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CN-121974391-A - Rare earth element doped anatase titanium oxide and preparation method and application thereof

CN121974391ACN 121974391 ACN121974391 ACN 121974391ACN-121974391-A

Abstract

The invention provides rare earth element doped anatase titanium oxide, a preparation method and application thereof. The rare earth element doped anatase titanium oxide component comprises rare earth element M doped TiO 2 , wherein M is one or more of Nd, yb and Y. The rare earth element doped anatase titanium oxide has a unique electronic structure and good stability, and the doping of the rare earth element effectively regulates and controls the surface charge distribution of TiO 2 and induces a large number of active sites, so that the rare earth element doped anatase titanium oxide has excellent catalytic activity and durability in an acidic oxygen evolution reaction.

Inventors

  • ZHU LIU
  • GAO YUE
  • PENG YONG
  • HU YANG
  • SHI BOWEN
  • XIAO YUFEI
  • LIU TINGYU
  • SUO ZHIGANG

Assignees

  • 兰州大学

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. A rare earth element doped anatase titanium oxide comprises rare earth element M doped TiO 2 , wherein M is one or more of Nd, yb and Y.
  2. 2. The titanium oxide according to claim 1, wherein the molar ratio of M to Ti element in the titanium oxide is (0.07-0.1): 1.
  3. 3. A method for preparing rare earth element doped anatase titanium oxide, which comprises the following steps: 1) Mixing glucose, urea and metal salt to prepare uniform precursor solution, wherein the elements contained in the metal salt are Ti and M, and M is one or more of Nd, yb and Y; 2) Presintering the precursor solution to obtain metal salt-loaded three-dimensional foam; 3) Calcining the obtained three-dimensional foam to obtain the rare earth element doped anatase titanium oxide.
  4. 4. The method according to claim 3, wherein the metal salt comprises a titanium source and a rare earth source, preferably the rare earth source is selected from one or more of a neodymium source, an ytterbium source, and an yttrium source; Preferably, the titanium source is selected from titanium chloride, and/or The neodymium source is selected from neodymium chloride and/or neodymium nitrate, and/or The ytterbium source is selected from ytterbium chloride and/or ytterbium nitrate, and/or The yttrium source is selected from yttrium chloride and/or yttrium nitrate; Preferably, the rare earth metal source is selected from one or more of neodymium chloride, ytterbium chloride and yttrium chloride.
  5. 5. The process according to claim 4, wherein in step 1), the mass ratio of glucose to urea is 1 (0.1-0.3), and/or The molar ratio of the titanium source to the rare earth metal source is 1 (0.01-0.3), preferably 1 (0.05-0.2), more preferably 1 (0.05-0.15), still more preferably 1 (0.05-0.1), and/or The mass ratio of the rare earth metal source to the urea is (0.01-0.1): 1, preferably (0.01-0.05): 1.
  6. 6. A method according to claim 3, wherein in step 2) the pre-sintering temperature is 120 ℃ to 160 ℃, preferably 130 ℃ to 150 ℃, more preferably 135 ℃ to 145 ℃, and/or The presintering time is 8 to 12 hours, more preferably 8 to 10 hours, and/or In step 3), the calcination is carried out in air, preferably at a temperature of 350 to 550 ℃, preferably 400 to 500 ℃, and/or The calcination time is 8 to 12 hours, more preferably 10 to 12 hours.
  7. 7. An OER catalyst comprising the titanium oxide of any one of claims 1-2 or the titanium oxide prepared by the method of any one of claims 3-6.
  8. 8. The OER catalyst of claim 7, further comprising a substrate on which the titanium oxide is supported, preferably the substrate is a conductive substrate, more preferably the substrate is a carbon cloth, preferably the titanium oxide is supported on the substrate at a loading of 2 mg/cm 2 -10 mg/cm 2 .
  9. 9. Use of the titanium oxide of any one of claims 1-2 or the titanium oxide prepared by the preparation method of any one of claims 3-6 or the OER catalyst of claim 7 or 8 in the catalysis of a water splitting anode.
  10. 10. A method of water electrolysis using the titanium oxide of any one of claims 1-2 or the titanium oxide prepared by the method of any one of claims 3-6 or the OER catalyst of claim 7 or 8 for the catalytic electrolysis of water.

Description

Rare earth element doped anatase titanium oxide and preparation method and application thereof Technical Field The invention relates to the field of electrochemical catalysis, in particular to rare earth element doped anatase titanium oxide, and a preparation method and application thereof. Background With the continuous growth of global energy demand and increasing awareness of environmental protection, the development of clean, renewable energy to replace traditional fossil fuels has become urgent. The hydrogen energy is regarded as an ideal clean energy carrier because of the advantages of high energy density, no pollution of combustion products and the like. Among various hydrogen production technologies, the acidic electrolyzed water technology based on a Proton Exchange Membrane (PEM) has wide industrialization prospect due to the advantages of high efficiency, high hydrogen purity, rapid response and the like. However, the problems of slow Oxygen Evolution Reaction (OER) dynamics, high overpotential and the like of the anode of the technology severely restrict the energy efficiency and the economy of the whole hydrogen production system. Developing OER electrocatalyst with high performance and high stability becomes a key for improving the practicability of the water electrolysis hydrogen production technology. At present, noble metal-based catalysts (such as IrO 2 and RuO 2) exhibit excellent OER activity in acidic media, but their high cost and limited reserves greatly prevent their large-scale application. Non-noble metal catalysts (such as transition metal oxides, sulfides and the like) become research hot spots due to abundant resources and low price, but the materials have the problems of insufficient active sites, poor structural stability and the like under the strong acid and high potential working condition, and are difficult to meet the practical application requirements. Among them, anatase titanium dioxide (TiO 2) itself has excellent chemical stability and corrosion resistance in acidic medium, and is low in cost, but its intrinsic conductivity is low, surface reaction kinetics is poor, and its application in OER catalysis is limited. Disclosure of Invention In order to solve the technical problems, the invention provides rare earth element doped anatase titanium oxide, and a preparation method and application thereof. The energy band of the TiO 2 material is regulated and controlled by doping rare earth elements and utilizing a special electronic structure of the rare earth metals, so that the energy band structure of the material can be obviously improved, the catalytic reaction activity of the material can be improved, and the anatase titanium oxide material has excellent activity, stability and lower oxygen evolution reaction energy barrier. In a first aspect, the present invention provides a rare earth element doped anatase titanium oxide having a composition comprising rare earth element M doped TiO 2, wherein M is one or more of Nd, yb, Y. In the present invention, tiO 2 has an anatase structure. Rare earth elements (such as Nd, yb and Y) have unique 4f electronic layer structure and stronger coordination regulation and control capability, can effectively regulate the electronic structure and surface property of the material, optimize the adsorption energy of a reaction intermediate, enhance the charge transmission efficiency, and possibly induce the generation of active centers such as oxygen vacancies and the like, thereby improving the intrinsic catalytic performance. The invention utilizes the special electronic structure of rare earth metal (especially Nd, yb and Y) to regulate and control the energy band of the TiO 2 material, can obviously improve the energy band structure of the material, is beneficial to improving the catalytic reaction activity of the material, and ensures that the anatase titanium oxide material has excellent activity, stability and lower oxygen evolution reaction energy barrier. Further, the Nd 3+ of the present application achieves a perfect balance between structural stability and controlled redox activity due to its unique 4f 3 configuration, thereby having an optimal catalytic effect when applied to OER catalysts. Y 3+ optimizes the electron density of Ti/O site through electronegativity without introducing valence disturbance, thereby having better catalytic effect when applied to OER catalyst. Yb 3+ is used as an inert and stable anchor point, and the full 4f shell layer is extremely stable under OER potential, so that the catalyst has better catalytic effect when applied to OER catalysts. While other rare earth elements such as Ce and Gd, due to their respective unique electronic structures, induce adverse side effects at the TiO 2 interface, are less effective when applied to OER catalysts. In some embodiments, the rare earth element doping is in the range of 5% to 30% mole based on 100% TiO 2. In some embodiments, the rare earth element dopin