CN113600142B - Preparation method and application of formed layered double hydroxide and derivative thereof - Google Patents

Preparation method and application of formed layered double hydroxide and derivative thereof Download PDF

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CN113600142B
CN113600142B CN202110955550.9A CN202110955550A CN113600142B CN 113600142 B CN113600142 B CN 113600142B CN 202110955550 A CN202110955550 A CN 202110955550A CN 113600142 B CN113600142 B CN 113600142B
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straw
ldhs
layered double
double hydroxide
shaped layered
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CN113600142A (en
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王光辉
李德昌
张潜
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form

Abstract

The invention relates to the technical field of biomass functional materials, in particular to a preparation method and application of a formed layered double hydroxide and a derivative thereof. Selecting corn straw with honeycomb ordered macropores as a carrier or a template, and uniformly growing LDHs on the surface of straw cells through a dipping-hydrothermal process to obtain the LDHs loaded by the corn straw. The metal oxide, carbide, sulfide or phosphide which maintains the straw biological structure and the LDHs nano sheet morphology can be obtained by further carrying out aerobic calcination, carbon doping, sulfuration or phosphatization and other processes. The biological structure of the corn straw and the maintenance of the morphology of the LDHs nano sheet are conducive to mass transfer and exposure of active sites, and the method has the advantages of low preparation cost, simple process, wide universality, green and sustainable performance and good large-scale application prospect.

Description

Preparation method and application of formed layered double hydroxide and derivative thereof
Technical Field
The invention relates to the technical field of biomass functional materials, in particular to a preparation method and application of a formed layered double hydroxide and a derivative.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Layered double hydroxides (LDHs for short, comprising hydrotalcite and hydrotalcite-like compound) are layered composite metal hydroxides composed of divalent metal and polyvalent metal sharing oxygen octahedral edge, and have a structural general formula of [ M ] 2+ 1-x M 3+ x (OH) 2 ] x+ [(A n- ) x/n ·mH 2 O] x- Wherein M is 2+ (M 3+ )、A n- X and M are respectively divalent (trivalent) metal cations, interlayer anions and M 3+ /(M 2+ +M 3+ ) Molar ratio and amount of crystal water. Due to the repulsive interaction between high-valence metal ions, the metals are generally highly dispersed and doped, and the composition of the material can be regulated and controlled at the atomic level by controlling the types and the proportions of the metals. In addition, LDHs can be converted into other functional materials through the processes of ion exchange, high-temperature calcination, C/P/S doping and the like, and the porosity are maintainedRegular morphology. Therefore, the LDHs and the derivative materials thereof have wide application in the fields of catalysis, adsorption, medicine and the like.
However, in the practical application process, in order to improve convenience in transportation, application, separation and other processes, a molding treatment is generally required to be performed on the powdery LDHs by means of an adhesive or high pressure, and this process can inhibit exposure of mass transfer and reaction sites, and seriously affect exertion of intrinsic properties thereof. In recent years, researchers have developed a variety of supported LDHs materials, and the porous support selected mainly comprises: nickel foam, carbon cloth, aerogel, and the like. These searches provide solutions for improving the mass transfer properties of three-dimensionally formed LDHs. However, these carriers are expensive to prepare, complex in process, and poor in sustainability, and limit their large-scale application.
Disclosure of Invention
In order to solve the problems, the present disclosure provides a preparation method and application of a formed layered double hydroxide and a derivative thereof, wherein corn stalks are used as carriers or templates, the biological structure of the corn stalks is conducive to mass transfer and exposure of active sites, and the preparation method has the advantages of low cost, simple process, wide universality, green and sustainable properties, and has a good large-scale application prospect.
Specifically, the technical scheme of the present disclosure is as follows:
in a first aspect of the present disclosure, a method of preparing a shaped layered double hydroxide comprises:
(1): soaking corn stalks in a solution containing metal salt and alkali precursor required for synthesizing LDHs;
(2): transferring the maize straw fully immersed with the solution into a reactor, heating, reacting, and nucleating and growing LDHs to obtain the LDHs loaded by the maize straw.
In a second aspect of the disclosure, a method for preparing a molded layered double hydroxide derivative, wherein the method comprises the steps of performing aerobic calcination on the corn straw-loaded LDHs prepared by the preparation method to remove the straw and obtain a metal oxide with a straw biological structure and an LDHs nano-sheet morphology; and (3) further carrying out carbon doping, vulcanization or phosphating process on the metal oxide to obtain metal carbide, sulfide or phosphide which keeps the corn stalk biological structure and the LDHs nano-sheet morphology.
In a third aspect of the disclosure, the layered double hydroxide with a corn stalk biological structure prepared by the preparation method and/or the layered double hydroxide derivative prepared by the preparation method.
In a fourth aspect of the disclosure, the layered double hydroxide and/or the layered double hydroxide derivative with a corn stalk biological structure is applied in the fields of adsorption, catalysis and the like.
One or more of the technical schemes in the disclosure have the following beneficial effects:
(1) The corn straw is a traditional agricultural waste, has large yield and green sustainability, and has economic benefit and environmental benefit when being used in value-added mode; the corn straw is used as a mass transfer channel and a supporting framework for corn growth, has rich porosity, oxygen-containing groups and good structural stability, and is an ideal three-dimensional carrier material; therefore, the method can solve the problems of expensive preparation cost, unsustainable and the like of the traditional forming LDHs.
(2) Selecting corn straw as a carrier or a template, immersing the LDHs precursor solution, and heating to realize uniform and dense growth of the LDHs on the surface of the corn straw to obtain LDHs/straw with a corn straw biological structure, wherein a micron-sized macroporous channel of the corn straw and an LDHs nanosheet are assembled in a three-dimensional way, thereby being beneficial to mass transfer and exposure of active sites; moreover, the method has the advantages of low cost, simple process, easy scale-up production and the like, and has better large-scale application prospect.
(3) The prepared hydrotalcite with the corn stalk biological structure and the derivative material thereof belong to formed block materials, and have good mechanical strength; the LDHs uniformly grow on the cell wall surface of the corn straw and are connected with each other in an interpenetration way, and after the straw template is removed, the biological structure of the corn straw can be completely etched again, so that the advantages of the LDHs in the aspects of porosity, mass transfer, active site exposure and the like are maintained; the micron order macropores formed by the re-engraving biological structure are difficult to obtain by a chemical synthesis method.
(4) The LDHs with the corn straw biological structure obtained by the method can be further converted into other functional materials with the corn straw biological structure and the LDHs morphology through the processes of ion exchange, aerobic calcination, doping and the like, and the LDHs has wide universality, is simple in method and is easy to produce in an amplifying way.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate and explain the exemplary embodiments of the disclosure and together with the description serve to explain the disclosure, and do not constitute an undue limitation on the disclosure.
Fig. 1: a) The pretreated straw; b) The NiAl-LDHs/straw prepared in example 1; c) Nickel aluminum oxide prepared in example 5; d) Nickel phosphide prepared in example 6;
fig. 2 is an SEM image of the pretreated straw of example 1, and fig. a, b, c, d is a schematic view of shooting angles and SEM at different shooting angles, and SEM at high magnification, respectively;
fig. 3 is a SEM image of NiAl-LDHs/straw obtained in example 1: a-b) is a low-magnification SEM image, which shows the biological structure of the straw; c-d) is a high magnification SEM image showing LDHs nanoplatelets on the surface of straw cells (example 1);
fig. 4 is an SEM image of nickel aluminum oxide prepared from NiAl-LDHs/straw of example 5: a-b) is a low-magnification SEM image, which shows the biological structure of the straw; c-d) is a high-magnification SEM image, which shows the NiAl-LDHs derived nano-sheets on the surface of straw cells;
FIG. 5 is the XRD patterns of examples 1, 5, 6;
FIG. 6 is an SEM image of comparative example 1;
FIG. 7 is an SEM image of comparative example 2;
FIG. 8 is an SEM image of comparative example 3;
fig. 9 is a graph showing comparison of phosphorus adsorption performance of LDHs with corn stalk biological structure and compression molding LDHs (example 8)
FIG. 10 is a graph showing the comparison of the conversion of methyl laurate by hydrodeoxygenation under the action of metal phosphide having straw biostructure and compression molding metal phosphide (example 9).
Detailed Description
The disclosure is further illustrated below in conjunction with specific embodiments. It should be understood that these examples are merely illustrative of the present disclosure and are not intended to limit the scope of the present disclosure. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are presented for illustrative purposes only.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments in accordance with the present disclosure. As used herein, the singular forms also are intended to include the plural forms unless the context clearly indicates otherwise, and furthermore, it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, and/or combinations thereof.
At present, the traditional forming LDHs has the problems of low mass transfer efficiency, insufficient exposure of reaction sites, high preparation cost, poor application performance and the like, and therefore, the present disclosure provides a preparation method and application of forming layered double hydroxides and derivatives thereof.
In one embodiment of the present disclosure, a method for preparing a shaped layered double hydroxide comprises:
(1): soaking corn stalks in a solution containing metal salt and alkali precursor required for synthesizing LDHs;
(2): transferring the maize straw fully immersed with the solution into a reactor, heating, reacting, and nucleating and growing LDHs to obtain the LDHs loaded by the maize straw.
Based on corn straw as a carrier or a template, LDHs with a corn straw biological structure can be obtained. The layered double hydroxide of this structure facilitates mass transfer and active site exposure. The preparation method is simple and the preparation cost is low.
Or, pre-treating the corn straw before dipping the corn straw; the corn stalk pretreatment comprises: peeling corn stalk, cutting, washing with acid, washing with water to neutrality, and drying; or, the acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid, and is preferably hydrochloric acid. By preprocessing the corn straw, the influence of background metal in the corn straw on LDHs growth can be eliminated, and the porosity and specific surface area are improved.
Or, in the step (1), the solvent of the solution is selected from one or more of water, ethanol and methanol, preferably water; or, in step (1), the metal is selected from one or more of Mg, ni, co, zn, cu, ni, ca, al, fe, cr, mn; or, in the step (1), the metal salt is selected from one or more of nitrate, sulfate, acetylacetonate, halogenated salt, acetate and metal acid salt; preferably, nickel nitrate and aluminum nitrate, wherein the molar ratio of Ni to Al is between 5:1 and 1:5, preferably between 4:1 and 2:1. By controlling the molar ratio, the loading and dispersibility of the active metal in the resulting double hydroxide can be optimized, which is advantageous for exposing more active sites.
Or, in the step (1), the concentration of the metal salt is between 0.01 and 5mol/L, preferably between 0.05 and 0.15 mol/L; or, in the step (1), the alkali precursor is selected from one or more of urea, cyclohexanetetramine, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide and potassium hydroxide, preferably urea; the molar ratio of urea to the total amount of metal (total amount of divalent and polyvalent metals) is between 50:1 and 1:1, preferably between 4:1 and 2:1. Based on the above base precursor, a hydroxide having a uniform structure can be obtained.
Or, in step (2), the reaction temperature is between 80 and 150 ℃, preferably between 90 and 110 ℃; the reaction time is between 1 and 48 hours, preferably between 12 and 24 hours.
Or, the metal composition in the LDHs can be changed in an ion exchange mode to obtain a more variety of LDHs/straw composite systems; further, the ion exchange refers to the exchange of metal ions in LDHs and other metal ions in a solution; the ion exchange time is between 1 and 48 hours. The ion exchange method is simpler. By ion exchange, LDHs of various structural compositions can be obtained.
In one embodiment of the disclosure, a preparation method of a formed layered double hydroxide derivative comprises the steps of performing aerobic calcination on corn straw-loaded LDHs prepared by the preparation method to remove straw and obtain metal oxide with a straw biological structure and LDHs nano-sheet morphology; further, the aerobic calcination temperature is between 350 and 2000 ℃, preferably between 600 and 800 ℃; the calcination time is 0.1 to 24 hours, preferably 0.5 to 2 hours. At the calcining temperature, the higher porosity and smaller metal particle size can be maintained on the premise of ensuring the removal of the corn straw template, and more active sites can be obtained. Further, the metal oxide is subjected to carbon doping, sulfuration or phosphating process to obtain metal carbide, sulfide or phosphide which maintains the corn stalk biological structure and the LDHs nano-sheet morphology. Further, the carbon doping process can be a temperature programming reduction method, a chemical vapor deposition method, a thermal decomposition method and the like; or, the vulcanization process can be a solvothermal method, a high-pressure reaction method, a chemical vapor deposition method and the like; or the phosphating process can be a solvothermal method, a temperature programming reduction method, a gas-solid reaction method and the like. Based on layered double hydroxides with a maize straw biological structure, different derivatives can be obtained by simple post-treatment. This method is very simple and efficient. In particular, the straw biological structure is kept, so that the rich porosity can be provided and more active sites are exposed.
In one embodiment of the disclosure, the layered double hydroxide with straw biological structure prepared by the preparation method and/or the layered double hydroxide derivative prepared by the preparation method.
In one embodiment of the disclosure, the layered double hydroxide and/or the layered double hydroxide derivative with the corn stalk biological structure is applied to the fields of adsorption, catalysis and the like. The application fields of the layered double hydroxides and the derivatives thereof are very wide, and compared with the traditional similar molding materials, the layered double hydroxides and the derivatives thereof have advantages in mass transfer and active site exposure, so that the layered double hydroxides and the derivatives thereof have potential advantages in a plurality of application scenes. In particular, the layered double hydroxide and the derivative with the corn stalk biological structure prepared by the method have more excellent performance in phosphorus adsorption and hydrodeoxygenation of fatty acid methyl ester in water.
Further, the application includes: the LDHs loaded by the corn straw is used for adsorbing the phosphorus in the water body: weighing LDHs material loaded by corn straw, placing the LDHs material into a centrifuge tube, and adding a potassium dihydrogen phosphate solution to perform adsorption reaction; further, the LDHs loaded by the corn straw are MgAl-LDHs.
Or, the formed layered double hydroxide derivative is used for catalyzing the reaction of preparing undecane/dodecane by hydrodeoxygenation of methyl laurate; further, the derivative is NiAl-LDHs/straw-derived nickel aluminum phosphide with a straw biological structure.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present disclosure, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
NiAl-LDHs/straw for preparing biological structures of corn straw:
a) Pretreating corn stalks, peeling the corn stalks, cutting the corn stalks into segments, washing the corn stalks with 1M dilute hydrochloric acid for 3 times, washing the corn stalks with water until the corn stalks are neutral, and drying the corn stalks to obtain pretreated corn stalks;
b) 4.5mmol Ni (NO) 3 ) 2 ·6H 2 O、1.5mmol Al(NO 3 ) 3 ·9H 2 O and 13.5mmol of urea are dissolved in 90mL of deionized water and stirredStirring until the mixture is clear;
c) Soaking the washed and dried straw in the solution, and fully soaking the straw to saturation;
d) Transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; and washing the obtained product with water for several times, removing the residual reactants, and drying to obtain the NiAl-LDHs/straw with the corn straw biological structure.
Example 2
Preparation of NiAl-LDHs/straw (high load) with corn straw biological structure:
a) Peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying;
b) 9mmol Ni (NO) 3 ) 2 ·6H 2 O、3mmol Al(NO 3 ) 3 ·9H 2 Dissolving O and 27mmol urea in 90mL deionized water, and stirring until the solution is clear;
c) Soaking the washed and dried straw in the solution, and fully soaking the straw to saturation;
d) Transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; and washing the obtained product with water for several times, removing the residual reactants, and drying to obtain the high-load NiAl-LDHs/straw with the corn straw biological structure.
Example 3
Preparing NiFe-LDHs/straw with a corn straw biological structure:
a) Peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying;
b) 9mmol Ni (NO) 3 ) 2 ·6H 2 O、3mmol Fe(NO 3 ) 3 ·9H 2 Dissolving O and 27mmol urea in 90mL deionized water, and stirring until the solution is clear;
c) Soaking the washed and dried straw in the solution, and fully soaking the straw to saturation;
d) Transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; and washing the obtained product with water for several times, removing the residual reactants, and drying to obtain the NiFe-LDHs/straw with the straw biological structure.
Example 4
Preparing NiCoFe-LDHs/straw with a corn straw biological structure through ion exchange:
a) Peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying;
b) 9mmol Ni (NO) 3 ) 2 ·6H 2 O、3mmol Fe(NO 3 ) 3 ·9H 2 Dissolving O and 27mmol urea in 90mL deionized water, and stirring until the solution is clear;
c) Soaking the washed and dried straw in the solution, and fully soaking the straw to saturation;
d) Transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; washing the obtained product with water for several times, removing the residual reactant, and drying to obtain NiFe-LDHs/straw with the straw biological structure maintained;
e) Dipping NiFe-LDHs/straw in Co (NO) of 50mmol/L 3 ) 2 Slowly stirring and soaking for 24 hours in the solution, washing the obtained product with water for several times, and drying to obtain NiCoFe-LDHs/straw with the straw biological structure maintained; example 5
Preparing Ni-Al oxide with corn straw biological structure derived from NiAl-LDHs:
placing the NiAl-LDHs/straw prepared in the embodiment 1 into a muffle furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, calcining for 1h, and cooling to obtain the Ni-Al oxide with the corn straw biological structure derived from the NiAl-LDHs.
Example 6
Preparing NiAl-LDHs derived phosphide with a corn straw biological structure:
placing the NiAl-LDHs/straw prepared in the embodiment 1 in a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, calcining for 1h, and cooling to obtain the oxide with the corn straw biological structure derived from the NiAl-LDHs; the oxide is then reacted with 10 times the mass of NaH 2 PO 2 Is placed in a tube furnace to be treated,after vacuumizing, heating to 450 ℃ at a heating rate of 5 ℃/min for 2 hours, and cooling to obtain Ni which is derived from NiAl-LDHs and has a corn straw biological structure 2 P。
Example 7
Preparing MgAl-LDHs/straw with corn straw biological structure:
peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying; 4.5mmol of Mg (NO 3 ) 2 ·6H 2 O、1.5mmol Al(NO 3 ) 3 ·9H 2 O and 13.5mmol urea are dissolved in a mixed solution of 45mL deionized water and 45mL ethanol, and stirred until the solution is clear; soaking the washed and dried straw in the solution, and fully soaking the straw to saturation; transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; and washing the obtained product with water for several times, removing the residual reactant, and drying to obtain MgAl-LDHs/straw with the straw biological structure maintained.
Example 8
The MgAl-LDHs/straw prepared in the embodiment 7 and kept with the straw biological structure is used for adsorbing phosphorus in water body:
80mg of MgAl-LDHs/straw material prepared in example 7 is weighed and placed in a 50mL centrifuge tube, 40mL of potassium dihydrogen phosphate solution with initial P concentration of 30ppm is added, the initial pH value is adjusted to 5.0, the rotary adsorption reaction is carried out on a rotary bed, and sampling and testing are carried out at intervals. The MgAl-LDHs particles (comparative example 4) formed by high-pressure compression molding with the same quality are taken as a control group, and performance test is carried out under the same condition.
As shown in fig. 9, the adsorption rate of MgAl-LDHs/straw with straw biological structure to P is obviously better than that of MgAl-LDHs particles formed by high-pressure compression, supporting the expectation that biological structure promotes mass transfer and active site exposure.
Example 9
The NiAl-LDHs/straw-derived nickel aluminum phosphide with a straw biological structure is used for catalyzing the reaction of preparing undecane/dodecane by hydrodeoxygenation of methyl laurate:
firstly, weighing 100mg of nickel aluminum phosphide catalyst prepared in example 6, filling the catalyst in a fixed bed reactor, charging hydrogen into the reactor to 3Mpa, setting the reaction temperature to 350 ℃, setting the flow rate of hydrogen to 110mL/min, and introducing methyl laurate into the reactor at the flow rate of 0.055 mL/min. Sampling and testing at intervals, wherein the internal standard is tetrahydronaphthalene, and detecting the reaction product by using a gas chromatograph and a gas chromatograph-mass spectrometer. The nickel-aluminum phosphide particles formed by high-pressure compression molding with the same quality are taken as a control group, and the performance test is carried out under the same condition.
As shown in FIG. 10, the conversion rate of methyl laurate is about 90% under the catalysis of nickel-aluminum phosphide with straw biological structure, which is obviously better than nickel-aluminum phosphide particles (54%) formed by high-pressure compression molding, and supports the expectation that the biological structure promotes mass transfer and active site exposure.
Comparative example 1
Preparing NiAl-LDHs powder without straw:
9mmol Ni (NO) 3 ) 2 ·6H 2 O、3mmol Al(NO 3 ) 3 ·9H 2 O and 27mmol urea are dissolved in 90mL deionized water, stirred until the mixture is clear, placed in a polytetrafluoroethylene hydrothermal kettle and placed in a 100 ℃ oven for reaction for 24 hours. And after the hydrothermal reaction is finished, filtering to separate out precipitate, washing with water for 3-5 times, and drying to obtain common NiAl-LDHs powder.
Comparative example 2
Preparing straw-free Ni-Al oxide powder:
placing the NiAl-LDHs powder obtained in the comparative example 1 into a muffle furnace for aerobic roasting, wherein the heating rate is 10 ℃/min, the roasting temperature is 800 ℃, and the temperature is kept for 1h; and cooling to obtain the Ni-Al oxide derived from the NiAl-LDHs.
Comparative example 3
Preparing NiO with a corn straw structure but without LDHs morphology:
a) Peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying;
b) 9mmol Ni (NO) 3 ) 2 ·6H 2 Dissolving O and 27mmol urea in 90mL deionized water, and stirring until the solution is clear;
c) Soaking the washed and dried straw in the solution, and fully soaking the straw to saturation;
d) Transferring the straw filled with the LDHs precursor solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; washing the obtained product with water for several times, removing residual reactants, and drying;
e) Placing the sample in a muffle furnace for aerobic roasting, wherein the temperature rising rate is 10 ℃/min, the roasting temperature is 800 ℃, and the sample is kept for 1h; and cooling to obtain NiO with a straw structure but without LDHs morphology.
Comparative example 4
Preparing MgAl-LDHs formed particles without biological structures:
9mmol of Mg (NO) 3 ) 2 ·6H 2 O、3mmol Al(NO 3 ) 3 ·9H 2 O and 27mmol urea are dissolved in 90mL deionized water, stirred until the mixture is clear, placed in a polytetrafluoroethylene hydrothermal kettle and placed in a 100 ℃ oven for reaction for 24 hours. And after the hydrothermal reaction is finished, filtering to separate out precipitate, washing with water for 3-5 times, and drying to obtain MgAl-LDHs powder. The obtained common MgAl-LDHs powder is placed in a tablet press and pressed and molded under the pressure of 5MPa, and then MgAl-LDHs particles are obtained.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (29)

1. A method for preparing a shaped layered double hydroxide, comprising:
(1): soaking corn stalks in a solution containing metal salt and alkali precursor required for synthesizing LDHs;
(2): transferring the maize straw fully immersed with the solution into a reactor, heating, reacting, and nucleating and growing LDHs to obtain LDHs/straw with a maize straw biological structure;
wherein, before the corn stalk is soaked, the corn stalk is pretreated; the corn stalk pretreatment comprises: peeling corn stalk, cutting, washing with acid, washing with water to neutrality, and drying.
2. A method of preparing a shaped layered double hydroxide according to claim 1, wherein the acid is selected from one or more of hydrochloric acid, sulfuric acid, and nitric acid.
3. A method for producing a shaped layered double hydroxide according to claim 2, wherein said acid is hydrochloric acid.
4. The method for producing a shaped layered double hydroxide according to claim 1, wherein in the step (1), the solvent of the solution is one or more selected from the group consisting of water, ethanol, and methanol.
5. The method for producing a shaped layered double hydroxide according to claim 4, wherein in the step (1), the solvent of the solution is water.
6. A method of producing a shaped layered double hydroxide according to claim 1, wherein in step (1), the metal is selected from one or more of Mg, ni, co, zn, cu, ca, al, fe, cr, mn.
7. The method for producing a shaped layered double hydroxide according to claim 1, wherein in the step (1), the metal salt is one or more selected from the group consisting of nitrate, sulfate, acetylacetonate, halide, acetate and metal salt.
8. The method for producing a shaped layered double hydroxide according to claim 7, wherein in the step (1), the metal salt is nickel nitrate and aluminum nitrate; wherein the molar ratio of Ni to Al is between 5:1 and 1:5.
9. The method for producing a shaped layered double hydroxide according to claim 8, wherein the molar ratio of Ni to Al is between 4:1 and 2:1.
10. The method for producing a shaped layered double hydroxide according to claim 1, wherein in the step (1), the concentration of the metal salt is between 0.01 and 5 mol/L.
11. The method for producing a shaped layered double hydroxide according to claim 10, wherein in the step (1), the concentration of the metal salt is between 0.05 and 0.15 mol/L.
12. The method for producing a shaped layered double hydroxide according to claim 1, wherein in the step (1), the base precursor is one or more selected from urea, cyclohexanetetramine, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide; the molar ratio of the base precursor to the total amount of metal is between 50:1 and 1:1.
13. The method for producing a shaped layered double hydroxide according to claim 12, wherein in the step (1), the base precursor is urea; the molar ratio of urea to the total amount of metal is between 4:1 and 2:1.
14. The method for producing a shaped layered double hydroxide according to claim 1, wherein in the step (2), the reaction temperature is 80 to 150 ℃; the reaction time is between 1 and 48 hours.
15. The method for producing a shaped layered double hydroxide according to claim 14, wherein in the step (2), the reaction temperature is between 90 and 110 ℃; the reaction time is between 12 and 24 hours.
16. The method for preparing the formed layered double hydroxide according to claim 1, wherein the metal composition of the LDHs loaded by the corn straw can be changed in an ion exchange manner to obtain a plurality of types of LDHs/straw composite systems.
17. The method for producing a shaped layered double hydroxide according to claim 16, wherein the ion exchange means that metal ions in LDHs are exchanged with other metal ions in a solution; the ion exchange time is between 1 and 48 and h.
18. A preparation method of a formed layered double hydroxide derivative is characterized by comprising the following steps:
(1) Removing the straw from the LDHs/straw prepared by the preparation method of any one of claims 1-17 through aerobic calcination to obtain metal oxide with corn straw biological structure and LDHs nano-sheet morphology;
(2) And further carrying out carbon doping, vulcanization or phosphating process on the metal oxide to obtain metal carbide, sulfide or phosphide with corn straw biological structure and LDHs nano-sheet morphology.
19. A method of preparing a shaped layered double hydroxide derivative according to claim 18, wherein the carbon doping process is a temperature programmed reduction process, a chemical vapor deposition process, or a thermal decomposition process.
20. A method of preparing a shaped layered double hydroxide derivative according to claim 18, wherein the sulfidation process is solvothermal, high pressure reaction, or chemical vapor deposition.
21. A method of preparing a shaped layered double hydroxide derivative according to claim 18, wherein the phosphating process is selected from the group consisting of solvothermal, temperature programmed reduction, and gas-solid reaction.
22. A process for the preparation of a shaped layered double hydroxide derivative according to claim 18, wherein the aerobic calcination temperature is between 350 ℃ and 2000 ℃; the calcination time is between 0.1 and 24 hours.
23. A process for the preparation of a shaped layered double hydroxide derivative according to claim 22, wherein the aerobic calcination temperature is between 600 ℃ and 800 ℃; the calcination time is 0.5-2h.
24. LDHs/straw with corn straw biological structure prepared by the preparation method of any one of claims 1-17 and/or the shaped layered double hydroxide derivative prepared by the preparation method of claims 18-23.
25. The use of LDHs/straw and/or shaped layered double hydroxide derivatives with a corn straw biological structure according to claim 24 in the adsorption and catalysis field.
26. The application of claim 25, wherein the application comprises: LDHs/straw is used for adsorbing phosphorus in water body: weighing LDHs/straw materials, placing the LDHs/straw materials into a centrifuge tube, and adding a potassium dihydrogen phosphate solution for adsorption reaction.
27. The use of claim 26, wherein the LDHs/straw is MgAl-LDHs/straw.
28. Use according to claim 25, wherein the shaped layered double hydroxide derivative is used to catalyze the reaction of methyl laurate hydrodeoxygenation to undecane/dodecane.
29. The use according to claim 28, wherein the derivative is NiAl-LDHs/straw-derived nickel aluminide having a straw biological structure.
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