CN-122013236-A - NiPO@Fe-NiS array catalyst, preparation method and application

CN122013236ACN 122013236 ACN122013236 ACN 122013236ACN-122013236-A

Abstract

The invention discloses a NiPO@Fe-NiS array catalyst and a preparation method and application thereof, and belongs to the technical field of catalyst materials. Adding diammonium hydrogen phosphate into ultrapure water, stirring uniformly, putting foam nickel into the ultrapure water, transferring the foam nickel into an autoclave, putting the autoclave into an oven, performing hydrothermal treatment to obtain NiP 4 O 11 (marked as NiPO), cooling to room temperature after the reaction is finished, and washing and drying; finally, niPO is put into an autoclave containing ferric nitrate nonahydrate and thiosulfate pentahydrate for second-step hydrothermal reaction to obtain NiPO@Fe-NiS, and the NiPO@Fe-NiS micro rod-nano sheet array catalyst combined with a dianion layer is prepared, wherein in a seawater electrolysis system of 6M KOH, the NiPO@Fe-NiS anode catalyst can respectively realize current densities of 100 mA/cm 2 、500 mA/cm 2 and 1000 mA/cm 2 only by overpotential of 199 mV, 245 mV and 265 mV, can stably run for 1500 hours under the condition of high current density of 500 mA/cm 2 , and has the comprehensive performance advantages of high catalytic activity and long-term durability in industrial alkaline seawater.

Inventors

Huang Chuqiang
TAO XIAOLONG
CHENG SHAOJUN
LIU YUNPENG
DENG BINGLU

Assignees

佛山大学

Dates

Publication Date: 20260512
Application Date: 20260129

Claims (10)

1. The NiPO@Fe-NiS array catalyst is characterized by comprising a NiPO micrometer rod substrate and Fe-NiS nano sheets grown on the surface of the substrate in situ to form a hierarchical micro-nano structure array, wherein Ni, fe, P, O and S elements are uniformly distributed on the NiPO@Fe-NiS array catalyst, and a PO 4 3- /SO 4 2- dianion layer is further arranged on the surface of the NiPO@Fe-NiS array catalyst.
2. A method for preparing a nipo@fe-NiS array catalyst, wherein the method is used for preparing the nipo@fe-NiS array catalyst according to claim 1, and the method comprises the following steps: s1, dissolving hydrogen phosphate in water, and uniformly stirring to obtain a phosphate solution; s2, immersing the cleaned bulk nickel into the phosphate solution, placing the solution in an autoclave, performing hydrothermal treatment, cooling, washing and drying to obtain NiPO precursor; s3, dissolving ferric salt and thiosulfate in water, and uniformly stirring to obtain a mixed solution containing iron and sulfur; S4, immersing the NiPO precursor into the mixed solution containing iron and sulfur, placing the mixed solution into an autoclave, performing hydrothermal treatment at 120-130 ℃ for 8-10 hours, cooling, washing and drying to obtain the NiPO@Fe-NiS micro rod-nano sheet array catalyst.
3. The method according to claim 2, wherein in step S1, the hydrogen phosphate is at least one of sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium dihydrogen phosphate.
4. The method according to claim 2, wherein in step S2, the bulk nickel is at least one of nickel foam, nickel flakes, nickel mesh or nickel felt.
5. The method according to claim 2, wherein in step S2, the hydrothermal treatment is performed at 150 ℃ to 180 ℃ for 10 hours to 12 hours.
6. The method according to claim 2, wherein in the step S3, the iron salt is at least one of ferric chloride and ferric nitrate, and the thiosulfate is at least one of sodium thiosulfate and potassium thiosulfate.
7. The preparation method according to claim 2, wherein in the step S1, the concentration of the phosphate solution is 1.5mmol/L to 2mmol/L.
8. The preparation method according to claim 2, wherein in step S3, the concentration of iron ions in the iron salt solution is 0.5mmol/L to 0.9mmol/L, and the concentration of sulfur in the thiosulfate solution is 0.5mmol/L to 1mmol/L.
9. The method according to claim 2, wherein in step S4, the drying temperature is 60 ℃ to 65 ℃ and the time is 2h to 3h.
10. The use of a nipo@fe-NiS array catalyst according to claim 1 in the preparation of an anode electrode.

Description

NiPO@Fe-NiS array catalyst, preparation method and application Technical Field The invention relates to the technical field of catalysts, in particular to a NiPO@Fe-NiS array catalyst, a preparation method and application thereof. Background Hydrogen energy, a clean, efficient secondary energy source, is considered to be one of the important ways to achieve the energy structure transformation and carbon neutralization goals. At present, in various hydrogen production technologies, water electrolysis hydrogen production driven by renewable energy sources is widely paid attention to because of clean process and strong sustainability. However, the traditional water electrolysis process is highly dependent on high-purity deionized water, so that the problem of fresh water resource shortage is further aggravated under the condition of large-scale application, and the popularization and application of the method are limited. Seawater occupies about 96% of the total amount of terrestrial water resources, is abundant in reserve and widely distributed, and is considered to be an almost inexhaustible hydrogen production raw material. The sea water electrolysis is combined with an offshore wind power or photovoltaic power generation system in coastal areas, so that the cost of links such as sea water desalination, transportation and storage can be reduced, and fresh water consumption and carbon emission can be effectively reduced. Therefore, direct seawater electrolysis is regarded as a sustainable hydrogen production path with important application prospect. However, seawater electrolysis still faces a number of technical challenges during actual operation, particularly focused on the anodic oxygen evolution reaction process. The natural seawater contains high-concentration chloride ions (Cl -), which are easy to cause competition reactions such as Chlorine Evolution Reaction (CER) and the like in the anode reaction process, and accelerate the corrosion and failure of electrode materials. Although thermodynamically more advantageous than under alkaline conditions, the kinetics of the reaction are more favourable since only two electron transfer processes are involved, and it is easy to take up part of the current in the actual reaction, resulting in a decrease of the energy efficiency and the generation of chlorine-containing species with corrosiveness and toxicity. Meanwhile, corrosion of Cl - can also cause metal dissolution and active site loss, so that the performance of the anode catalyst is quickly attenuated, and long-term stable operation is difficult to realize. Aiming at the problems of corrosion and side reaction caused by the anode end Cl -, a great deal of research has been carried out in the prior art, and the two aspects of catalyst composition regulation and interface structure design are mainly focused. On one hand, the catalyst is chemically regulated by introducing heterogeneous elements, so that the electronic structure of an active center can be changed, and the adsorption energy of an Oxygen Evolution Reaction (OER) intermediate is optimized, thereby improving the OER intrinsic activity and inhibiting the adsorption of Cl - to a certain extent. On the other hand, by constructing a protective layer rich in anions on the surface of the catalyst, a negatively charged barrier structure can be formed at the interface, and the electrostatic repulsion and the steric hindrance effect are utilized to prevent Cl - from migrating to an active site, and meanwhile, the effective transmission of OH - is maintained, so that the corrosion of Cl - is slowed down and the occurrence of chlorine evolution reaction is inhibited. In addition, studies have shown that surface adsorbed anions may also participate in the regulation of OER reaction pathways under specific conditions, positively affecting catalytic activity. Although the above strategies improve the performance of the seawater electrolysis anode to a certain extent, most of the prior art focuses on a single regulation mechanism, namely, the catalytic activity is improved through chemical regulation or the Cl - corrosion resistance is enhanced through physical protection, and it is difficult to simultaneously combine high activity and high stability under the conditions of high Cl - concentration and high current density. High activity catalysts tend to have insufficient durability in a strongly corrosive environment, while catalysts with a relatively strong corrosion protection capability may have limited active sites and slow reaction kinetics due to interfacial shielding effects. This inherent contradiction between activity and stability is particularly pronounced in long-term operation and under industrially relevant conditions. In addition, the existing single anion protective layer has limited rejection capability to Cl -, and long-term stable operation of the support electrode in a high Cl - concentration system is difficult to realize. there