CN111712338A - Method for producing atomic quantum clusters - Google Patents

Method for producing atomic quantum clusters Download PDF

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CN111712338A
CN111712338A CN201980009957.3A CN201980009957A CN111712338A CN 111712338 A CN111712338 A CN 111712338A CN 201980009957 A CN201980009957 A CN 201980009957A CN 111712338 A CN111712338 A CN 111712338A
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mixture
metal salt
metal
silver
polar solvent
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CN111712338B (en
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曼纽尔·阿图罗·洛佩斯金特拉
大卫·布塞塔费尔南德斯
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Universidade de Santiago de Compostela
Nanogap Sub NM Powder SA
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Nanogap Sub NM Powder SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material

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Abstract

The present invention provides an easy and scalable process for the production of Atomic Quantum Clusters (AQCs) in the presence of promoters in high yield and without the need for capping ligands. Further, the present invention provides a mixture comprising at least an atomic quantum cluster, optionally a metal salt, optionally a hole scavenger having a standard electrode potential lower than the HOMO orbital of the AQC, optionally an oxidant having a standard electrode potential higher than the standard electrode potential of the metal ion, and a polar solvent, wherein both the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other, and wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.

Description

Method for producing atomic quantum clusters
Technical Field
The present invention relates to a method for producing Atomic Quantum Clusters (AQCs).
Background
The high catalytic activity of metal clusters of minority Atoms (AQCs) compared to isolated atoms or nanoparticles is well known in the art [ A. Corma et al, Nature Chemistry, Vol.5, p. 775-781, 2013 ]. In particular, since Atomic Quantum Clusters (AQCs) are used in biosensors [ Peyser, l.a.; vinson, a.e.; bartko, a.p.; potential applications in the fields of Dickson, r.m., Science, 2001, 291, 103], electrocatalysis [ Boyen H-g, et al, Science 2002, 297, 1533], magnetic, photoluminescent or catalytic [ Nano eng. hydrogels for cell eng, 2012, Springer Netherlands, Bhushan, Bharat editors, page 2639-2648 ] have attracted considerable interest in the development of simple synthetic methods that can be scaled up to large scale for mass production of AQCs.
Several methods for the synthesis of stable AQCs have been developed in recent years. In particular, there are two main methods for synthesizing metal clusters by soft chemical methods: i) top-down approach (top-down approach) by etching small nanoparticles with an excess of strongly binding ligands; and ii) bottom-up approach (bottom-up appaach), using strongly binding ligands to inhibit growth, usually with strong reducing agents [ Nano eng. hydrogels for cell eng., 2012, Springer Netherlands, Bhushan, Bharat editors, p. 2639-2648 ]. However, ligands are often required in both approaches, which may hinder some important properties of AQCs, such as catalysis.
EP1914196a1(2008) at the university of san diego, de university of portspace reports a kinetic control method for the production of stable AQCs that does not require the use of strongly binding ligands or capping agents, wherein metal salts or metal ions are reduced by reducing agents, while maintaining a small rate constant and low reagent concentration. However, this method produces very low amounts of bare clusters (clusters without ligands) at about micromolar concentrations. In addition, the massive formation of nanoparticles as the reaction rate increases prevents the mass production of naked AQCs by this method due to the lack of ligands.
Thus, despite the reported methods, there remains a need in the art for new simple and scalable methods to produce AQCs at high concentrations and yields.
Disclosure of Invention
It is an object of the present invention to provide a scalable process for the production of AQCs in improved yields in the absence of ligand (naked AQCs). In view of the different stability of AQCs and nanoparticles under oxidative conditions, the present inventors have developed a new approach. Accordingly, in a first aspect, the present invention relates to a method for producing Atomic Quantum Clusters (AQCs), comprising the steps of:
a) providing a mixture comprising:
-a picomolar to micromolar concentration of the starting atomic quantum clusters,
-a metal salt of a metal selected from the group consisting of,
-a polar solvent, the solvent being a polar solvent,
a hole scavenger (HOMO) having a standard electrode potential lower than the Higher Occupied Molecular Orbital (HOMO) of the starting atomic quantum cluster,
wherein the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other;
wherein the number of equivalents of the hole scavenger in the mixture is higher than the number of equivalents of the metal salt;
b) applying a promoter to the mixture of step (a), wherein the promoter is photoradiation having an energy equal to or greater than the HOMO-LUMO gap of the starting atomic quantum cluster of the mixture of step (a); and
c) adding an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt;
wherein the oxidizing agent may be added to the mixture of step (a) and/or during and/or after the application of the promoter in step (b).
Furthermore, in a second aspect, the present invention relates to a mixture comprising:
-a cluster of atomic mass photons,
-a metal salt of a metal selected from the group consisting of,
-an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt,
-a hole scavenger having a standard electrode potential lower than the HOMO orbital of the atomic quantum cluster, and
-a polar solvent, the solvent being a polar solvent,
wherein both the metal salt and the hole scavenger are soluble in the mixture and are not reactive with each other, and
wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the written description, serve to explain the principles of the invention. In the drawings:
FIG. 1: ESI-Mass Spectroscopy of AQCs obtained by the method of the present invention (example 1).
FIG. 2: UV-VIS spectra of the reaction mixture of example 1at different times.
FIG. 3: UV-VIS spectra of the reaction mixture of example 2 at different times.
Detailed Description
The present invention provides a new and simple method for producing atomic quantum clusters with high yield. In particular, the methods of the present invention allow naked AQCs to be obtained in solution in the absence of ligand at a yield of about 40%.
The method of the present invention is a method for producing Atomic Quantum Clusters (AQCs) comprising the steps of:
a) providing a mixture comprising:
-a picomolar to micromolar concentration of the starting atomic quantum clusters,
-a metal salt of a metal selected from the group consisting of,
-a polar solvent, the solvent being a polar solvent,
a hole scavenger having a standard electrode potential lower than the Higher Occupied Molecular Orbital (HOMO) of the starting atomic quantum cluster,
wherein the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other;
wherein the number of equivalents of the hole scavenger in the mixture is greater than the number of equivalents of the metal salt;
b) applying a promoter to the mixture of step a), wherein the promoter is photoradiation having an energy equal to or greater than the HOMO-LUMO gap of the starting atomic quantum cluster of the mixture of step a); and
c) adding an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt;
wherein an oxidizing agent may be added to the mixture of step a) and/or to the mixture during and/or after the application of the promoter in step b).
In a particular embodiment, an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt is in the mixture of step (a).
The term "cluster" refers to nano/sub-nano species consisting of a well-defined structure of metal atoms having a size below about 1nm to 2 nm. Due to quantum effects, the clusters exhibit discrete energy levels and increasing bandgaps as the AQC size decreases.
According to the present invention, the terms "atomic quantum cluster", "bare atomic quantum cluster" or "AQC" mean a group of two or more zero-valent transition metal atoms in the absence of any ligands. Thus, the method of the present invention is a method for producing Atomic Quantum Clusters (AQCs) without ligands (i.e., naked AQCs).
Atomic Quantum Clusters (AQCs) are reported in ES2277531B2 and WO 2007/017550.
In the prior art, atomic quantum clusters are also referred to as "metal quantum clusters". AQCs consist of the same (mononuclear cluster) or different (heteronuclear cluster) transition metals. In the context of the present invention, the term "metal" refers to elements of the periodic table that are referred to as "metals", in particular "transition metals", but without reference to the electrical behavior of said elements. As reported in EP1914196a1, confinement of the electrodes in AQCs causes quantum separation of energy levels, which gives important changes in the properties of these materials. Thus, the metal atoms in the AQCs have a semiconductor-like or even insulation-like behavior.
AQC is represented as Mn, where M represents any zero-valent transition metal and n represents the number of atoms. The number of atoms in the AQCs is less than 100 atoms and the size of the AQCs is less than 1nm to 2 nm.
The term "starting atomic quantum cluster" refers to the atomic quantum cluster that initiates the method of the invention. Furthermore, the starting atomic quantum clusters act as catalysts in the process of the present invention. In a particular embodiment, the starting AQCs are formed from a transition metal selected from the group consisting of: platinum (Pt), gold (Au), rhodium (Rh), iridium (Ir), palladium (Pd), ruthenium (Ru), osmium (Os), silver (Ag), copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), titanium (Ti), vanadium (V), chromium (Cr), or bimetallic and multi-metallic combinations thereof. Preferably, the metal of the AQC is selected from Au, Ag, Cu, Pd and Pt or a bimetallic combination thereof. More preferably, the metal of the starting AQC is selected from Au and Ag or a bimetallic combination thereof; even more preferably, the metal of the starting AQC is Ag.
Suitable starting atomic quantum clusters include any AQC available on the market or obtained in the laboratory by methods known in the art. Furthermore, some of the metal salts available on the market may already contain small amounts of AQCs, which can serve as starting AQCs (Peyser, l.a.; Vinson, a.e.; Bartko, a.p.; Dickson, r.m. science 2001, 291, 103-. However, it is recommended to strictly control the amount of clusters present in the metal salt in order to obtain reproducible results.
According to the invention, the mixture provided in step a) comprises picomoles (1 × 10)-12M) to micromolar concentration (1 × 10)-6M) starting atomic quantum clusters. In thatIn a preferred embodiment, the mixture of step a) of the process of the invention is 1 × 10-10M to 1 × 10-7M, preferably 1 × 10-9M to 1 × 10-8The concentration of M, more preferably, comprises the starting atomic quantum clusters in nanomolar concentration.
In the context of the present invention, the term "metal salt" refers to a compound consisting of a metal cation (positively charged ion) and an anion (negative ion) such that the resulting net charge in the metal salt is zero. In a particular embodiment, the metal salt is a limiting reactant (limiting reactant) in the process of the invention, as understood in the art.
In a particular embodiment, the metal of the metal salt is selected from silver, platinum, palladium, gold, copper, iridium, rhodium, ruthenium, nickel, iron, cobalt, or bimetallic and polymetallic combinations thereof. Preferably, the metal of the metal salt is selected from Au, Ag, Cu, Pd and Pt or a bimetallic combination thereof; more preferably Ag, Cu, Pd and Pt; even more preferably Ag.
In a particular embodiment, the metal of the metal salt and the metal of the starting AQC are the same metal or different metals; preferably different metals. In another particular embodiment, the metal of the metal salt and the metal of the starting AQC are different metals and therefore the metal of the AQC produced is the same as the metal of the metal salt.
In a particular embodiment, the metal of the metal salt and the metal of the starting AQC are the same metal, preferably silver.
In a particular embodiment, the metal salt is a silver salt, preferably a silver salt selected from the group consisting of silver bromate, silver bromite, silver chlorate, silver perchlorate, silver chlorite, silver fluoride, silver nitrate, silver nitrite, silver acetate, silver permanganate, and mixtures thereof; preferably silver nitrate.
The metal salt and the hole scavenger of the reaction mixture of the process of the invention are soluble in the polar solvent and do not react with each other.
The mixture of step a) of the process of the invention also comprises a polar solvent in which the metal salt and the hole scavenger are soluble. In a preferred embodiment, the polar solvent is selected from the group consisting of water, acetonitrile, chloroform, dichloromethane, acetic acid, toluene, and mixtures thereof.
In the context of the present invention, the term "hole scavenger" refers to a sacrificial agent that is oxidized by holes generated by the excitation of the starting AQCs. In the methods of the present invention, the standard electrode potential of the hole scavenger is lower than the HOMO orbital (higher occupied molecular orbital) of the starting AQC, such that when the promoter is applied to the reaction mixture, the hole scavenger provides an electron with a standard electrode potential sufficient to fill the hole generated in the starting AQC.
The term "standard electrode potential" is well known in the art and means in the standard state, i.e. at an effective concentration of 1mol dm-3Is measured against the single potential of the electrode at 25 c, in the case of a gas with a pressure of 1 atm. The standard electrode potential is typically represented by E °. The standard electrode potential is also referred to as reduction potential because the higher the value of the standard electrode potential, the more easily the element is reduced (accepts electrons); therefore, they are better oxidants.
As previously reported (J.Calvo, J.Rivas and M.A.L. Lopez-Quintela, Synthesis of Subnometric Nanoparticles, Encyclopedia of Nanotechnology, B.Bharat. editor, Springer Verlag, Dordrecht, 2012, 2639. sup. 2648; N.Vilar-Vidal, J.Rivas and M.A.L. pez-Quintela, ACS Catalysis, 2012, 2, 1693. sup. 16997), HOMO-LUMO interstitial energy (E.C. Catalysis, 2012, 2, 1693. sup. 1699) of the AQC can be obtained from the HOMO-LUMO interstitial energy of the AQCg) HOMO orbital energy E to complete AQCHOMOCan be calculated by the Jellium model or by the UV-vis absorption spectrum and corresponding fermi level (E) of the AQCF) Experimentally calculated, and can be estimated from the fermi levels of the respective metals: eHOMO＝-EF-1/2Eg. Can be used for AQC E through ultraviolet light electronic energy spectrumHOMOA more accurate estimation is performed. In the process of the present invention, the hole scavenger is not reactive with the metal salt. In addition, the hole scavengers as well as the metal salts are soluble in the reaction mixture of the process of the invention.
In a particular embodiment, the hole scavenger is selected from linear or branched alcohols having from 2 to 6 carbon atoms. Preferably, the hole scavenger is ethanol, propan-1-ol, isopropanol, butan-1-ol, butan-2-ol, isobutanol, 1-dimethyl-ethanol, pentan-1-ol, pentan-2-ol, pentan-3-ol, 2-methylbutan-1-ol, 3-methylbutan-2-ol, 2-dimethylpropan-1-ol, hexan-2-ol, hexan-3-ol, 2-methylpentan-1-ol, 3-methylpentan-1-ol, 4-methylpentan-1-ol, 2-methylpentan-2-ol, 2-methylbutan-1-ol, 2-methylbutan-2-ol, 2-methylbutan-1-ol, 2, 3-methylpent-2-ol, 4-methylpent-2-ol, 2-methylpent-3-ol, 3-methylpent-3-ol, 2-dimethylbut-1-ol, 3-dimethylbut-1-ol, 2, 3-dimethylbut-2-ol, 3-dimethylbut-2-ol, 2-ethylbuta-1-ol and mixtures thereof. In another particular embodiment, the hole scavenger is selected from the group consisting of hydroquinone, iodide salts, oxalic acid, acetic acid, formic acid, sodium formate, sulfites, and mixtures thereof.
In the context of the present invention, other suitable hole scavengers include glycerol, vinyl alcohol, polyvinyl alcohol, alcohol amines such as triethanolamine, and mixtures thereof.
The number of equivalents of hole scavenger in the mixture of step a) of the process of the invention is higher than the number of equivalents of metal salt. The term "equivalent number" refers to the number of moles of an ion in solution multiplied by the valence of the ion.
In a particular embodiment, the mixture of step a) comprises:
-1×10-12m to 1 × 10-6Atomic quantum cluster of M, preferably 1 × 10-10M to 1 × 10-7M, more preferably 1 × 10-9M to 1 × 10-8M，
0.1mM to 1M of a metal salt, preferably 0.5mM to 0.5M, preferably 1mM to 0.05M, more preferably 10mM,
-1mM to 10M of an oxidizing agent, preferably 10mM to 1M, more preferably 50mM,
-from 1% v/v to 90% v/v of a hole scavenger, preferably from 10% v/v to 60% v/v, more preferably 40% v/v, and
-10% v/v to 99% v/v polar solvent, preferably 40% v/v to 90% v/v, more preferably 60% v/v.
Furthermore, the mixture of step a) may comprise an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt; preferably above the standard electrode potential of the metal ion of the metal salt.
In a particular embodiment, the oxidizing agent in the process of the invention is selected from the group consisting of nitric acid, hydrogen peroxide, permanganate, perchlorate, ozone, persulfate, hypochlorite, chlorite, hypobromite, dichromate, and mixtures thereof. Preferably, the oxidizing agent in the process of the invention is selected from nitric acid or hydrogen peroxide.
In a more particular embodiment, the mixture of step (a) consists of: a picomolar to micromolar concentration of the starting atomic quantum cluster; a metal salt; a polar solvent; a hole scavenger having a standard electrode potential lower than a Higher Occupied Molecular Orbital (HOMO) of an initial atomic mass cluster; and an oxidizing agent having a standard electrode potential higher than that of the metal salt; wherein the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other; and wherein the number of equivalents of said hole scavenger in the mixture is higher than the number of equivalents of the metal salt.
Applying a promoter to the mixture of step a) according to step b), wherein the promoter is a photo-radiation having an energy equal to or greater than the HOMO-LUMO gap of the starting atomic quantum cluster of the mixture of step a).
In the process of the present invention, the term "accelerator" refers to light radiation having a wavelength shorter than or equal to the excitation wavelength of the starting atomic quantum cluster; i.e., photoradiation having an energy equal to or higher than the HOMO-LUMO gap (higher occupied molecular orbital-lower unoccupied molecular orbital gap) of the starting AQC.
Approximate estimates of AQC excitation wavelengths can be determined experimentally by UV-vis absorption spectroscopy or theoretically by the Jellium model, as described in european patent applications EP11382196 and EP113823751 (see e.g. j.calvo et al, Encyclopedia of Nanotechnology, b.bhushan editors, Springer Verlag, 2011).
In a preferred embodiment, the acceleratorIs light radiation having a wavelength in the UV, visible and/or near IR range. Preferably, the accelerator is of a wavelength of 200nm to 800nm, preferably 350nm to 750nm, more preferably 400nm to 700nm, even more preferably 500nm to 600nm and an intensity of 0.01 milliwatts/cm2To 10 watts/cm2Preferably 0.2 milliwatts/cm2To 0.8 milliwatt/cm2And even more preferably 0.4 milliwatts/cm2To 0.6 milliwatt/cm2Of the light radiation. In a more preferred embodiment, the accelerator is about 1 milliwatt/cm2And light radiation from the lamp at a wavelength of 250 nm.
The photocatalytic activity of the starting AQCs depends on their ability to absorb light from the promoter and generate electron-hole pairs (excitons), i.e., the ability to induce charge separation by generating charge carriers (electrons and holes) that can subsequently undergo a photocatalytic process, such as a reduction-oxidation (redox) reaction, by transferring the charge carriers to a charge acceptor (i.e., an electron acceptor or a hole acceptor).
Without being bound by any theory, the inventors believe that the promoter causes excitation of the starting AQC in the reaction mixture, thereby generating excitons (electron-hole pairs) in the starting AQC. The holes oxidize the hole scavengers in the reaction mixture, while the electrons reduce the metal cations of the metal salt to produce nascent AQCs. The reaction generally proceeds rapidly, primarily due to the presence of the starting AQC acting as a catalyst in the reduction of the metal ions. After the first batch of nascent AQCs was formed, the reaction was further carried out to form nanoparticles. However, an oxidizing agent in the reaction mixture, having a standard electrode potential higher than the standard electrode potential of the metal ion (reduction standard potential), oxidizes the metal nanoparticles to metal ions, causing the dissolution of the metal nanoparticles and the subsequent formation of metal salts, thereby again initiating the process of producing more nascent AQCs and more nanoparticles. Due to the high stability of the clusters in the presence of the oxidizing agent, the concentration of the clusters increases with time in the process of the invention, while less stable species comprising metal ions and nanoparticles in the reaction mixture are continuously reduced or oxidized.
In a particular embodiment, the reaction time of the process of the invention is from 0.1 hour to 60 hours, preferably from 1.5 hours to 10 hours, even more preferably 3 hours.
In the context of the present invention, the term "metal nanoparticles" refers to any bulk (bulk) metal particles having a size of the order of nanometers. Typical metal nanoparticles range in size from two nanometers to tens of nanometers. Nanoparticles generally exhibit a core-shell structure in which the core of the bulk metal is surrounded by a shell of disordered atoms.
The method of the present invention comprises a step (c) of adding an oxidizing agent having a standard electrode potential higher than that of the metal salt; wherein an oxidizing agent may be added to the mixture of step (a) and/or during and/or after the application of the promoter in step (b). According to the process of the present invention, an oxidizing agent may be present in the mixture of step a) and/or added to the mixture during and/or after the application of the promoter in step b). Thus, in a particular embodiment, the oxidizing agent is present in the mixture of step a) of the process of the invention and is also added to the mixture during the application of the promoter. In another particular embodiment, the oxidizing agent is present in the mixture of step a) of the process of the invention and is also added to the mixture during and after the application of the promoter. In another particular embodiment, the oxidizing agent is present in the mixture of step a) of the process of the invention and is also added to the mixture after, preferably immediately after, the application of the promoter. In another particular embodiment, the oxidizing agent is added to the mixture of step a) during the application of the promoter. In another particular embodiment, the oxidizing agent is added to the mixture of step a) during and after the application of the promoter. In another particular embodiment, the oxidizing agent is added to the mixture of step a) after the application of the promoter. In another particular embodiment, an oxidizing agent is added to the mixture of step a).
In the method of the present invention, the oxidizing agent having a standard electrode potential higher than that of the metal salt is capable of oxidizing the metal nanoparticles produced by the reduction of the metal ions of the metal salt. Thus, for example, if the metal of the metal salt is silver, the standard electrode potential of the oxidizing agent of the process of the invention is higher than the standard electrode potential of silver, i.e. higher than + 0.80V. Furthermore, the yield of the process is increased if the amount of oxidant in the reaction mixture is higher than the amount of metal salt. Thus, in a particular embodiment, the amount of oxidant in the mixture of the process of the invention is higher than the amount of metal salt.
Furthermore, although the AQCs of the reaction mixture are stable in the presence of strong oxidants, i.e.: they retain the atomic number and its characteristics, but the metal nanoparticles are oxidized in the presence of an oxidizing agent. The stability of several AQCs has been reported in the prior art (Ag)3、Ag5、Ag9、Cu5(S.Huseyinova, J.Blanco, F.G.Requejo, J.Ramallo-L Lo Paz, M.C.Blanco, D.Buceta and M.A.L Lo pez-Quintel.J.Phys.Chem.C, 2016, 120, 15902-.
The term "nascent AQC" refers to an AQC produced by the methods of the present invention, as compared to the starting AQC. Advantageously, the methods of the present invention allow AQCs to be obtained in high yields; preferably "the nascent AQCs are obtained in high yield". In a particular embodiment, the present invention relates to a process wherein atomic quantum clusters are produced in a yield of greater than 10%, preferably greater than 20%, more preferably about 40%. In a preferred embodiment, the atomic quantum clusters are produced in a yield of 60%, preferably higher than 80%, even more preferably 100%. In a particular embodiment, all metals in the reaction mixture are ultimately converted to AQCs, thus producing atomic quantum clusters in 100% yield. In a particular embodiment, the present invention relates to a process wherein atomic quantum clusters are produced on a scale of at least milligrams. The conditions of the process of the invention can be optimized by routine work in the laboratory.
In a preferred embodiment, the process of the invention produces a mixture comprising atomic quantum clusters, wherein the amount of atomic quantum clusters is higher than in step (a).
In a preferred embodiment, the method of the invention produces a mixture comprising nascent atomic quantum clusters; preferably, wherein the nascent atomic quantum cluster is different from the starting atomic quantum cluster of step (a); more preferably, wherein the nascent atomic quantum cluster is produced in a yield of greater than 10%, preferably greater than 20%, more preferably about 40%.
In a preferred embodiment, the method of the invention produces a mixture comprising nascent atomic quantum clusters; wherein the amount of nascent atomic quantum clusters increases with reaction time.
In a preferred embodiment, the process of the invention comprises a reaction mixture of: wherein the reaction mixture is produced after the addition of the oxidizing agent of step (c) and the application of the promoter of step (b); preferably, the reaction mixture comprises nascent atomic quantum clusters; more preferably, nascent atomic quantum clusters are generated over reaction time in the reaction mixture.
In a particular embodiment, the invention relates to such a method: wherein the atomic quantum clusters are produced in a concentration higher than the concentration of the starting atomic quantum clusters of step (a), preferably in a concentration higher than the micromolar concentration.
In a preferred embodiment, the process of the invention produces a mixture comprising atomic quantum clusters; wherein the concentration of the atomic quantum clusters is higher than the concentration of the atomic quantum clusters of step (a); preferably, the concentration of the atomic quantum clusters is higher than the micromolar concentration.
In a preferred embodiment, the method of the invention produces a mixture comprising nascent atomic quantum clusters; wherein the amount of the nascent atomic quantum cluster is higher than the amount of the starting atomic quantum cluster in step (a); preferably, the concentration of the nascent atomic quantum clusters is higher than micromolar. In a particular embodiment, the atomic quantum clusters in step (a) are catalysts.
In a preferred embodiment, the method of the present invention is a method for producing Atomic Quantum Clusters (AQCs), comprising the steps of:
a) providing a mixture comprising:
-a picomolar to micromolar concentration of the starting atomic quantum clusters,
-a metal salt of a metal selected from the group consisting of,
-a polar solvent, the solvent being a polar solvent,
-a hole scavenger having a standard electrode potential lower than the Higher Occupied Molecular Orbital (HOMO) of the starting atomic quantum cluster, and
wherein the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other;
wherein the number of equivalents of the hole scavenger in the mixture is greater than the number of equivalents of the metal salt;
b) applying a promoter to the mixture of step a), wherein the promoter is photoradiation having an energy equal to or greater than the HOMO-LUMO gap of the starting atomic quantum cluster of the mixture of step a); and
c) adding an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt of step (a);
wherein the oxidizing agent is added to the mixture of step a), and/or to the mixture during and/or after the application of the promoter in step b); and
wherein atomic mass quantum clusters are produced, preferably nascent atomic mass quantum clusters are produced; more preferably, the nascent atomic quantum clusters are produced in a yield of more than 10%, preferably more than 20%, more preferably about 40%.
In a more preferred embodiment, the amount of AQC is increased by the methods of the present invention; more preferably, the amount of nascent AQCs is increased by the methods of the present invention.
In a particular embodiment, the metal of the nascent AQC is the same or different from the metal of the starting AQC in step (a); preferably the same; more preferably silver.
In a more particular embodiment, the metal of the nascent AQC is different from the metal of the starting AQC in step (a).
In a more preferred embodiment, the yield of AQC is increased by the method of the invention. Preferably, the yield of nascent AQCs is increased.
In the context of the present invention, the term "yield" is understood to be the percentage yield calculated from the amount of desired product obtained and from the theoretical yield (the theoretical yield) calculated on the basis of stoichiometric calculations based on the number of moles of limiting reactant, as known in the art. In addition, the calculation of the theoretical yield assumes that only one reaction occurs and limits the complete reaction of the reactants. Preferably, the metal salts of the present invention are limiting reactants in calculating the yield of the present invention. More preferably, in the present invention, atomic quantum clusters are produced in 100% yield when all metals in the reaction mixture are ultimately converted to AQCs; in particular, atomic quantum clusters are produced in 100% yield when all the metals of the metal salts of the present invention are converted to nascent AQCs. Additionally, in a particular embodiment, when the metal of the starting metal AQC is the same as the metal of the metal salt of the invention and the metal of the metal AQC produced, the starting atomic quantum cluster is not taken into account in calculating the yield of the process of the invention, or the amount of the starting atomic quantum cluster is so small that they do not have a significant effect on the calculation; preferably, they are not considered in calculating the yield.
In a particular embodiment, the yield of the invention is calculated as the percentage yield calculated from the molar amount of AQC obtained and the theoretical yield calculated from the number of moles of limiting reactant; preferably, wherein the calculation of the theoretical yield assumes that the reactants are limited to reacting completely and only in one reaction.
In a more particular embodiment, the yield of the invention is calculated as the percentage yield by dividing the molar amount of metal of the metal AQC obtained by the theoretical yield calculated by stoichiometric calculations based on the moles of metal of the metal salt of the invention; where the calculation of the theoretical yield assumes that only one reaction takes place and that the metal salts of the invention are fully reacted.
In an even more particular embodiment, the yield of the invention is calculated as the percent yield by dividing the molar amount of metal of the metal AQC obtained by the theoretical yield calculated by stoichiometric calculations based on the moles of metal of the metal salt of the invention; where the calculation of the theoretical yield assumes that only one reaction takes place and that the metal salts of the invention are fully reacted.
In an even more particular embodiment, the yield of the invention is calculated as the percent yield by dividing the molar amount of metal of the metal AQC obtained by the theoretical yield calculated by stoichiometric calculations based on the moles of metal of the metal salt of the invention; wherein the calculation of the theoretical yield assumes that only one reaction takes place and that the metal salts of the invention are fully reacted;
preferably, when the metal of the starting AQC is the same as the metal of the metal salt, the initial moles of starting AQC are not considered in the yield calculation; preferably, the initial moles of starting AQCs are not taken into account in calculating the moles of metal of the nascent metal AQCs obtained; more preferably, the initial moles of the starting AQCs are subtracted from the total moles of metal of the obtained metal AQCs to calculate the moles of metal of the nascent AQCs;
more preferably, when the metal of the starting AQC is the same as the metal of the metal salt, the initial moles of starting AQC are not considered in the yield calculation; preferably, the initial moles of the starting AQCs are not taken into account in calculating the moles of metal of the AQCs obtained;
even more preferably, the initial moles of the starting AQCs are subtracted from the total moles of metal of the metal AQCs obtained.
The AQCs obtained by the methods of the present invention can be identified by electrospray ionization (ESI) mass spectrometry. FIG. 1 shows ESI-mass spectra of Ag AQCs obtained by the method of the present invention. The peaks detected were identified as the following Ag AQCs: ag2(230)、Ag3(401)、Ag5(570 and 786), Ag7(912 and 1081), Ag9(1248)。
In a preferred embodiment, the metal atoms of the AQCs obtained by the process of the present invention are selected from the group consisting of platinum (Pt), gold (Au), rhodium (Rh), iridium (Ir), palladium (Pd), ruthenium (Ru), osmium (Os), silver (Ag), copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), titanium (Ti), vanadium (V), chromium (Cr), or bimetallic and multimetallic combinations thereof. Preferably, the metal of the AQC is selected from Au, Ag, Cu, Pd and Pt or a bimetallic combination thereof.
Furthermore, the method of the present invention allows the production of AQCs of different metal atom numbers by optimising the conditions of the method such as the concentration and type of metal salt, the concentration of photocatalytic AQCs, the concentration and type of hole scavenger and the wavelength of the promoter. In a particular embodiment, the AQCs obtained by the process of the present invention have a number of metal atoms in the range of from 2 to 50. In a preferred embodiment, the AQCs produced by the methods of the present invention consist of less than 30 metal atoms (M)nN < 30), preferably less than 15 metal atoms (M)nN < 15), even more preferably the AQCs of the present invention consist of 2 to 10 (M)n，2<n<10) Metal atoms are formed.
In a particular embodiment, the AQCs produced by the process of the present invention have an average size of from 0.3nm to 1.5nm, preferably an average size of less than 1nm, more preferably from about 0.3nm to 0.9 nm.
Furthermore, the concentration of AQC in the solution can be measured by UV-VIS spectroscopy. Thus, for example, FIG. 2 shows UV-VIS spectra of the reaction of the process of the invention at different times. After 5 hours and before the addition of the oxidizing agent, the figure shows a plasmon band at about 420nm (plasmon band) correlated with the presence of nanoparticles; and a band at about 280nm associated with the presence of clusters. In contrast, after 5 hours and after addition of the oxidizing agent, only the energy bands of the clusters remain.
In another aspect, the present invention also relates to a mixture or composition comprising:
-a cluster of atomic mass photons,
-a metal salt of a metal selected from the group consisting of,
-an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt,
-a hole scavenger having a standard electrode potential lower than the HOMO orbital of the atomic quantum cluster, and
-a polar solvent, the solvent being a polar solvent,
wherein the metal salt and the hole scavenger are both soluble in the mixture and are not reactive with each other, and wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.
In a particular embodiment, the atomic quantum clusters of the mixture of the invention are the starting atomic quantum clusters; preferably at picomolar to micromolar concentrations.
In a particular embodiment, the present invention relates to the mixture or composition of step a), comprising:
-at least a cluster of atomic mass photons,
-a metal salt of a metal selected from the group consisting of,
-optionally an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal ions,
-a hole scavenger having a standard electrode potential lower than the HOMO orbital of at least an atomic quantum cluster, and
-a polar solvent, the solvent being a polar solvent,
wherein the metal salt and the hole scavenger are both soluble in the mixture and are not reactive with each other, and wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.
In a preferred embodiment, the mixture or composition of step a) comprises:
-1×10-12m to 1 × 10-6Atomic quantum cluster of M, preferably 1 × 10-10M to 1 × 10-7M, more preferably 1 × 10-9M to 1 × 10-8M，
0.1mM to 1M of a metal salt, preferably 0.5mM to 0.5M, preferably 1mM to 0.05M, more preferably about 10mM,
-1mM to 10M of an oxidizing agent, preferably 10mM to 1M, more preferably about 50mM,
-from 1% v/v to 90% v/v of a hole scavenger, preferably from 10% v/v to 60% v/v, more preferably about 40% v/v, and
-10% v/v to 99% v/v polar solvent, preferably 40% v/v to 90% v/v, more preferably about 60% v/v.
The volume percentages are calculated assuming that the AQCs, metal salts and oxidizing agent do not increase the volume of the mixture. In addition, they add volume in rare cases, and the sum of the volumes of the polar solvent and the hole scavenger will be adjusted to 100% to maintain their relationship and take into account the final volume added by the other components.
In the mixture or composition of step a) of the method of the present invention, the AQCs present in the mixture correspond to the starting AQCs which initiate the method of the present invention.
In another embodiment, the invention relates to a mixture or composition obtained by the process of the invention, preferably comprising:
-1×10-5atomic quantum clusters of M to 1M, preferably 1 × 10-3M to 0.1M, preferably about 5mM,
0M to 0.9M of a metal salt, preferably about 5mM,
-0M to 5M of an oxidizing agent,
-from 0% v/v to 80% v/v of a hole scavenger, preferably from 30% v/v to 50% v/v, and
-20% v/v to 100% v/v of a polar solvent, preferably 50% v/v to 70% v/v.
In another particular embodiment, the invention relates to a mixture or composition obtained by the process of the invention, preferably comprising:
-1×10-5atomic quantum clusters of M to 1M, preferably 1 × 10-3M to 0.1M, preferably about 5mM,
0.01M to 0.9M of a metal salt, preferably about 5mM,
-0.01M to 5M of an oxidizing agent,
-from 0.01% v/v to 80% v/v of a hole scavenger, preferably from 30% v/v to 50% v/v, and
-20% v/v to 100% v/v of a polar solvent, preferably 50% v/v to 70% v/v.
The volume percentages are calculated assuming that the AQCs, metal salts and oxidizing agents do not increase the volume of the mixture. In addition, they add volume in rare cases, and the sum of the volumes of the polar solvent and the hole scavenger will be adjusted to 100% to maintain their relationship and take into account the final volume added by the other components.
In a preferred embodiment, the AQC is assumed not to increase the volume of the mixture comprising 100% v/v polar solvent and 1 × 10-5M to 1M AQC, while in rare cases they add volume, the volume of the polar solvent will be adjusted to 100% to maintain their relationship.
The atomic quantum clusters in the mixtures of the present invention include any AQC available on the market or in the laboratory. In a preferred embodiment, the AQCs of the mixture are formed from a transition metal selected from the group consisting of: platinum (Pt), gold (Au), rhodium (Rh), iridium (Ir), palladium (Pd), ruthenium (Ru), osmium (Os), silver (Ag), copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), titanium (Ti), vanadium (V), chromium (Cr), and bimetallic and multi-metallic combinations thereof. More preferably, the metal of the AQC is selected from Au, Ag, Cu, Pd and Pt or a bimetallic combination thereof, even more preferably, the metal of the AQC is selected from Au and Ag or a bimetallic combination thereof.
In a preferred embodiment, the metal of the metal salt in the mixture or composition is selected from silver, platinum, palladium, gold, copper, iridium, rhodium, ruthenium, nickel, iron, cobalt, or bimetallic and polymetallic combinations thereof. Preferably, the metal of the metal salt is selected from Au, Ag, Cu, Pd and Pt or a bimetallic combination thereof. In a preferred embodiment the metal of the metal salt and the metal of the starting AQC in the mixture according to the invention are the same metal or different metals. In a more preferred embodiment, the metal salt is a silver salt, preferably a silver salt selected from the group consisting of silver bromate, silver bromite, silver chlorate, silver perchlorate, silver chlorite, silver fluoride, silver nitrate, silver nitrite, silver acetate, silver permanganate, and mixtures thereof.
The hole scavengers as well as the metal salts are soluble in the mixture of the invention. Furthermore, the hole scavengers in the mixtures of the present invention are not reactive with the metal salts.
In a preferred embodiment, the hole scavenger is selected from linear or branched alcohols having 2 to 6 carbon atoms. More preferably, the hole scavenger is selected from the group consisting of ethanol, propan-1-ol, isopropanol, butan-1-ol, butan-2-ol, isobutanol, 1-dimethyl-ethanol, pentan-1-ol, pentan-2-ol, pentan-3-ol, 2-methylbutan-1-ol, 3-methylbutan-2-ol, 2-dimethylpropan-1-ol, hexan-2-ol, hexan-3-ol, 2-methylpentan-1-ol, 3-methylpentan-1-ol, 4-methylpentan-1-ol, 2-methylpentan-2-ol, and mixtures thereof, 3-methylpent-2-ol, 4-methylpent-2-ol, 2-methylpent-3-ol, 3-methylpent-3-ol, 2-dimethylbut-1-ol, 3-dimethylbut-1-ol, 2, 3-dimethylbut-2-ol, 3-dimethylbut-2-ol, 2-ethylbuta-1-ol and mixtures thereof. In another preferred embodiment, the hole scavenger is selected from the group consisting of hydroquinone, iodide salts, oxalic acid, acetic acid, formic acid, sodium formate, sulfites, and mixtures thereof. Other suitable hole scavengers include glycerol (glicerol), vinyl alcohol, polyvinyl alcohol, alcohol amines such as triethanolamine, and mixtures thereof.
In a preferred embodiment, the oxidizing agent in the mixture of the invention is selected from nitric acid, hydrogen peroxide, permanganates, perchlorates, ozone, persulfates, hypochlorites, chlorites, hypobromites, bromites, perchromates and mixtures thereof, even more preferably from nitric acid or hydrogen peroxide.
In a preferred embodiment, the polar solvent is selected from the group consisting of water, acetonitrile, chloroform, dichloromethane, acetic acid, toluene, and mixtures thereof.
The present invention also relates to a mixture or composition obtainable by the process of the invention, preferably comprising:
-1×10-5atomic quantum clusters of M to 1M, preferably 1 × 10-3M to 0.1M, preferably about 5mM,
0M to 0.9M of a metal salt, preferably about 5mM,
-0M to 5M of an oxidizing agent,
-from 0% v/v to 80% v/v of a hole scavenger, preferably from 30% v/v to 50% v/v, and
-20% v/v to 100% v/v of a polar solvent, preferably 50% v/v to 70% v/v,
wherein the metal salt and the hole scavenger are both soluble in the mixture and are not reactive with each other, and wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.
The volume percentages are calculated assuming that the AQCs, metal salts and oxidizing agents do not increase the volume of the mixture. In addition, they add volume in rare cases, and the sum of the volumes of the polar solvent and the hole scavenger will be adjusted to 100% to maintain their relationship and take into account the final volume added by the other components.
Examples
Example 1
750mL of H2O Milli-Q, 750mL of 2-propanol (hole scavenger), 1.2g of AgNO already containing about 0.3 micrograms of AgAQC3(0.5g/L of Ag) was added to a 2L beaker. Then, under continuous stirring, with ≈ 1 milliwatt/cm2And a lamp with a wavelength of 250nm irradiated the sample for 5 hours. During this time, a far excess of 1mL HNO for the silver salt was added 30 minutes after the start of irradiation3(65% v/v) and 0.5mL was added after 5 hours of irradiation. Ag remaining in solution+The final concentration (measured by an ion selective electrode) of (2) was 0.3 g/L. The remainder (0.2g/L) corresponds to the bare AQCs, which are the only stable species under the strong oxidative conditions used.
Clusters were identified by ESI-mass spectrometry (see fig. 1). The peaks observed in the ESI-mass spectrum correspond to the following Ag AQCs: ag2(230)、Ag3(401)、Ag5(570 and 786), Ag9(1248)。
Considering that the extinction coefficient of Ag AQC is about 1000M-1cm-1The concentration of clusters (J.Neissa, C.Perez-Arnaiz, V.Porto, N.Busto, E.Borrajo, J.M.Leal, M.A.Lopez-Quintela, B.Garcia and F.Dominguez, chem.Sci., 2015, 6, 6717-.Giovanetti, F.G.Requejo, B.Garcia and M.A.L. Lopez-Quintela.Angew.chem.int.Engl. editor 2015, 54(26): 7612-6). FIG. 2 shows the uv-vis spectra of the reaction at different times: A) initial (0') -solid line, B) dotted line after 5 hours (300') of reaction (before addition of oxidant), and C) dashed line after 5 hours (300') of reaction and after addition of oxidant.
After 5 hours of reaction (fig. 2), Ag plasmon bands at about 420nm can be seen, indicating the presence of Ag nanoparticles. In addition, the band at 275nm due to the clusters can be clearly seen. However, after 5 hours of reaction and after addition of the oxidizing agent, only bands of clusters remained, indicating that the clusters were stable in the presence of the oxidizing agent, but the nanoparticles were oxidized (fig. 2).
Furthermore, figure 2 shows that the final absorbance at 275nm (using a 1cm cuvette) (see previous references) associated with AQC is ≈ 0.45, whereby a concentration of Ag AQC (considering the average cluster size of 5 atoms) can be obtained of: 0.45/1000M-1cm-1× 1 cm-0.45 mM-0.24 g/l although this value includes some uncertainty in the value and average cluster size, this value fits well with the previous calculations.
Example 2
1350mL of H2O Milli-Q, 150mL 2-propanol (hole scavenger), 1.2g AgNO already containing about 0.3 micrograms of AgAQC3(0.5g/L of Ag), 1mL of HNO in far excess to the silver salt3(65% v/v) was added to a 2L beaker. Then, under continuous stirring, with ≈ 1 milliwatt/cm2And a lamp with a wavelength of 250nm irradiated the sample for 5 hours. Figure 3 shows that the final absorbance at 275nm (using a 1cm cuvette) associated with AQC (see previous examples) is 0.15, from which the concentration of Ag AQC can be obtained: 0.15/1000M-1cm-1× 1 cm-0.15 mM ≈ 80mg/l the concentration of AgAQC in this example is less than in the previous example because the concentration of hole scavenger is also smaller.

Claims (15)

1. A method for producing Atomic Quantum Clusters (AQCs), comprising the steps of:
a) providing a mixture comprising:
-a picomolar to micromolar concentration of the starting atomic quantum clusters,
-a metal salt of a metal selected from the group consisting of,
-a polar solvent, the solvent being a polar solvent,
a hole scavenger having a standard electrode potential lower than the Higher Occupied Molecular Orbital (HOMO) of the starting atomic quantum cluster,
wherein the metal salt and the hole scavenger are soluble in the polar solvent and do not react with each other;
wherein the number of equivalents of the hole scavenger in the mixture is greater than the number of equivalents of the metal salt;
b) applying a promoter to the mixture of step a), wherein the promoter is photoradiation having an energy equal to or greater than the HOMO-LUMO gap of the starting atomic quantum cluster of the mixture of step a); and
c) adding an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt;
wherein the oxidizing agent can be added to the mixture of step (a) and/or to the mixture during and/or after the application of the promoter in step (b).
2. The method of claim 1, wherein the amount of oxidant in the mixture is greater than the amount of metal salt.
3. The process according to claim 1 or 2, wherein the polar solvent of step a) is selected from water, acetonitrile, chloroform, dichloromethane, acetic acid, toluene and mixtures thereof.
4. The method of any one of claims 1 to 3, wherein the hole scavenger is selected from linear or branched alcohols having from 2 to 6 carbon atoms.
5. The method of any one of claims 1 to 3, wherein the hole scavenger is selected from the group consisting of hydroquinone, iodide salts, oxalic acid, acetic acid, formic acid, sodium formate, sulfites, and mixtures thereof.
6. The process according to any one of claims 1 to 5, wherein the metal of the metal salt in step a) is selected from silver, platinum, palladium, gold, copper, iridium, rhodium, ruthenium, nickel, iron, cobalt, or bimetallic and multimetallic combinations thereof.
7. The process according to any one of claims 1 to 6, wherein the metal salt in step a) is a silver salt selected from the group consisting of: silver bromate, silver bromite, silver chlorate, silver perchlorate, silver chlorite, silver fluoride, silver nitrate, silver nitrite, silver acetate, silver permanganate, and mixtures thereof.
8. The method of any one of claims 1 to 7, wherein the oxidizing agent is selected from the group consisting of nitric acid, hydrogen peroxide, permanganate, perchlorate, ozone, persulfate, hypochlorite, chlorite, hypobromite, dichromate, and mixtures thereof.
9. The method according to any one of claims 1 to 8, wherein the mixture of step a) comprises:
-1×10-12m to 1 × 10-6The atomic-quantum cluster of M,
-0.1mM to 1M of a metal salt,
-1mM to 10M of said oxidizing agent,
-from 1% v/v to 90% v/v of a hole scavenger, and
-10% v/v to 99% v/v of a polar solvent.
10. The method of any one of claims 1 to 9, wherein the mixture of step a) comprises a nanomolar concentration of atomic quantum clusters.
11. The method according to any one of claims 1 to 10, wherein atomic quantum clusters are produced in a yield of more than 10%, preferably about 40%.
12. The method of any one of claims 1 to 11, wherein the atomic quantum clusters are produced on a scale of at least milligrams.
13. A mixture, comprising:
-a cluster of atomic mass photons,
-a metal salt of a metal selected from the group consisting of,
-an oxidizing agent having a standard electrode potential higher than the standard electrode potential of the metal salt,
-a hole scavenger having a standard electrode potential lower than the HOMO orbital of the atomic quantum cluster, and
-a polar solvent, the solvent being a polar solvent,
wherein the metal salt and the hole scavenger are both soluble in the polar solvent and do not react with each other, and
wherein the number of equivalents of hole scavenger in the mixture is higher than the number of equivalents of metal salt in the mixture.
14. The mixture of claim 13, comprising:
-1×10-12m to 1 × 10-6The atomic-quantum cluster of M,
-0.1mM to 1M of a metal salt,
-1mM to 10M of said oxidizing agent,
-1% v/v to 90% v/v of the hole scavenger, and
-10% v/v to 99% v/v of a polar solvent.
15. The mixture of claim 13, comprising:
-1×10-5m to 1M of atomic quantum clusters,
-0M to 0.9M of a metal salt,
-0M to 5M of said oxidizing agent,
-0% v/v to 80% v/v of the hole scavenger, and
-20% v/v to 100% v/v of a polar solvent.
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