 wt.%) with CNHS in comparative example 1 and Ni in comparative example 2 2 P/CNHS, PCNHS in comparative example 3, pt@pcnhs in comparative example 4.
FIG. 8 is Ni in example 1 2 P@PCNHS@Ni 2 P (Ni content 3.80 wt.%) vs. PCNHS@Ni in comparative example 5 2 P (Ni content 0.05 wt.%) Ni in comparative example 6 2 P@pcnhs (Ni content 3.19 wt.%) photocatalytic hydrogen production activity comparison graph.
FIG. 9 is Ni in example 1 2 P@PCNHS@Ni 2 P (Ni content 3.80 wt.%) vs. PCNHS@Ni in comparative example 5 2 P (Ni content 0.05 wt.%) Ni in comparative example 6 2 P@pcnhs (Ni content 3.19 wt.%) activity comparison graph after photocatalytic hydrogen production quality normalization.
FIG. 10 is Ni in example 1 2 P@PCNHS@Ni 2 P (Ni content 3.80 wt.%) vs. PCNHS@Ni in comparative example 5 2 P (Ni content 0.05 wt.%) Ni in comparative example 6 2 P@pcnhs (Ni content of 3.19 wt.%) photocatalytic water splitting activity in the absence of the sacrificial agent triethanolamine.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. 4.35mL of ammonia (32 wt.%) was added to a mixture of 75mL of ethanol and 10mL of deionized water, and after stirring at 30℃for 30min, 5.6mL of tetraethyl orthosilicate (TEOS) was added and stirring was continued for 1h to obtain a homogeneous mixture
Figure BDA0003881427510000041
Silica sol. Will->
Figure BDA0003881427510000042
Directly centrifuging, drying and grinding silica sol to obtain SiO with particle diameter of about 300nm 2 And (3) microspheres. 1.2g of SiO 2 The microspheres were refluxed with 3mL of gamma-aminopropyl triethoxysilane and 63mL of isopropanol at 80℃for 2h, centrifuged and dried, and the dried product was then mixed with 50mL of a solution containing 28mg of NiCl 2 ·6H 2 Stirring the aqueous solution of O for 8h, centrifuging, drying and mixing with 47mg NaH 2 PO 2 ·H 2 O is ground and mixed, the temperature is increased to 350 ℃ at the heating rate of 5 ℃/min under flowing argon, the mixture is calcined for 2 hours, and the mixture is ground after natural cooling, thus obtaining the loaded Ni 2 Non-porous SiO of P 2 And (3) microspheres.
2. 4.35mL of ammonia (32 wt.%) was added to a mixture of 75mL of ethanol and 10mL of deionized water, and after stirring at 30℃for 30min, 1.2g of Ni-loaded was added 2 Non-porous SiO of P 2 Microsphere, stirring was continued for 30min, and 4.5mL (4.17 g) of TEOS and 2.15mL (1.87 g) of octadecyltrimethoxysilane (C) were added dropwise under stirring 18 TMOS), and then the mixed solution was allowed to stand at room temperature for reaction for 3 hours. After the reaction, it was centrifuged and dried at 70 ℃Calcining at 550deg.C in air for 6 hr, soaking in 1mol/L HCl aqueous solution, washing, and drying at 80deg.C for 10 hr to obtain Ni 2 P-SiO 2 And (5) a template. The process is carried out by TEOS and C 18 TMOS on load Ni 2 Non-porous SiO of P 2 Cohydrolysis and condensation on the microsphere to form a layer of mesoporous SiO on the surface 2 A shell.
3. 2g Ni 2 P-SiO 2 Adding a template into 10g of a cyanamide aqueous solution with the mass concentration of 50%, rotationally mixing for 3 hours at 50ppm under the vacuum degree of 90Pa, sequentially carrying out ultrasonic treatment at 60 ℃ for 2 hours and stirring at 60 ℃ for 8 hours, centrifugally separating the obtained mixture, drying at 80 ℃ for 24 hours in air, finally transferring the obtained solid into a porcelain boat, heating to 550 ℃ at the heating rate of 4.4 ℃/min under flowing argon, calcining for 4 hours, and naturally cooling to room temperature to obtain the Ni-coated ceramic 2 Unetched carbon nitride nanospheres of P (CNHS@Ni) 2 P), wherein the content of Ni is 0.05wt.%.
4. 1.12g CNHS@Ni 2 P was dispersed in 50mL deionized water, then 168mg NiCl was added with vigorous stirring 2 ·6H 2 O, stirring for 10h, drying at 100deg.C, mixing the dried product with 500mg NaH 2 PO 2 ·H 2 O is transferred to a magnetic boat after being mixed, and is heated to 350 ℃ at a heating rate of 5 ℃/min under flowing argon and calcined for 2 hours. Then naturally cooling to room temperature, using 4mol/L NH 4 HF 2 Aqueous etching for 12h to remove SiO 2 Centrifugally collecting a powdery product, washing the powdery product with deionized water, and drying the powdery product in a 60 ℃ oven to obtain Ni-loaded inner and outer surfaces 2 P mesoporous P doped carbon nitride hollow nanospheres, denoted Ni 2 P@PCNHS@Ni 2 P, wherein the Ni content is 3.80%.
Comparative example 1
1. 4.35mL of ammonia (32 wt.%) was added to a mixture of 75mL of ethanol and 10mL of deionized water, and after stirring at 30℃for 30min, 5.6mL of tetraethyl orthosilicate (TEOS) was added and stirring was continued for 1h to obtain a homogeneous mixture
Figure BDA0003881427510000051
Silica sol. Stirring while stirring4.5mL (4.17 g) of TEOS and 2.15mL (1.87 g) of octadecyltrimethoxysilane (C) 18 TMOS) is added dropwise to->
Figure BDA0003881427510000052
In the silica sol, the mixed solution was then allowed to stand at room temperature for reaction for 3 hours. After the reaction, centrifuging, drying at 70 ℃ and calcining at 550 ℃ in air for 6 hours, finally soaking and washing with 1mol/L HCl aqueous solution, and drying at 80 ℃ for 10 hours to obtain SiO 2 And (5) a template.
2. 2g of SiO 2 Adding a template into 10g of a cyanamide aqueous solution with the mass concentration of 50%, rotationally mixing for 3 hours at 50ppm under the vacuum degree of 90Pa, sequentially carrying out ultrasonic treatment at 60 ℃ for 2 hours and stirring at 60 ℃ for 8 hours, centrifugally separating the obtained mixture, drying at 80 ℃ for 24 hours in air, finally transferring the obtained solid into a porcelain boat, heating to 550 ℃ at the heating rate of 4.4 ℃/min under flowing argon, calcining for 4 hours, naturally cooling to room temperature, and then using 4mol/L NH 4 HF 2 Aqueous etching for 12h to remove SiO 2 And (3) centrifugally collecting a powdery product, washing the powdery product with deionized water, and drying the powdery product in a 60 ℃ oven to obtain the carbon nitride hollow nanospheres (CNHS).
Comparative example 2
50mg of NiCl is taken 2 ·6H 2 O and 84mg NaH 2 PO 2 ·H 2 O is ground, and then is transferred into a magnetic boat to be heated to 400 ℃ under flowing Ar at a heating rate of 2 ℃/min, and is calcined for 2 hours. Naturally cooling to room temperature, washing with deionized water and ethanol for 3 times, and drying at 60deg.C for 10 hr to obtain pure Ni 2 P crystal powder. 100mg of CNHS (preparation method same as comparative example 1) was dispersed in 30mL of deionized water, and 3mg of pure Ni was added 2 Stirring the P crystal for 10h, washing with deionized water, and drying at 60deg.C for 10h to obtain Ni 2 P/carbon nitride hollow nanosphere composite catalyst (Ni 2 P/CNHS)。
Comparative example 3
2g of SiO 2 Template (preparation method same as comparative example 1 step 1) was added to 10g of a 50% by mass aqueous solution of cyanamide at a vacuum of 90Pa and a pressure of 5Mixing at 0ppm for 3 hr, sequentially ultrasonic treating at 60deg.C for 2 hr, stirring at 60deg.C for 8 hr, centrifuging, drying at 80deg.C in air for 24 hr, transferring the obtained solid into porcelain boat, heating to 550deg.C at 4.4deg.C/min under flowing argon, calcining for 4 hr, naturally cooling to room temperature, and mixing with 500mg NaH 2 PO 2 ·H 2 Grinding O, transferring to a magnetic boat, heating to 350deg.C at a heating rate of 5deg.C/min under flowing argon, calcining for 2 hr, naturally cooling to room temperature, and adding 4mol/L NH 4 HF 2 Aqueous etching for 12h to remove SiO 2 And (3) centrifugally collecting a powdery product, washing the powdery product with deionized water, and drying the powdery product in a 60 ℃ oven to obtain the phosphorus-doped carbon nitride hollow nanospheres (PCNHS).
Comparative example 4
100mg of PCNHS (preparation method same as comparative example 3) was dispersed in 30mL of deionized water, and 150. Mu.L of 6.59mg Pt/mL of H was added 2 PtCl 6 The aqueous solution is stirred uniformly and then 200mg of NaBH is added 4 Stirring is continued for 10 hours, deionized water and ethanol are used for washing for 3 times respectively, and finally drying is carried out for 10 hours at 80 ℃ to obtain the Pt-loaded phosphorus-doped carbon nitride hollow nanospheres (Pt@PCNHS).
Comparative example 5
1. 4.35mL of ammonia (32 wt.%) was added to a mixture of 75mL of ethanol and 10mL of deionized water, and after stirring at 30℃for 30min, 5.6mL of tetraethyl orthosilicate (TEOS) was added and stirring was continued for 1h to obtain a homogeneous mixture
Figure BDA0003881427510000061
Silica sol. Will->
Figure BDA0003881427510000062
Directly centrifuging, drying and grinding silica sol to obtain SiO 2 Reflux the microsphere with 3mL of gamma-aminopropyl triethoxysilane and 63mL of isopropanol at 80 ℃ for 2h, centrifuging and drying to obtain SiO 2 Refluxing microsphere with 3mL of gamma-aminopropyl triethoxysilane and 63mL of isopropanol at 80deg.C for 2 hr, centrifuging, drying, and mixing the dried product with 50mL of Ni with different mass (28 mg, 84mg, 168mg, 252mg, 336 mg)Cl 2 ·6H 2 The aqueous solution of O was stirred for 8 hours, centrifuged and dried, and then mixed with 500mg NaH 2 PO 2 ·H 2 O is ground and mixed, the temperature is increased to 350 ℃ at the heating rate of 5 ℃/min under flowing argon, the mixture is calcined for 2 hours, and the mixture is ground after natural cooling, thus respectively obtaining the loaded Ni with different Ni contents 2 Non-porous SiO of P 2 And (3) microspheres.
2. 2g Ni 2 P-SiO 2 Template (preparation method is the same as example 1 step 2) is added into 10g of cyanamide aqueous solution with 50% mass concentration, mixed for 3h at 50ppm rotation under 90Pa, then ultrasonic treated for 2h at 60 ℃ and stirring for 8h at 60 ℃ in sequence, the obtained mixture is centrifugally separated and dried for 24h at 80 ℃ in air, finally the obtained solid is transferred into a porcelain boat, heated to 550 ℃ at a heating rate of 4.4 ℃/min under flowing argon, calcined for 4h, naturally cooled to room temperature and then mixed with 500mg NaH 2 PO 2 ·H 2 O is transferred to a magnetic boat after grinding, and is heated to 350 ℃ at a heating rate of 5 ℃/min under flowing argon and calcined for 2 hours. Then cooled to room temperature, and treated with 4mol/L NH 4 HF 2 Aqueous etching for 12h to remove SiO 2 Centrifugally collecting powdery product, washing with deionized water, drying in a 60 ℃ oven to obtain Ni-coated inner part 2 Mesoporous phosphorus doped carbon nitride hollow nanospheres of P (PCNHS@Ni) 2 P). According to NiCl added in step 1 2 ·6H 2 The mass of O is different to obtain PCNHS@Ni with the Ni content of 0.05%, 0.15%, 0.03%, 0.45% and 0.60% respectively 2 P。
Comparative example 6
2g of SiO 2 Adding a template (the preparation method is the same as that in the step 1 of the comparative example 1) into 10g of a cyanamide aqueous solution with the mass concentration of 50%, rotating and mixing for 3 hours at 50ppm under the vacuum degree of 90Pa, sequentially carrying out ultrasonic treatment at 60 ℃ for 2 hours and stirring at 60 ℃ for 8 hours, centrifugally separating the obtained mixture, drying at 80 ℃ for 24 hours in air, finally transferring the obtained solid into a porcelain boat, heating to 550 ℃ at the heating rate of 4.4 ℃/min under flowing argon, calcining for 4 hours, and naturally cooling to room temperature to obtain the unetched carbon nitride nanospheres. Taking 1.12g of unetched carbon nitride nanospheresDispersing into 50mL deionized water, and adding 56mg, 112mg, 168mg, 224mg, 280mg NiCl under vigorous stirring 2 ·6H 2 O, stirring for 10h, drying at 100deg.C, mixing the dried product with 500mg NaH 2 PO 2 ·H 2 O is transferred to a magnetic boat after being mixed, the temperature is raised to 350 ℃ at the heating rate of 5 ℃/min under flowing argon, calcined for 2 hours, naturally cooled to room temperature, and then 4mol/L NH is used 4 HF 2 Aqueous etching for 12h to remove SiO 2 Centrifuging to collect powdery product, washing with deionized water, and drying in oven at 60deg.C to obtain externally loaded Ni 2 Mesoporous phosphorus-doped carbon nitride hollow nanospheres of P (Ni 2 P@pcnhs). According to the NiCl added 2 ·6H 2 The mass of O is different to obtain Ni with the content of 1.86%, 3.19%, 4.63%, 5.98% and 7.31% of Ni respectively 2 P@PCNHS。
The samples prepared in example 1 and comparative examples 1 to 6 were respectively subjected to structural characterization, and the results are shown in fig. 1 to 6. As shown in fig. 1, both the pure CNHS and all composites had two distinct diffraction peaks at 13.1 ° and 27.6 °, the peak at 13.1 ° being due to periodic stacking of the continuous triazine ring network in the carbon nitride plane, the peak at 27.6 ° being related to stacking with the graphite layered structure (002) plane of the conjugated aromatic hydrocarbon system, ni 2 P@PCNHS@Ni 2 P and Ni 2 The XRD pattern of P@PCNHS has obvious diffraction peaks at 40.7 degrees, 44.5 degrees, 47.3 degrees and 54.3 degrees, and points to hexagonal Ni respectively 2 The (111), (201), (210), (300) planes of P (JCPDS 03-0953) indicate Ni 2 Successful loading of P promoter; PCNHS@Ni 2 No observation of the XRD pattern of P with Ni 2 P-dependent reflection due to Ni loading inside 2 P is covered with carbon nitride and Ni 2 The content of P is low. As can be seen from fig. 2 and 3, ni 2 P@PCNHS@Ni 2 Ni in P 2 The P nano particles are respectively supported on the inner surface and the outer surface, the lattice fringes of the nano particles supported on the outer surface are still obvious through HRTEM, the interplanar spacing d=0.22 nm (see figure 4), but the lattice fringes of the nano particles in the inner part are not obvious due to the obstruction of the carbon nitride (see figure 5) but still can be matched with Ni 2 The lattice spacing of P is identical. In addition, we tested Ni 2 P@PCNHS@Ni 2 The result of energy dispersive X-ray (EDX) and element mapping (see FIG. 6) of P shows that C, N, ni and P are distributed inside and outside the hollow nanospheres, the light spots outside are obvious, while the internal light spots are weak due to the blocking of PCNHS, thereby further proving that both the inside and the outside of PCNHS are successfully loaded with Ni 2 P。
In order to demonstrate the beneficial effects of the present invention, photocatalytic decomposition of aqueous hydrogen activity tests were performed using the samples prepared in example 1 and comparative examples 1 to 6, respectively, as catalysts. Under the irradiation of visible light, a heat-resistant glass reactor with a top quartz glass sheet and a closed glass gas renewable circulation system are used for testing, and the specific operation steps are as follows: adding 90mL deionized water and 10mL triethanolamine into a reactor, stirring for dissolving, adding 20mg catalyst, stirring, vacuumizing for 30min to remove air in the device and reaction solution, and irradiating with visible light (light intensity is 1.12W/cm) 2 ) The reaction was carried out at 20 ℃. The final hydrogen produced was tested by pumping through a Thermal Conductivity Detector (TCD) of gas chromatography (Shiweipx GC 7806) at regular time intervals (1 h), the results of which are shown in fig. 7-10.
As can be seen from fig. 7, the catalysts corresponding to comparative examples 1, 2, and 3 were found to be based on triethanolamine as a hole sacrificial agent under irradiation of visible light: CNHS, ni 2 The hydrogen production rates of P/CNHS and PCNHS are respectively 0.1, 1.65 and 1.86 mu mol g -1 ·h -1 . Description of Ni on load 2 After P, the hydrogen production rate is improved to 1.65 mu mol.g -1 ·h -1 The element doping can also effectively improve the photocatalytic activity, so that Ni is loaded in the preparation process 2 P element is doped into CNHS at the same time, and the two elements also produce a synergistic effect, and the photocatalytic hydrogen evolution rate of PCNHS is 1.86 mu mol.g -1 ·h -1 But Ni when both exist at the same time 2 P@PCNHS@Ni 2 The P hydrogen evolution rate can reach 817.90 mu mol.g -1 ·h -1 Even higher than the hydrogen evolution rate 339.22 mu mol.g of Pt loaded on PCNHS (Pt@PCNHS) -1 ·h -1 (2.4 times).As can be clearly seen from FIG. 8, PCNHS@Ni with different Ni contents 2 P(W Ni =0.05 to 0.60 wt.%) with Ni 2 P@PCNHS(W Ni =1.86 to 7.50 wt.%) the photocatalytic hydrogen production performance is far less than Ni 2 P@PCNHS@Ni 2 P. To further confirm the synergistic activity in both the internal and external, PCNHS@Ni of comparative example 5 was selected 2 P(W Ni =0.60 wt.%) and Ni in comparative example 6 2 P@PCNHS(W Ni =3.19 wt.%), the sum of the contents of Ni is added to Ni in example 1 2 P@PCNHS@Ni 2 P(W Ni =3.80 wt.%) the same catalyst was subjected to photocatalytic hydrogen evolution activity comparison. As shown in FIG. 9, ni 2 P@PCNHS@Ni 2 P(W Ni =3.80 wt.%) hydrogen evolution activity was greater than pcnhs@ni in comparative example 5 2 P(W Ni =0.60 wt.%) and Ni in comparative example 6 2 P@PCNHS(W Ni =3.19 wt.%) and much greater than the sum of the two, show synergy. Calculated Ni in terms of Ni content per unit 2 P@PCNHS@Ni 2 P(W Ni =3.80 wt.%) the hydrogen evolution rate can reach 21.52mmol·g Ni -1 ·h -1 PCNHS@Ni, respectively 2 P(3.00mmol·g Ni -1 ·h -1 ) And Ni 2 P@PCNHS(16.67mmol·g Ni -1 ·h -1 ) 7 times and 1.3 times of (a). As shown in FIG. 10, the photocatalytic water splitting activity of the three catalysts having the same content as described above was further tested, PCNHS@Ni under irradiation of visible light 2 The P hydrogen evolution rate can reach 2.02 mu mol.g -1 ·h -1 ，Ni 2 The hydrogen evolution rate of P@PCNHS can reach 3.35 mu mol.g -1 ·h -1 ，Ni 2 P@PCNHS@Ni 2 The P hydrogen evolution rate can reach 12.70 mu mol.g -1 ·h -1 The internal and external synergistic effect of 1+1 > 2 is realized.

Claims (7)

1. Ni is simultaneously loaded on inner and outer surfaces 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of:
(1) SiO is made of 2 Microsphere and gamma-aminopropyl triethoxysilane, isopropanol in 70-to-70Refluxing at 80 ℃ for 2-3 h, centrifuging and drying, mixing and stirring the dried product and nickel chloride aqueous solution for 6-10 h, centrifuging and drying, grinding and mixing with excessive sodium phosphite, calcining at 350-400 ℃ for 1.5-2.5 h under flowing argon to obtain the loaded Ni 2 Non-porous SiO of P 2 A microsphere;
(2) Adding ammonia water into the mixed solution of ethanol and deionized water, stirring uniformly, adding Ni-loaded solution 2 Non-porous SiO of P 2 Microspheres, after being evenly stirred, tetraethyl orthosilicate and octadecyl trimethoxy silane are added dropwise under the stirring condition, the obtained mixed solution is stood at room temperature for reaction of 2-4 h, after the reaction is finished, the mixture is centrifuged and dried, and calcined in the air at 500-600 ℃ for 5-6 h, and then the Ni is obtained through hydrochloric acid soaking, deionized washing and drying 2 P-SiO 2 A template;
(3) Ni is added with 2 P-SiO 2 Adding a template into a cyanamide aqueous solution, rotationally mixing under vacuum for 2-4 h, sequentially carrying out ultrasonic treatment at 50-60 ℃ for 2-3 h and stirring at 50-60 ℃ for 6-10 h, centrifugally separating, drying, transferring the obtained mixture into a porcelain boat, and calcining at 500-600 ℃ for 3-5 h under flowing argon to obtain the Ni-coated ceramic 2 P is unetched carbon nitride nanospheres;
(4) Wrapping Ni inside 2 Dispersing P unetched carbon nitride nanospheres into deionized water, adding nickel chloride under stirring, stirring for 8-10 h, drying at 80-100 ℃, mixing the dried product with excessive sodium phosphite, transferring into a magnetic boat, calcining for 2-3 h at 350-400 ℃ under flowing argon, naturally cooling to room temperature, and using 4mol/L NH 4 HF 2 Aqueous etching to remove SiO 2 Centrifugally collecting powdery product, washing with deionized water, and drying to obtain Ni-loaded inner and outer surfaces 2 And the mesoporous P of P is doped with carbon nitride hollow nanospheres.
2. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in step (1), the SiO 2 Microsphere and gamma-aminopropyl triethoxysilaneThe mixing ratio of isopropyl alcohol is 1 g:2-3 mL:50-60 mL; the SiO is 2 The mass ratio of the microspheres to the nickel chloride and the sodium phosphite is 1:0.015-0.030:0.025-0.06.
3. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 or 2 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in step (1), the SiO 2 The particle size of the microsphere is 300-500 nm.
4. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in the step (2), the volume ratio of the ammonia water to the ethanol, the deionized water, the tetraethyl orthosilicate and the octadecyl trimethoxy silane is 1:15-20:2-2.5:1-1.1:0.4-0.6, and the Ni is loaded 2 Non-porous SiO of P 2 The charging ratio of the microsphere and the tetraethyl orthosilicate is 1 g:3-4 mL.
5. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in step (3), the Ni 2 P-SiO 2 The mass ratio of the template to the cyanamide is 1:2-4.
6. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in the step (3), the vacuum degree of the vacuum is 10-80 Pa, and the rotating speed is 30-100 rpm.
7. The simultaneous loading of inner and outer surfaces with Ni according to claim 1 2 The preparation method of the mesoporous P-doped carbon nitride hollow sphere catalyst is characterized by comprising the following steps of: in the step (4), the inside is coated with Ni 2 The mass ratio of the unetched carbon nitride nanospheres to the nickel chloride and the sodium phosphite is 1:0.1-0.3:0.4-0.5.
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