CN-121976231-A - Lignin carbon modified hydrogen evolution reaction catalyst and preparation method thereof

CN121976231ACN 121976231 ACN121976231 ACN 121976231ACN-121976231-A

Abstract

The invention relates to a lignin carbon modified hydrogen evolution reaction catalyst which comprises the steps of 1) dissolving lignin in deionized water to obtain a solution B, 2) respectively dissolving nickel salt, manganese salt and molybdenum salt in the solution B to obtain a mixed solution C, adding the mixed solution C and a pretreated nickel-based carrier into a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out a reaction solution in the reaction kettle for filtering, cleaning a filter cake and drying to obtain a primary sample, and 3) calcining the primary sample prepared in the step 2) at a high temperature in a mixed atmosphere environment of hydrogen and argon to obtain the lignin carbon modified hydrogen evolution reaction catalyst. According to the invention, lignin is used as a carbon source, nickel salt, manganese salt and molybdenum salt are used as metal sources, the lignin and metal ions are subjected to chelation through hydrothermal reaction synthesis, and then high-temperature calcination reduction is carried out, so that the lignin carbon-modified hydrogen evolution reaction catalyst is obtained. The catalyst prepared by the invention has the advantages of simple method, low cost and high activity.

Inventors

Qian Guangfu
WANG GUORONG
HUANG QIUYI
HUANG JIACHENG
MENG CHENGWEN
WEI XITING
Bu Guizhou
CAO XINYU
Li Liancen
LI JIAWEI
ZHANG RUYU
XU YIHAO
LU JIAXING
YAO YUAN

Assignees

广西大学

Dates

Publication Date: 20260505
Application Date: 20251225

Claims (9)

1. The preparation method of the lignin carbon modified hydrogen evolution reaction catalyst is characterized by comprising the following operation steps of: 1) Dissolving lignin in deionized water to obtain a solution A; 2) Respectively dissolving nickel salt, manganese salt and molybdenum salt in the solution A to obtain a mixed solution B, adding the mixed solution B and the pretreated nickel-based carrier into a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out the reaction solution in the reaction kettle for filtering, and washing and drying a filter cake to obtain a primary sample; The input mass ratio of the nickel salt to the manganese salt to the molybdenum salt to the lignin is 4.75-13.72:1:1.47-3.35:1; the ratio of the input mass of the nickel salt to the surface area of the pretreated nickel-based carrier is 0.9-4.2:8 g/cm 2 ; The hydrothermal reaction temperature is 120-250 ℃ and the reaction time is 4-15 hours; 3) Placing the preliminary sample prepared in the step 2) in a calciner, introducing mixed gas of hydrogen and argon, wherein the volume fraction of the hydrogen in the mixed gas is 10-20%, heating to 300-1000 ℃ at the heating rate of 5-15 ℃ per minute, and calcining at high temperature for 1-8 hours to obtain the lignin carbon modified hydrogen evolution reaction catalyst.
2. The method for preparing a lignin carbon modified hydrogen evolution reaction catalyst according to claim 1, wherein the lignin in the step 1) is one of alkaline lignin, calcium lignosulfonate, ammonium lignosulfonate, sodium lignosulfonate, dealkalized lignin, kraft lignin, sulfite lignin, hydrolyzed lignin, organosolv lignin, pyrolyzed lignin, enzymatically hydrolyzed lignin, ground lignin, carboxymethylated lignin, aminated lignin, phosphorylated lignin, carboxylated lignin, acidified lignin, acetylated lignin, sulfonated lignin or sulfurized lignin.
3. The method for preparing lignin carbon modified hydrogen evolution reaction catalyst according to claim 1 wherein the nickel salt in step 2) is one of nickel chloride, nickel molybdate, nickel borate, nickel chlorate, nickel perchlorate, nickel hypochlorite, nickel acetate, nickel bromide, nickel iodide, nickel nitrate, nickel sulfate, nickel hypophosphite, nickel sulfamate, basic nickel carbonate, nickel formate, nickel sulfide; the manganese salt in the step 2) is one of manganese chloride, manganese sulfate, manganese nitrate, manganese carbonate, manganese acetate, manganese oxalate, manganese phosphate, manganese bromide, manganese iodide, manganese fluoride, manganese perchlorate, manganese citrate, manganous sulfate, manganous acetate, manganous oxalate, manganous hydrogen phosphate, manganese pyrophosphate, manganese silicate and manganese metasilicate; the molybdenum salt in the step 2) is one of sodium molybdate, ammonium molybdate tetrahydrate, ammonium heptamolybdate, ammonium octamolybdate, ammonium dimolybdate, molybdenum trichloride, molybdenum tetrachloride, molybdenum dichloride, molybdenum chloride, lithium molybdate, potassium molybdate and ammonium tetrathiomolybdate.
4. The method for preparing a lignin carbon modified hydrogen evolution reaction catalyst according to claim 1, wherein the nickel-based carrier in the step 2) is one of a sheet nickel mesh, an annular nickel mesh, a square nickel mesh, a cylindrical nickel mesh, a special nickel mesh, a nickel wire, a nickel foil or a nickel sheet.
5. The method for preparing lignin carbon modified hydrogen evolution reaction catalyst according to claim 4, wherein the flaky nickel screen is one of rectangular nickel screen, square nickel screen and circular nickel screen; the annular nickel screen is one of an elliptical annular nickel screen, a square annular nickel screen, a rectangular annular nickel screen and a hexagonal annular nickel screen; The square nickel screen is square nickel screen or cuboid nickel screen; the cylindrical nickel screen is one of a straight cylindrical nickel screen and a spiral cylindrical nickel screen; The special-shaped nickel screen is one of a corrugated nickel screen and a cylindrical nickel screen.
6. The method for preparing a lignin carbon modified hydrogen evolution reaction catalyst according to claim 1, wherein in the step 3), after the preliminary sample is placed in a calciner and calcined, two or more nickel salts, manganese salts, molybdenum salts and one or more nickel salts, manganese salts and molybdenum salts are calcined to form an alloy, and one or more nickel salts, manganese salts and molybdenum salts are calcined to form a metal oxide, the alloy forms a heterojunction with the metal oxide and is supported on a self-supporting nickel-based carrier, the formed alloy is one or a mixture ：NiMoP、NiMoN、NiMoO、NiMo、Ni 2 Mo、MoNi 4 、NiMo、NiMo 28 、Ni 2 Mo、Ni 3 Mo、NiMo 3 、Ni 7 Mo 6 、Ni 6 Mo 5 、Mo 2 Ni 3 、Ni 5 Mo、NiMo 2 、Mo 5 Ni 3 ; of the following or the mixture of the two, and the formed metal oxide is one or a mixture of the two of the following ：NiO,Ni 2 O 3 ,Ni(OH) 2 ,Mn 2 O 3 ,MnO 2 ,Mn 3 O 4 ,MnO,Mn(OH) 2 ,MnO(OH),MoO 3 ,MoO 2 ,Mo 4 O 11 ,Mo 8 O 23 ,MoO 3 ·H 2 O,Ni 3 O 4 ,NiMn 2 O 4 ,MnNi 2 O 4 ,NiMoO 4 ,NiMo 2 O 8 ,Ni 2 Mo 3 O 12 ,MnMoO 4 ,Mn 2 Mo 3 O 12 ,MnMo 2 O 8 ,MnMoO.
7. The method for preparing the lignin carbon modified hydrogen evolution reaction catalyst according to claim 1, wherein the pretreatment method of the nickel-based carrier is characterized in that the untreated nickel-based carrier is sequentially washed with absolute ethyl alcohol, 0.5-5.0 mol/L hydrochloric acid and deionized water, each washing time is 1-6 times, and each washing time is 5-60 minutes.
8. The method for preparing the lignin carbon modified hydrogen evolution reaction catalyst according to claim 1, wherein in the step 2), nickel salt, manganese salt and molybdenum salt are respectively dissolved in the solution A to obtain a mixed solution B, the mixed solution B is subjected to ultrasonic stirring and dispersion until the mixed solution B is completely dissolved to obtain a mixed suspension liquid, and the mixed suspension liquid and the pretreated nickel-based carrier are added into a reaction kettle together for hydrothermal reaction.
9. A lignin carbon modified hydrogen evolution reaction catalyst is characterized in that the catalyst is prepared by the preparation method of one of claims 1-8.

Description

Lignin carbon modified hydrogen evolution reaction catalyst and preparation method thereof Technical Field The invention relates to the technical field of catalysts for producing hydrogen by electrolyzing water, in particular to a lignin carbon modified hydrogen evolution reaction catalyst and a preparation method thereof. Background Hydrogen energy is considered to be the most potential future energy carrier because of its high energy density and the fact that the combustion products are only water. Among the various hydrogen production technologies, electrolytic water hydrogen production is attracting attention due to advantages of clean process, high product purity, etc., wherein Hydrogen Evolution Reaction (HER) is a key step that requires a high-efficiency catalyst to reduce the reaction energy barrier and improve the hydrogen production efficiency. Therefore, the development of efficient, stable and low cost HER catalysts is key to reducing the energy consumption of electrolyzed water, driving its large scale application. The HER catalyst which is currently applied industrially takes a noble metal platinum (Pt) base material as a core, the catalytic activity of the HER catalyst is close to the thermodynamic limit, but the crust abundance of platinum is extremely low, so that the cost of the catalyst is high, agglomeration and loss are easy to occur after long-term use, and the large-scale popularization of the water electrolysis hydrogen production technology is severely restricted. Under the background, the transition metal oxide is a core research object for replacing the noble metal-based catalyst to become a HER catalyst due to the advantages of abundant reserves, low cost, adjustable electronic structure and the like. However, pure transition metal oxide heterojunctions suffer from poor conductivity, insufficient active site exposure, poor stability, and the like. In addition, the pH environment of the practical water electrolysis system has remarkable diversity (acid electrolytic tank, alkaline electrolytic tank, neutral seawater electrolysis and the like), most of non-noble metal catalysts only show excellent activity under the single pH condition, and the problem of poor wide pH adaptability severely limits the applicable scene. To solve the above problems, the introduction of high performance carriers or modifiers is a key improvement strategy. The biomass-derived carbon material is an ideal catalytic system modification material because of wide sources, rich pore structures, excellent conductivity, and rich active functional groups such as hydroxyl groups, carboxyl groups and the like on the surface. Lignin is used as a main component of agricultural and forestry waste, is an aromatic polymer with the most abundant reserves in nature, has the carbon content of 60-70 percent, is renewable and has extremely low cost, and can be converted into lignin-based carbon materials with high specific surface area and high conductivity through simple processes such as pyrolysis, activation and the like. Therefore, the invention takes lignin as a carbon-based material to modify the heterojunction of nickel-molybdenum alloy-molybdenum-manganese oxide to prepare the hydrogen evolution reaction catalyst, and aims to develop a HER catalyst with low cost, high activity, long stability and wide pH adaptability. Disclosure of Invention In order to solve the technical problems, the invention provides a lignin carbon modified hydrogen evolution reaction catalyst with low cost, high activity and wide pH applicability and a preparation method thereof. To achieve the above object, the present inventors provide a method for preparing a lignin carbon modified hydrogen evolution reaction catalyst, comprising the steps of: 1) Dissolving lignin in deionized water to obtain a solution A; 2) Respectively dissolving nickel salt, manganese salt and molybdenum salt in the solution A to obtain a mixed solution B, adding the mixed solution B and the pretreated nickel-based carrier into a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out the reaction solution in the reaction kettle for filtering, and washing and drying a filter cake to obtain a primary sample; The input mass ratio of the nickel salt to the manganese salt to the molybdenum salt to the lignin is 4.75-13.72:1:1.47-3.35:1; the ratio of the input mass of the nickel salt to the surface area of the pretreated nickel-based carrier is 0.9-4.2:8 g/cm 2; The hydrothermal reaction temperature is 120-250 ℃ and the reaction time is 4-15 hours; 3) Placing the preliminary sample prepared in the step 2) in a calciner, introducing mixed gas of hydrogen and argon, wherein the volume fraction of the hydrogen in the mixed gas is 10% -20%, heating to 300-1000 ℃ at the heating rate of 5-15 ℃ per minute, and calcining at high temperature for 1-8 hours to obtain the lignin carbon modified hydrogen evolution reaction catalyst