Method of producing hydrogen gas using nanocomposite catalyst
12485405 ยท 2025-12-02
Assignee
Inventors
- Mohamed Nady Abd El-Hameed Ibrahim (Riyadh, SA)
- Mohamed Khairy Omran (Riyadh, SA)
- Babiker Yagoub Elhadi Abdulkhair (Riyadh, SA)
Cpc classification
C01B3/065
CHEMISTRY; METALLURGY
B01J23/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J23/02
PERFORMING OPERATIONS; TRANSPORTING
B01J37/34
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A method of producing hydrogen comprising hydrolyzing sodium borohydride (NaBH.sub.4) with water at a temperature of from about 20 to about 75 C. in the presence of a particulate crystalline nanocomposite catalyst, wherein the ratio by weight of sodium borohydride to the particulate crystalline nanocomposite catalyst is from about 1:1 to about 5:1. The particulate crystalline nanocomposite catalyst comprises: a monoclinic Bi.sub.2O.sub.3 crystalline phase; a CaSiO.sub.3 crystalline phase; and, a graphitic-C.sub.3N.sub.4 crystalline phase, wherein at least a fraction of the graphitic-C.sub.3N.sub.4 is in the form of mesoporous nanosheets.
Claims
1. A method of producing hydrogen gas, the method comprising: hydrolyzing sodium borohydride (NaBH.sub.4) with water at a temperature of from about 20 to about 75 C. in the presence of a particulate crystalline nanocomposite catalyst, wherein the ratio by weight of sodium borohydride to the particulate crystalline nanocomposite catalyst is from about 1:1 to about 5:1, wherein the particulate crystalline nanocomposite catalyst comprises: a monoclinic Bi.sub.2O.sub.3 crystalline phase; a CaSiO.sub.3 crystalline phase; and, a graphitic-C.sub.3N.sub.4 crystalline phase, wherein at least a fraction of the graphitic-C.sub.3N.sub.4 is in the form of mesoporous nanosheets.
2. The method according to claim 1, wherein the ratio by weight of Bi.sub.2O.sub.3 to CaSiO.sub.3 to graphitic-C.sub.3N.sub.4 in the particulate crystalline nanocomposite is about (0.8-1.2):(0.8-1.2):(0.8-1.2).
3. The method according to claim 1, wherein the ratio by weight of Bi.sub.2O.sub.3 to CaSiO.sub.3 to graphitic-C.sub.3N.sub.4 in the particulate crystalline nanocomposite is about 1.0:1.0:1.0.
4. The method according to claim 1, wherein at least a fraction of the Bi.sub.2O.sub.3 and at least a fraction of the CaSiO.sub.3 of the crystalline nanocomposite are in the form of nanowires.
5. The method according to claim 4, wherein: at least 50 wt. % of the Bi.sub.2O.sub.3 is in the form of nanowires; and, at least 50 wt. % of the CaSiO.sub.3 is in the form of nanowires.
6. The method according to claim 4, wherein the nanowires of Bi.sub.2O.sub.3 and CaSiO.sub.3 have a median length of from about 20 to about 100 nm, as determined by Transmission Electron Microscopy.
7. The method according to claim 1, wherein at least 50 wt. % of the graphitic-C.sub.3N.sub.4 is in the form of mesoporous nanosheets.
8. The method according to claim 1, wherein the crystalline nanocomposite has a multimodal pore size distribution, as determined by Barrett-Joyner-Halenda (BJH) desorption analysis.
9. The method according to claim 1, wherein the crystalline nanocomposite has a trimodal pore size distribution, as determined by BJH desorption analysis.
10. The method according to claim 9, wherein the trimodal pore size distribution of the crystalline nanocomposite has: a first mode in the range of from about 2 to about 6 nm; a second mode in the range of from about 8 to about 12 nm; and, a third mode in the range of from about 14 to about 18 nm.
11. The method according to claim 1, wherein the crystalline nanocomposite has a surface area of from about 60 to about 100 m.sup.2/g, as determined by Brunauer-Emmett-Teller (BET) analysis.
12. The method according to claim 1, wherein the crystalline nanocomposite has a surface area of from about 70 to about 90 m.sup.2/g, as determined by BET analysis.
13. The method according to claim 1, wherein the crystalline nanocomposite has a pore volume of from about 0.1 to about 0.5 cm.sup.3/g, as determined by BJH desorption analysis.
14. The method according to claim 1, wherein the crystalline nanocomposite has a pore volume of from about 0.2 to about 0.3 cm.sup.3/g, as determined by BJH desorption analysis.
15. The method according to claim 1 further comprising preparing the particulate crystalline nanocomposite by: forming a solution of a calcium salt and an alkali metal silicate in a solvent comprising water and a C.sub.1-C.sub.4 alkanol; heating the solution at a temperature of from about 150 to about 250 C. to form a dry product of CaSiO.sub.3; forming graphitic-C.sub.3N.sub.4 by heating urea in a closed vessel at a temperature of from about 500 to about 700 C.; forming an acidified solution in a polar protic solvent of a bismuth salt and reducing sugar; heating the acidified solution at a temperature of from about 150 to about 250 C. for a sufficient duration to carbonize the reducing sugar to form a carbonized product; comminuting the carbonized product of the heating stage; calcining the comminuted carbonized product at a temperature of from about 500 to about 1200 C. for a duration of from about 1 to about 5 hours to form Bi.sub.2O.sub.3; dispersing the CaSiO.sub.3, graphitic-C.sub.3N.sub.4 and Bi.sub.2O.sub.3 in a polar protic solvent and heating the dispersion at a temperature of from about 150 to about 250 C. at a pressure of from about 2 to about 8 Bar; and, separating the solid crystalline nanocomposite from the heated dispersion.
16. The method according to claim 1, wherein the ratio by weight of sodium borohydride to the particulate crystalline nanocomposite catalyst is from about 1:1 to about 3:1.
17. The method according to claim 1, wherein sodium borohydride is hydrolyzed with water at a temperature of from about 25 to about 70 C.
18. The method according to claim 1, wherein sodium borohydride is hydrolyzed with water at a temperature of from about 35 to about 60 C.
19. The method according to claim 1 having a hydrogen generation rate of from about 100 to about 1500 mL min.sup.1 g.sup.1 based on the weight of the sodium borohydride.
20. The method according to claim 1 having a hydrogen generation rate of from about 200 to about 1500 mL min.sup.1 g.sup.1 based on the weight of the sodium borohydride.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) A more complete appreciation of this disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
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DETAILED DESCRIPTION
(11) Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying drawings wherever applicable, in that some, but not all, embodiments of the disclosure are shown.
(12) When describing the present disclosure, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
(13) As used herein, the words a, an and the like generally carry a meaning of one or more, unless stated otherwise.
(14) Furthermore, the terms approximately, approximate, about, and similar terms generally refer to ranges that include the identified value within a margin of 20%, 10%, or preferably 5%, and any values therebetween.
(15) When amounts, concentrations, dimensions and other parameters are expressed in the form of a range, a preferable range, an upper limit value, a lower limit value or preferable upper and limit values, it should be understood that any ranges obtainable by combining any upper limit or preferable value with any lower limit or preferable value are also specifically disclosed, irrespective of whether the obtained ranges are clearly mentioned in the context.
(16) A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. For example, if a particular element or component in a composition or article is said to have 5 wt. %, it is understood that this percentage is in relation to a total compositional percentage of 100%.
(17) As used herein, the term room temperature refers to a temperature range of 23 degrees Celsius ( C.)+2 C. in the present disclosure. As used herein, ambient conditions means the temperature and pressure of the surroundings in which the substance, composition or article is located.
(18) The temperature parameters in the present application, if not specifically limited, are both allowed to be constant temperature processing and also allowed to be varied within a certain temperature interval. It should be understood that the constant temperature processing allows the temperature to fluctuate within the precision range of the instrument control. It is allowed to fluctuate in the range of, for example, 5 C., 4 C., 3 C., 2 C., or 1 C.
(19) As used herein, the term fraction refers to a numerical quantity which defines a part up to, but not including, 100 percent or the entirety of the thing in question.
(20) As used herein the term disposed refers to being positioned, placed, deposited, arranged or distributed in a particular manner.
(21) As used herein, the term number average molecular weight (Mn) and weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the eluent in accordance with DIN 55672-1:2007-08.
(22) As used herein, the term Scanning Electron Microscopy or SEM refers to a surface-imaging technique that produces images of a sample by scanning the sample with a focused beam of electrons. Unless otherwise specified, the SEM shall include all imaging techniques using electron beams for imaging.
(23) As used herein, the term high-resolution transmission electron microscopy (HRTEM) refers to a powerful imaging technique used to observe the fine details of materials at the atomic scale. In HRTEM, a high-energy electron beam is transmitted through a thin sample, and the transmitted electrons are used to form detailed images with extremely high resolution.
(24) As used herein, the term X-ray diffraction or XRD or X-ray crystallography refers to basic technique for obtaining information on the atomic structure of crystalline materials used as a standard laboratory technique. Unless otherwise specified, the XRD shall include an analytical technique based on the diffraction of X-rays by matter, especially for crystalline materials.
(25) As used herein with respect to X-ray diffraction analysis, JCPDS denotes the Joint Committee on Powder Diffraction Standards.
(26) The term unit cell as used herein refers to the smallest and simplest volume element (i.e., parallelpiped-shaped block) of a crystal that is completely representative of the unit or pattern of the crystal, such that the entire crystal can be generated by translation of the unit cell. The dimensions of the unit cell are defined by six numbers: dimensions a, b and c; and, angles , and (Blundel et al., 1976, Protein Crystallography, Academic Press, the disclosure of which is incorporated herein by reference in its entirety). A crystal is an efficiently packed array of many unit cells.
(27) The term triclinic crystalline phase refers to a crystal structure in which the unit cell is characterized by three mutually perpendicular aces of unequal length (abc) wherein further a.
(28) An orthorhombic crystalline phase refers to a crystal structure having three mutually perpendicular axes of unequal lengths (abc) but wherein the crystal lattice forms a rectangular prism where the edges represent the three axes, all intersecting at 90-degree angles (===90).
(29) A cubic crystalline phase refers to a crystal structure where the unit cell is shaped like a cube, with three equal-length axes that are perpendicular to each other (at 90 angles). In this crystal system, the atoms or ions are arranged in a repeating pattern within the cubic lattice. The cubic crystalline structure is highly symmetric, possessing four threefold rotational axes and three fourfold rotational axes, permitting rotations of 90 around its specific axes and rotations of 120 about the body diagonals of the cube, while maintaining the same structure.
(30) A monoclinic crystalline phase refers to a crystal structure in which the unit cell of the material is characterized by three unequal axes, with two of them forming an angle that is not 90, while the third axis is perpendicular to the plane formed by the other two axes. In other words, the monoclinic crystal system has one axis that is tilted, resulting in a lack of orthogonality between all three axes. The unit cell in the monoclinic phase is thus asymmetrical, with distinct axial lengths and one non-90 angle.
(31) A tetragonal crystalline phase refers to a crystal structure in which the unit cell of the lattice has two axes of equal-length and a third axis that is of different length, but wherein all axes are at right angles (90) to each other. This crystal system may be represented as a square base (with two equal axes) and a height (the third axis) which is different, resulting in a rectangular prism-like shape. The tetragonal crystal structure possesses a four-fold rotational symmetry around its unique axis.
(32) As used herein, the term average crystallite size refers to the mean size of the crystalline domains or particles within a material. It is typically determined using X-ray diffraction (XRD) analysis, where the broadening of diffraction peaks is related to the size of the crystallites. The average crystallite size provides insight into the degree of crystallinity and the structural characteristics of the material. It is commonly expressed in nanometers (nm) and reflects the typical dimensions of the crystalline regions in the material, excluding any amorphous regions or defects.
(33) As used herein, the term particle refers to a small object that acts as a whole unit with regard to its transport and properties. As used herein, nanoparticlessometimes contracted herein to NPsrefers to particles having a particle size of 1 nanometer (nm) to 1000 nm.
(34) Unless otherwise stated, the term particle size refers to the largest axis of the particle. In the case of a generally spherical particle, the largest axis is the diameter.
(35) The term median volume particle size (Dv50), as used herein, refers to a particle size corresponding to 50% of the volume of the sampled particles being greater than and 50% of the volume of the sampled particles being smaller than the recited Dv50 value. Similarly, if used, the term Dv90 refers to a particle size corresponding to 90% of the volume of the sampled particles being smaller than and 10% of the volume of the sampled particles being greater than the recited Dv90 value. Particle size is determined herein by Scanning Electron Microscopy (SEM).
(36) As used herein, the term nanocomposite refers to a composite material in which at least one dimension of a component thereof is in the nanometer size scale (<100 nm). The nanocomposites are thus poly-phase solid materials made up of two or more nanomaterials. The term includes all types of multiphase solid material in which one of the phases has one, two, or three dimensions of less than 100 nm, or structures having nanoscale repeat distances between the different phases that make up the material.
(37) As used herein, the term porosity refers to a measure of the void or vacant spaces within a material. As used herein, the term pore volume refers to the total volume of void spaces (pores) within a material that is capable of being filled by a gas or liquid: it is typically expressed in cubic centimeters per gram (cm.sup.3/g). As used herein, the term pore diameter refers to the median width or size of the pores (void spaces) within a material, typically measured in nm or angstroms ().
(38) Pores may be micropores, mesopores, macropores, and/or a combination thereof. The pores exist in the bulk material, not necessarily in the molecular structure of the material. The term microporous means that particulate crystalline nanocomposite have pores with an average pore width (i.e., diameter) of less than 2 nm. The term mesoporous means the pores of the nanocomposite have an average pore width of 2-50 nm. The term macroporous means the pores of the nanocomposite have an average pore width larger than 50 nm. Pore size may be determined by methods including, but not limited to, gas adsorption (e.g., N.sub.2 adsorption), mercury intrusion porosimetry, and imaging techniques such as SEM and X-ray computed tomography (XRCT).
(39) Having regard to a parameter distribution of the disclosed material, the term monomodal references only one peak being observed in a frequency distribution graph of said parameter. The term polymodal references a distribution with two or more distinct peaks or modes. The terms bimodal and trimodal may be utilized herein to reference the presence of two or three modes, respectively.
(40) As used herein, the Brunauer-Emmett-Teller (BET) analysis references the method of measuring the specific surface area (m.sup.2/g) of a solid material via the adsorption of gas molecules onto the surface of the solid, as detailed in standard NF ISO 5794-1, Appendix E (June 2010).
(41) As used herein, the Barrett, Joyner, and Halenda (BJH) desorption analysis refers to the method of determining the volume of mesopores per unit mass (mL/g) of a solid material utilizing the adsorption and desorption isotherms associated with gas molecules inside the mesopores of the solid, as detailed in Technical Standard DIN 66134:1998-02.
(42) As used herein, the term porous particulate nanocomposite refers to a material composed of discrete particles that form a structure with interconnected pores or voids. These pores allow for the passage of fluids or gases, contributing to the material's overall porosity. The composite typically consists of two or more distinct phases, which may include various inorganic or organic components, and is characterized by its unique morphology, such as irregularly shaped particles or aggregates.
(43) The term graphitic carbon nitride often abbreviated to g-C.sub.3N.sub.4, refers to a family of carbon nitride compounds with a layered structure similar to graphene. Graphitic carbon nitride may be considered a synthetic polymer primarily composed of carbon and nitrogen, with some hydrogen impurities.
(44) The term powder, as used herein, means a composition that consists of finely dispersed solid particles that are free-flowing.
(45) The term dry as used herein means comprising less than 5 wt. % of any compound or composition being in liquid form when measured at 25 C. under ambient conditions. For instance, the term dry includes comprising less than 3 wt. %, less than 2 wt. %, less than 1%, or even about 0% of said compound or composition being in liquid form when measured at 25 C. under ambient conditions. Exemplary such compounds or compositions include water, oils, organic solvents and other wetting agents.
(46) The term polar solvent as used herein refers to a solvent having a dielectric constant () of more than 5 as measured at 25 C. The determination of dielectric constant () is known in the art: the use of measured voltages across parallel plate capacitors in such determinations may be mentioned. The term polar solvent may encompass both aprotic and protic solvents, wherein protic solvents are those solvents which are capable of yielding or accepting a proton and aprotic solvents are those solvents that do not yield or accept a proton.
(47) Water, for use as a (co-)solvent or diluent herein, is intended to mean water of low solids content as would be understood by a person of ordinary skill in the art. The water may, for instance, be distilled water, demineralized water, deionized water, reverse osmosis water, boiler condensate water, or ultra-filtration water. Tap water may be tolerated in certain circumstances.
(48) As used herein, comminuting refers to process of reducing the average size of solid materials into smaller particles, by crushing, grinding, cutting, vibrating, or other processes.
(49) The term hydrolysis, as used herein, is the chemical reaction of a molecule with water to produce two or more smaller molecules.
(50) As used herein, hydrogen generation rate (HGR) refers to the amount of hydrogen gas produced per unit of time during a chemical reaction.
(51) The term sonication refers to a process that uses sound energy (sonic waves) to agitate particles in a sample. As used herein, the term ultrasonication refers to irradiation with ultrasonic waves having a frequency of at least 20 kHz. Without intention to limit the present disclosure, (ultra) sonication may be performed using an (ultra)sonic bath or an (ultra)sonic probe.
(52) As used herein, the term calcination refers to a thermal treatment process which is conducted in the absence of, or under a restricted supply of ambient oxygen. This is performed to remove impurities or volatile substances and/or to induce thermal decomposition or a change in the thermally treated material.
(53) The term actinic radiation includes light with wavelengths of electromagnetic radiation ranging from the ultraviolet (UV) light range, through visible light range, and into the infrared range. Actinic radiation generally has a wavelength of from 150 to 2000 nm.
(54) As used herein, C.sub.1-C.sub.n alkyl group refers to a monovalent group that contains from 1 to n carbons atoms, that is a radical of an alkane and includes straight-chain and branched organic groups. As such, a C.sub.1-C.sub.4 alkyl group refers to a monovalent group that contains from 1 to 4 carbons atoms, that is a radical of an alkane and includes straight-chain and branched organic groups. Examples of alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; and, tert-butyl. In the present disclosure, such alkyl groups may be unsubstituted or may be substituted with one or more halogen. Where applicable for a given moiety (R), a tolerance for one or more non-halogen substituents within an alkyl group will be noted in the specification.
(55) In addition, the present disclosure is intended to include all isotopes of atoms occurring in the present compounds and complexes. Isotopes include those atoms having the same atomic number but different mass numbers. By way of general example, and without limitation, isotopes of hydrogen include deuterium and tritium, and isotopes of carbon include .sup.13C and .sup.14C. Isotopes of oxygen include .sup.16O, .sup.17O, and .sup.18O. Isotopically-labelled compounds of the disclosure may generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described herein, using an appropriate isotopically-labelled reagent in place of the non-labelled reagent otherwise employed.
(56) The present disclosure is intended to include all hydration states of a given compound or formula, unless otherwise noted or when heating a material.
(57) Aspects of the present disclosure are directed towards a particulate crystalline nanocomposite, including Bi.sub.2O.sub.3/CaSiO.sub.3/g-C.sub.3N.sub.4, designed to function as a catalyst to enhance the hydrolysis of sodium borohydride (NaBH.sub.4) with water for efficient production of hydrogen gas. The catalyst facilitates the safe and rapid release of hydrogen from NaBH.sub.4, making it an efficient solution for clean hydrogen production. The present disclosure circumvents the drawbacks of prior art by addressing key limitations, such as high catalyst costs, slow reaction rates, and environmental concerns. Traditional catalysts often require expensive materials, resulting in inefficient or slow hydrogen production. In contrast, the present disclosure uses a cost-effective catalyst that promotes faster hydrogen generation without relying on toxic or scarce materials. The simplicity of its preparation and its high catalytic activity also ensures scalability and practical applicability, making it a more efficient and sustainable alternative to existing catalytic materials. A method of producing hydrogen gas is described. The method includes hydrolyzing sodium borohydride (NaBH.sub.4) with water at a temperature of from about 20 to about 75 C. in the presence of a particulate crystalline nanocomposite catalyst. Herein, hydrolyzing sodium borohydride refers to the chemical reaction in which NaBH.sub.4 reacts with water, typically releasing hydrogen gas. In the process, NaBH.sub.4 is broken down by water, generating hydrogen as a by-product. The hydrolysis of NaBH.sub.4 is generally catalyzed to lower the activation energy of the reaction, to improve efficiency and to control the reaction rate.
(58) The particulate crystalline nanocomposite comprises, as determinable by X-Ray diffraction: a monoclinic Bi.sub.2O.sub.3 crystalline phase; a CaSiO.sub.3 crystalline phase; and, a graphitic-C.sub.3N.sub.4 crystalline phase. The presence of the monoclinic crystalline phase of Bi.sub.2O.sub.3 does not, however, preclude the presence of further crystalline phases of this trioxide compound, typically as the minority phases.
(59) In some embodiments, the ratio by weight of Bi.sub.2O.sub.3 to CaSiO.sub.3 to graphitic-C.sub.3N.sub.4 in the crystalline nanocomposite is about (0.8-1.2):(0.8-1.2):(0.8-1.2). For example, the ratio by weight of Bi.sub.2O.sub.3 to CaSiO.sub.3 to graphitic-C.sub.3N.sub.4 in the crystalline nanocomposite may be about (0.9-1.1):(0.9-1.1):(0.9-1.1). These ranges each encompass a ratio by weight of Bi.sub.2O.sub.3 to CaSiO.sub.3 to graphitic-C.sub.3N.sub.4 of in the crystalline nanocomposite of about 1.0:1.0:1.0, which itself represents a preferred embodiment of the nanocomposite.
(60) TEM is primarily known for its ability to reveal fine structural details at atomic and molecular levels, it may also provide information about the size, shape, distribution, and morphology of pores in porous materials. TEM may reveal the fine details of pore structures, especially in materials with pores in the nanometer range (e.g., mesoporous materials). By imaging thin sections of the material, it may provide high-resolution images that help identify the size, shape, and arrangement of the pores.
(61) In certain embodiments, the graphitic carbon nitride (g-C.sub.3N.sub.4) may be present in at least one of the following morphologies: nanorectangles; nanotriangles; nanopentagons; nanohexagons; nanoribbons; nanodiscs; nanoflakes; nanofoils; and, nanobelts.
(62) In some embodiments, TEM images of the crystalline nanocomposite showed a two-dimensional porous structure constructed with curled and wrinkled nanosheets and platelets of the g-C.sub.3N.sub.4. In some embodiments, at least a fraction of the graphitic-C.sub.3N.sub.4 is in the form of mesoporous nanosheets; for example at least about 50 wt. %, at least about 55 wt. %, at least about 60 wt. %, at least about 65 wt. %, at least about 70 wt. %, at least about 75 wt. %, or at least about 80 wt. % of the graphitic-C.sub.3N.sub.4 is in the form of mesoporous nanosheets.
(63) In some embodiments, at least a fraction of the Bi.sub.2O.sub.3 and at least a fraction of the CaSiO.sub.3 of the crystalline nanocomposite are in the form of nanowires. For example, at least about 50 wt. %, at least about 55 wt. %, at least about 60 wt. %, at least about 65 wt. %, at least about 70 wt. %, at least about 75 wt. %, or at least about 80 wt. % of each of the Bi.sub.2O.sub.3 and the CaSiO.sub.3 of the crystalline nanocomposite are in the form of nanowires. The nanowires of Bi.sub.2O.sub.3 and CaSiO.sub.3 may have a median length, as determined by Transmission Electron Microscopy, of from about 20 to about 100 nm, for example from about 25 to about 95 nm, from about 30 to about 90 nm, from about 35 to about 85 nm, from about 40 to about 90 nm, from about 45 to about 90 nm, from about 50 to 90 nm, from about 55 to about 90 nm, from about 60 to about 90 nm, from about 65 to about 90 nm, from about 70 to about 90 nm, from about 75 to about 90 nm, from about 80 to 90 nm or from about 85 to about 90 nm. In a specific embodiment, the nanowires of Bi.sub.2O.sub.3 and CaSiO.sub.3 have a median length of about 87 nm, as determined by Transmission Electron Microscopy.
(64) In some embodiments, the particulate crystalline nanocomposite has a surface area, as determined by Brunauer-Emmett-Teller (BET) analysis, of from 60 to about 100 m.sup.2/g, for example from about 65 to about 95 m.sup.2/g, from about 70 to about 90 m.sup.2/g, from about 75 to about 85 m.sup.2/g or from about 77 to about 83 m.sup.2/g. In a preferred embodiment, the surface area of the crystalline nanocomposite is 79.5 m.sup.2/g.
(65) Typically the crystalline nanocomposite has a polymodal pore size distribution, as determined by Barrett-Joyner-Halenda (BJH) desorption analysis. In some embodiments, the crystalline nanocomposite has a trimodal pore size distribution, as determined by BJH desorption analysis. In exemplary embodiments, the trimodal pore size distribution of the crystalline nanocomposite has: a first mode in the range of from about 2 to about 6 nm, for example from about 3 to about 5 nm, or about 3.9 nm; a second mode in the range of from about 8 to about 12 nm, for example from about 9 to about 11 nm, or about 10.3 nm; and, a third mode in the range of from about 14 to about 18 nm, for example from about 15 to about 17 nm, or about 16.39 nm. A polymodal or trimodal pore size distribution in the particulate crystalline nanocomposites, as determined by BJH desorption analysis, enhances the material's functionality by offering multiple distinct pore sizes. The diversity improves adsorption capacity, catalytic efficiency, and mass transport by providing various pore environments that accommodate different molecule sizes.
(66) In some embodiments, the crystalline nanocomposite has a pore volume, as determined by BJH desorption analysis of from about 0.1 to about 0.5 cubic centimeter per gram (cm.sup.3/g), for example from about 0.2 to about 0.4 cm.sup.3/g, or from about 0.2 to about 0.3 cm.sup.3/g. y In an exemplary embodiment, the crystalline nanocomposite has a pore volume of 0.247 cm.sup.3/g, as determined by BJH desorption analysis.
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(68) At step 52, the method 50 includes forming a solution of a calcium salt and an alkali metal silicate in a solvent which comprises water and a C.sub.1-C.sub.4 alkanol.
(69) Exemplary calcium salts, which may be present alone or in combination, include but are not limited to calcium chloride, calcium sulfate, calcium carbonate, calcium phosphate, calcium acetate, calcium citrate, calcium lactate, calcium gluconate, calcium formate, calcium oxalate, calcium tartrate, calcium ascorbate, calcium benzoate, calcium propionate, calcium stearate, calcium hydroxide, calcium peroxide, calcium iodate, calcium molybdate, calcium hypochlorite, calcium thiocyanate, calcium chromate, calcium ferrite, calcium bromide, calcium fluoride, calcium sulfide, calcium arsenate, calcium tungstate, calcium borate, calcium perchlorate, and calcium hydride. In an embodiment, the calcium salt is selected from the group consisting of calcium sulfate (CaSO.sub.4), calcium nitrate (Ca(NO.sub.3).sub.2), calcium chloride (CaCl.sub.2)) and calcium acetate (Ca(CH.sub.3COO).sub.2). In a preferred embodiment, calcium salt is calcium nitrate.
(70) Exemplary alkali metal silicates, which may be present alone or in combination, include but are not limited to potassium silicate, lithium silicate, rubidium silicate, cesium silicate, sodium orthosilicate, potassium orthosilicate, lithium orthosilicate, rubidium orthosilicate, cesium orthosilicate, sodium disilicate, potassium disilicate, lithium disilicate, rubidium disilicate, cesium disilicate, sodium trisilicate, potassium trisilicate, lithium trisilicate, rubidium trisilicate, cesium trisilicate, sodium tetrasilicate, potassium tetrasilicate, lithium tetrasilicate, rubidium tetrasilicate, cesium tetrasilicate, sodium hexasilicate, potassium hexasilicate, lithium hexasilicate, rubidium hexasilicate, and cesium hexasilicate. In a preferred embodiment, alkali metal silicate is sodium metasilicate.
(71) In some embodiments, the molar ratio of the calcium salt to the alkali metal silicate is from about 1:5 to 5:1, for example about 1:4 to 4:1, about 3:1 to 1:3, about 1:2 to 2:1, or about 1:1. Exemplary C.sub.1-C.sub.4 alkanols, which may be present alone or in combination, include but are not limited to methanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, methylpropanol, dimethylpropanol, ethylpropanol, cyclopropanol, fluoromethanol, chloromethanol, bromomethanol, and iodomethanol. In a preferred embodiment, the C.sub.1-C.sub.4 alkanol comprises or consists of ethanol.
(72) In an embodiment of step 52, the volume-by-volume (v/v) ratio of water to C.sub.1-C.sub.4 alkanol is in the range of about 1:5 to 5:1, for example about 1:4 to 4:1, about 1:3 to 3:1, or about 1:2 to 2:1. In a preferred embodiment, the v/v ratio of water to C.sub.1-C.sub.4 alkanol is 1:1.
(73) At step 54, the method 50 includes heating the solution at a temperature of from about 150 to about 250 C. to form a dry product of CaSiO.sub.3. This step involves the chemical reaction and dehydration process that are necessary for converting the precursor materials into the desired solid product. In some embodiments, heating takes place at temperature of from about 110 to about 210 C., for example from about 120 to about 220 C., from about 130 to about 230 C., from about 140 to about 220 C., from about 150 to about 210 C., from about 160 to about 200 C., from about 170 to about 190 C., or about 180 C. to form the dry product of CaSiO.sub.3. The solution is preferably heated in an autoclave; optionally, other known heating appliances may be used.
(74) At step 56, the method 50 includes forming graphitic-C.sub.3N.sub.4 by heating urea in a closed vessel at a temperature of about 500 to about 700 C. In some embodiments, the urea is heated in a closed vessel at a temperature in a range from about 500 to about 700 C., for example from about 550 to about 700 C., from about 600 to about 700 C., or from about 650 to about 700 C. In a preferred embodiment, the urea is heated in a closed vessel at about 600 C. In some embodiments, the urea is heated in a closed vessel for a duration of from about 10 to about 60 minutes, for example from about 20 to about 60 minutes, from about 30 to about 60 minutes, from about 40 to about 60 minutes, from about 50 to about 60 minutes. In a preferred embodiment, the urea is heated in a closed vessel for about 45 minutes.
(75) At step 58, the method 50 includes forming an acidified solution in a polar protic solvent of a bismuth salt and a reducing sugar.
(76) Exemplary acids having utility in the acidifying of the solution include, but are not limited to, phosphoric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chloric acid, bromic acid, iodic acid, selenic acid, telluric acid, carbonic acid, silicic acid, boric acid, chromic acid, manganic acid, periodic acid, arsenic acid, antimonic acid, stannic acid, phosphorous acid, hypophosphorous acid, hypochlorous acid, chlorous acid, hypobromous acid, bromous acid, hypoiodous acid, iodous acid, perbromic acid, periodic acid and carbonic acid. In some embodiments, the acidified solution may include an acid selected from the group consisting of hydrochloric acid (HCl), sulfuric acid (H.sub.2SO.sub.4), perchloric acid (HClO.sub.4), boric acid (H.sub.3BO.sub.3), and nitric acid (HNO.sub.3). In an exemplary embodiment, the acid is HNO.sub.3.
(77) Independently of, or additional to the use of these acids, it is preferred that the acidified aqueous solution has a pH of from about 2 to about 6, for example of from about 2 to about 5 or from about 3 to about 5.
(78) Exemplary bismuth salts, which may be used alone or in combination, include bismuth nitrate, bismuth subsalicylate and bismuth carbonate. In a preferred embodiment, the bismuth salt is bismuth nitrate.
(79) Suitable examples of reducing sugar include, but are not limited to, glucose, fructose, galactose, ribose, maltose and lactose. These reducing sugars may facilitate the reduction of various metallic ions to their lower oxidation states in an acidified aqueous solution, depending on the specific reaction and desired product. In some embodiments, the reducing sugar may be selected from monosaccharides, disaccharides, oligosaccharides, or polysaccharides. In a preferred embodiment, the reducing sugar is a monosaccharide selected from the group consisting of trioses, tetroses, pentoses, hexoses and heptoses. In another preferred embodiment, the reducing sugar is selected from the group consisting of erythrose, threose, erythrulose, ribose, arabinose, xylose, lyxose, ribulose, arabulose, xylulose, lyxulose, glucose, mannose, galactose, allose, altrose, talose, gulose, idose, fructose, psicose, sorbose, tagatose, and sedoheptulose. In yet another preferred embodiment, the reducing sugar is xylose.
(80) Exemplary polar protic solvents for step 58, which may be used alone or in combination, include but are not limited to: water and C.sub.1-C.sub.4 alkanols. In a preferred embodiment, the polar protic solvent of step 58 comprises or consists of water.
(81) In some embodiments, the w/w ratio of the bismuth salt to the reducing sugar is about 1:5 to 5:1, for example from about 1:4 to 4:1, from about 1:3 to 3:1, from about 1:2 to 2:1, or about 1:1.
(82) At step 60, the method 50 includes heating the acidified solution at a temperature of from about 150 to about 250 C. for a sufficient duration to carbonize the reducing sugar, such as xylose, in the presence of the acidified solution. The temperature range ensures efficient carbonization while preventing decomposition of the desired product. During the heating stage, the reducing sugar undergoes dehydration and polymerization to form a black carbonaceous material, which serves as the precursor for further processing.
(83) In some embodiments, the acidified solution is heated at a temperature in a range from 150 to 250 C., for example from about 175 to about 250 C. or from about 175 to about 2225 C. In a preferred embodiment, the solution is heated at 200 C. In some embodiment, the acidified solution is heated for a duration of from about 1 to about 5 hours, for example from about 1.5 to about 5 hours, from about 2 to about 5 hours, from about 2.5 to about 5 hours, from about 3 to about 5 hours, from about 3.5 to about 5 hours, from about 4 to about 5 hours, or from about 4.5 to about 5 hours. In a preferred embodiment, the acidified solution is heated for 3 hours.
(84) At step 62, the method 50 includes comminuting the carbonized product of the heating stage, typically by grinding or milling in a mortar and pestle or a ball mill, to reduce the particle size to a desired range, such as from about 50 to about 200 microns, to facilitate further processing. The comminution process ensures uniformity in the particle size, which is crucial for subsequent calcination and synthesis steps.
(85) At step 64, the method 50 includes calcining the comminuted carbonized product at a temperature of from about 500 to about 1200 C., for example from about 510 to about 650 C., or about 550 C. Without intention to limit the present disclosure, calcination may be performed for a duration of from about 1 to about 5 hours, for example from about 2.5 to about 4.5 hours, or about 4 hours to form Bi.sub.2O.sub.3. The calcination is carried out by heating it to a high temperature under a restricted supply of ambient oxygen. This is performed to remove impurities or volatile substances and to incur thermal decomposition. Typically, the calcination is carried out in a furnace, conventionally equipped with a temperature control system, which may provide a heating rate of up to about 50 C./min, for example up to 40 C./min, up to about 30 C./min, up to about 20 C./min, up to about 10 C./min, or up to about 5 C./min.
(86) At step 66, the method 50 includes dispersing the CaSiO.sub.3, graphitic-C.sub.3N.sub.4 and Bi.sub.2O.sub.3 in a polar protic solvent and heating the dispersion: at a temperature of from about 150 to about 250 C.; and, at a pressure of from about 2 to about 8 Bars. In some embodiments, the mixture may optionally be further sonicated or ultrasonicated to enhance the dispersion of CaSiO.sub.3, graphitic-C.sub.3N.sub.4, and Bi.sub.2O.sub.3 in the polar protic solvent by using (ultra) sonic waves to break up agglomerates and promote a uniform mixture.
(87) Exemplary polar protic solvents for step 66 include, but are not limited to, methanol, isopropanol, n-propanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, formamide, mono(C.sub.1-C.sub.4)alkyl ethers of ethylene glycol, mono(C.sub.1-C.sub.4)alkyl ethers of propylene glycol dimethylformamide (DMF), acetic acid, propionic acid, lactic acid, formic acid, citric acid, phosphoric acid, trifluoroacetic acid, water, ammonia, methylamine, ethylamine, isopropylamine, n-propylamine, butylamine, sec-butylamine, tert-butylamine, diethylamine, dipropylamine, dimethylamine, triethylamine, triethanolamine, n-methylformamide (NMF), n-methylacetamide (NMA), hydrazine, hydroxylamine, and urea. In an exemplary embodiment, the polar protic solvent is a C.sub.1-C.sub.4 alkanol. In a preferred embodiment, the polar protic solvent is selected from the group consisting of mono(C.sub.1-C.sub.4)alkyl ethers of ethylene glycol. An exemplary polar protic solvent is ethylene glycol monomethyl ether.
(88) In some embodiments, the solution is heated at a temperature in a range from about 150 to about 250 C., for example from about 170 to about 250 C., from about 190 to about 250 C., from about 210 to about 250 C., or from about 230 to about 250 C. In an exemplary embodiment, the solution is heated at about 180 C. In some embodiments, the solution is heated for a duration of from about 1 to about 5 hours, for example from about 1.5 to about 5 hours, from about 2 to about 5 hours, from about 2.5 to about 5 hours, from about 3 to about 5 hours, from about 3.5 to 5 hours, from about 4 to about 5 hours, from about 4.5 to about 5 hours. In an exemplary embodiment, the solution is heated for a duration of from about 2 to about 4 hours. In an alternative embodiment, the solution is heated for about 1 hour. In some embodiments, the solution is heated at about 180 C. at pressure ranging from about 2 to about 8 bar, for example from about 3 to about 8 bar, from about 4 to about 8 bar, from about 5 to about 8 bar, from about 6 to about 8 bar, or from about 7 to about 8 bar. In a preferred embodiment, the solution is heated at a pressure is about 5 bar.
(89) At step 68, the method 50 includes separating the solid crystalline nanocomposite from the heated dispersion. This separation may be achieved using techniques such as filtration (e.g., gravity filtration, vacuum filtration, pressure filtration, or membrane filtration), centrifugation, decantation, gas flotation, capacitance-based separation, or microfiltration. Alternative separation methods include natural and forced sedimentation, magnetic separation, vacuum distillation, chemical conversion, and chromatography. In a preferred embodiment, filtration is performed via a Buchner system.
(90) It is not precluded that the separated particulate crystalline nanocomposite be subjected to further processing. Such further processing may be performed in a single stage or multistage manner and may include one or more of: washing with water; drying; and, comminuting the nanocomposite in order to moderate particle morphology or the particle size distribution thereof. Exemplary drying conditions include a temperature of from about 50 to about 200 C., such as from about 100 to about 200 C. or from about 120 to about 180 C. Such drying may be carried out using known heating methods, such as a vacuum oven, rotary evaporator, microwave-assisted drying process, freeze-drying, and infrared drying.
(91) The method comprises hydrolyzing NaBH.sub.4 in the presence of the Bi.sub.2O.sub.3/CaSiO.sub.3/g-C.sub.3N.sub.4 catalyst at a temperature of about 25 to about 70 C., for example from about 27 to about 30 C., or about 28 C. In some embodiments, sodium borohydride is hydrolyzed with water at a temperature of from about 35 to about 60 C., for example from about 37 to about 40 C., or about 38 C.
(92) The ratio by weight of sodium borohydride to the particulate crystalline nanocomposite catalyst is from about 1:1 to 5:1, for example from about 1:1 to 4.5:1, about 1:1 to 3:1, or about 1.8:1 to 2.2:1.
(93) In embodiments of the hydrolysis method, the NaBH.sub.4, in solid form, is mixed with the nanocomposite in solid form to provide a solid composition that is stable and storable at room temperature: there may be no decomposition to form hydrogen when the solid mixture of the NaBH.sub.4 and the nanocomposite is stored under anhydrous conditions. The stable composition is later used as a source of hydrogen via the addition of water thereto. In alternate embodiments, the NaBH.sub.4, in solid form and the nano composite are mixed immediately prior to contact with water.
(94) It is preferred in the hydrolysis reaction that the median volume particle size (Dv50) of the nanocomposite catalyst is substantially less than the median volume particle size (Dv50) of the NaBH.sub.4. The NaBH.sub.4 may, for example, have a median volume particle size (Dv50) that is at least 5 or even at least 10 times the median volume particle size of the nanocomposite. Differences in the particle size between the two solids provide a means by which the rate of formation of hydrogen gas is buffered. For example, the rate of hydrogen gas formation achieved by adding liquid water to a mixture of particles of NaBH.sub.4 and particles of the nanocomposite having essentially the same particle size may be from 2 to 6 times the rate of hydrogen formation provided by adding water to a mixture of particles of the NaBH.sub.4 and the nano composite in which the NaBH.sub.4 particles have an average particle size that is at least five times, preferably at least 10 times the particle size of the nanocomposite.
(95) The hydrogen gas evolved as a hydrolysis product should be captured. This is often accomplished via gas collection equipment, such as inverted jars or specialized balloons, which allow the gas to gather securely. As the hydrogen forms, it is directed into these containers to keep it from escaping. Safety precautions are crucial since hydrogen is highly flammable. Once captured, hydrogen may be refined and stored for use in a variety of applications, including fuel cells and energy generation, making it an important resource for sustainable energy solutions.
(96) The method has a hydrogen generation rate of from about 100 to about 1500 milliliters per minute per gram (mL min.sup.1 g.sup.1) based on the weight of the sodium borohydride, for example from about 200 to about 1500 mL min.sup.1 g.sup.1, or from about 225 mL min.sup.1 g.sup.1 to about 1330 mL min.sup.1 g.sup.1. Hydrogen generation rate refers to the amount of hydrogen gas produced per unit of time.
(97) In some embodiments, the method of present disclosure may be adapted to other borohydride salts, including, but not limited to, potassium borohydride, calcium borohydride, magnesium borohydride, aluminum borohydride, zinc borohydride, barium borohydride, cesium borohydride, rubidium borohydride, strontium borohydride, tetrabutylammonium borohydride, ammonium borohydride, trimethylammonium borohydride, benzyltrimethylammonium borohydride, potassium tetraphenylborate, lithium tetrafluoroborate, potassium tetrafluoroborate, sodium tetrafluoroborate, copper borohydride, nickel borohydride, iron borohydride, lead borohydride, copper (II) borohydride, thallium borohydride, gold borohydride, silver borohydride, rhodium borohydride, palladium borohydride, antimony borohydride, and/or combinations thereof may also be used.
EXAMPLES
(98) The following examples demonstrate the preparation and properties of a Bi.sub.2O.sub.3/CaSiO.sub.3@g-C.sub.3N.sub.4 nanocomposite and the use of said nanocomposite as a catalyst in the hydrolysis of NaBH.sub.4 in water for producing hydrogen gas. The examples are provided solely for illustration and are not to be construed as limitations of the present disclosure, as many variations thereof are possible without departing from the spirit and scope of the present disclosure.
Example 1. Method of Preparation
(99) Equimolar amounts of calcium nitrate and sodium metasilicate were dispersed in 100 milliliters (ml) of ethanol:water (ratio by volume, 1:1) in a 150 mL glass beaker and sonicated for 15 min. The mixture was transferred to a 200 mL autoclave and then placed in an oven operated at 180 C. for 2.0 hours. The product was dispersed in 500 ml distilled water with an ultrasonic bath for 10 minutes, filtered via a Buchner system, rinsed with distilled water, and dried at 120 C. for 1.0 hour.
(100) About 30.0 grams (g) of urea was placed in a 250 mL porcelain crucible, covered with its porcelain cover, then the whole crucible and cover were wrapped with three layers of aluminum foil to reduce urea loss by evaporation. The crucible was heated via a furnace set at 600 C. for 45 minutes.
(101) About 10.0 bismuth nitrate and 10.0 g of xylose were placed in a 500 ml beaker. 100 mL ethylene glycol monomethyl ether was added to the mixture which was then heated until a clear solution was obtained. 10 mL of concentrated nitric acid was added to the mixture, which was then heated until the carbonization of xylose. The mixture was placed in an oven set at 200 C. for 3.0 hours; the black carbonized product was milled in a mortar, placed in a 150 mL porcelain dish, and calcined at 550 C. for 4.0 hours.
(102) Equal amounts of CaSiO.sub.3, g-C.sub.3N.sub.4, and Bi.sub.2O.sub.3 was transferred to a mono wave-200 vial (G30), dispersed in 20 mL ethylene glycol monomethyl ether via an ultrasonic bath for 30 minutes. The vial was closed with its Teflon cover and placed in the Anton-Baar Monowave-200 operated at 180 C. and 5.0 bar pressure for one hour. The product was dispersed in 1 L distilled water with an ultrasonic bath for 30 minutes, filtered via a Buchner system, rinsed with distilled water, and dried at 150 C. for 2.0 hours.
(103) The crystallinity and phases identification present in the Bi.sub.2O.sub.3/CaSiO.sub.3/g-C.sub.3N.sub.4 catalyst was analyzed by X-ray diffraction (XRD), and the results are given in
(104) Transmission electron microscopy (TEM) images of the synthesized Bi.sub.2O.sub.3/CaSiO.sub.3@ g-C.sub.3N.sub.4 nanocomposite are presented in
(105)
(106) The results of hydrolysis of NaBH.sub.4 with and without a fixed amount (0.5 g) of Bi.sub.2O.sub.3/CaSiO.sub.3/g-C.sub.3N.sub.4 catalyst are shown in
(107) Numerous modifications and variations of the present disclosure are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.