CN115472846A - Carbon-supported rhodium-based ordered intermetallic compound, preparation and application as catalyst - Google Patents

Carbon-supported rhodium-based ordered intermetallic compound, preparation and application as catalyst Download PDF

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CN115472846A
CN115472846A CN202211035137.1A CN202211035137A CN115472846A CN 115472846 A CN115472846 A CN 115472846A CN 202211035137 A CN202211035137 A CN 202211035137A CN 115472846 A CN115472846 A CN 115472846A
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rhodium
carbon
salt
intermetallic compound
chloride
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王得丽
申涛
王双
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a carbon-supported rhodium-based ordered intermetallic compound, a preparation method thereof and an application thereof as a catalyst, belonging to the technical field of liquid fuel cells. The preparation method comprises the steps of dispersing the carbon carrier into a solution of rhodium salt and non-noble metal salt, or dispersing the carbon carrier into a solution of rhodium salt, other platinum group metal salts and non-noble metal salt, and loading the metal salt on the carbon carrier; and grinding the dried sample, and sequentially carrying out two-step heat treatment at low temperature and high temperature in a reducing atmosphere to obtain the carbon-supported rhodium-based intermetallic compound. The rhodium-based intermetallic compound electrocatalyst reduces the overpotential of formic acid oxidation reaction, improves the catalytic activity, is obviously superior to the catalytic performance of single metal rhodium, has simple and feasible synthesis method, and is suitable for mass preparation.

Description

Carbon-supported rhodium-based ordered intermetallic compound, preparation and application as catalyst
Technical Field
The invention belongs to the technical field of liquid fuel cells, and particularly relates to a carbon-supported rhodium-based ordered intermetallic compound, a preparation method thereof and an application thereof as a catalyst, in particular to a preparation method of the carbon-supported rhodium-based ordered intermetallic compound and an application thereof as an electro-catalyst for formic acid electro-oxidation reaction.
Background
The fuel cell has the advantages of high energy conversion efficiency, environmental friendliness and the like. When liquid is used as fuel, the energy density is further improved, and the liquid transportation is more portable. Formic acid, when used as a fuel, is less likely to diffuse through the polymer membrane to the cathode. The anodic formic acid electrooxidation reaction releases two electrons for formic acid molecules to generate carbon dioxide, and is mainly divided into a direct path and an indirect path through a carbon monoxide intermediate. Since the carbon monoxide intermediate in the adsorbed state needs a very high overpotential for further oxidation into carbon dioxide, the carbon monoxide intermediate is considered as a toxic intermediate, and the formation of the toxic intermediate is avoided, which is beneficial to improving the energy conversion efficiency. However, catalytically active platinum group metals typically catalyze formic acid oxidation reactions in an indirect pathway. In order to promote the platinum group metal to catalyze the formic acid oxidation through a direct path, the bonding strength of the platinum group metal to a carbon monoxide intermediate can be weakened through inhibiting continuous metal sites, and the selectivity of the catalytic formic acid oxidation reaction is improved. At present, research on catalyzing formic acid oxidation by rhodium is limited, overpotential of catalyzing formic acid oxidation by single-metal rhodium is large, and how to simultaneously improve selectivity and activity of catalyzing formic acid oxidation by rhodium needs to further optimize coordination environment of rhodium-based catalyst.
Disclosure of Invention
The invention aims to provide a carbon-supported rhodium-based ordered intermetallic compound and a preparation method thereof.
According to a first aspect of the invention, a preparation method of the carbon-supported rhodium-based ordered intermetallic compound is provided, which comprises the following steps:
(1) Dispersing a carbon carrier in a metal salt solution, fully and uniformly mixing the metal salt solution containing rhodium salt and non-noble metal salt, and evaporating the solvent to dry so that the metal salt is adsorbed on the carbon carrier;
(2) Grinding the intermediate product obtained in the step (1), placing the ground intermediate product in a reducing atmosphere, and heating the ground intermediate product at a low temperature of between 150 and 300 ℃ to reduce the metal salt into disordered nano particles; then heating at the high temperature of 500-700 ℃ to obtain the carbon-supported rhodium-based ordered intermetallic compound.
Preferably, the metal salt solution further contains a platinum group metal salt other than rhodium.
Preferably, the rhodium salt is at least one of rhodium chloride, rhodium nitrate, rhodium acetate and rhodium triacetylacetonate.
Preferably, in the step (2), the heating time under the low-temperature condition is 1-3 h, and the heating time under the high-temperature condition is 2-10 h; the heating rate of heating under the low temperature condition and the heating rate of heating under the high temperature condition are both 5-10 ℃/min.
Preferably, the other platinum group metal salt other than rhodium is a platinum salt, an iridium salt or a ruthenium salt;
preferably, the platinum salt is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum acetylacetonate, platinum dichloride and platinum tetrachloride; the iridium salt is at least one of iridium acetate, iridium chloride, iridium sodium chlorate, iridium tetrachloride hydrate, iridium acetylacetonate and potassium hexachloroiridate; the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate, ruthenate, potassium ruthenate, ammonium ruthenate chloride, sodium ruthenate chloride and potassium ruthenate chloride.
Preferably, the non-noble metal salt is an iron salt, a zinc salt or a bismuth salt;
preferably, the iron salt is at least one of ferric chloride, ferrous chloride, ferric acetylacetonate, ferric acetate, ferric sulfate and ferric nitrate; the zinc salt is at least one of zinc chloride, zinc acetate, zinc acetylacetonate hydrate, zinc sulfate and zinc nitrate hydrate; the bismuth salt is at least one of bismuth chloride, bismuth acetate, bismuth sulfate and bismuth nitrate pentahydrate.
Preferably, the carbon support is at least one of carbon nanotubes, carbon nanofibers, carbon black, graphene oxide, and reduced graphene oxide.
According to another aspect of the invention, there is provided a carbon-supported rhodium-based ordered intermetallic compound produced by any of the methods described herein.
Preferably, the mass fraction of rhodium element in the carbon-supported rhodium-based ordered intermetallic compound is 20-50%.
According to another aspect of the invention, the application of the carbon-supported rhodium-based ordered intermetallic compound is provided, and the carbon-supported rhodium-based ordered intermetallic compound is used for anode catalysts of formic acid fuel cells.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The invention discloses a preparation method of a carbon-supported rhodium-based ordered intermetallic compound, which comprises the steps of dispersing a carbon carrier in a solution containing rhodium and non-noble metals (iron, zinc or bismuth), dispersing the carbon carrier in a solution containing rhodium, other platinum group metals (platinum, iridium or ruthenium) and non-noble metals (iron, zinc or bismuth), evaporating the solvent to dryness, grinding, placing in a reducing atmosphere, and carrying out two heat treatment steps of low temperature and high temperature to obtain carbon-supported binary or ternary rhodium-based intermetallic compound nanoparticles. In the carbon-supported rhodium-based ordered intermetallic compound, rhodium atoms are isolated by other metal atoms, the combination of the rhodium atoms on carbon monoxide intermediates and hydrogen atoms is weakened, and the combination of single metal rhodium with continuous rhodium sites on the carbon monoxide intermediates is stronger, so that formic acid molecules are directly oxidized into carbon dioxide by preparing the rhodium-based ordered intermetallic compound, and the overpotential is reduced.
(2) The binary intermetallic compound enables rhodium active sites to be isolated through a group effect, overpotential generated by formic acid oxidation reaction is reduced, and further the ternary rhodium-based ordered intermetallic compound is prepared, has two active sites and optimizes an electronic structure mutually, so that the activity and the stability are improved.
(3) The carbon-supported rhodium-based ordered intermetallic compound nanoparticles prepared by the method reduce the overpotential of formic acid oxidation reaction, improve the catalytic activity and enable the rhodium-based catalyst to become a potential novel anode fuel cell catalyst.
Drawings
Fig. 1 is an X-ray diffraction pattern of carbon-supported binary rhodium-iron intermetallic compounds, rhodium-zinc intermetallic compounds, rhodium-bismuth intermetallic compounds, ternary rhodium-platinum-iron intermetallic compounds, rhodium-iridium-iron intermetallic compounds, rhodium-ruthenium-iron intermetallic compounds.
Fig. 2 is an X-ray diffraction pattern of carbon-supported rhodium iron after treatment at different temperatures.
Figure 3 is a linear sweep voltammogram of carbon-supported binary and ternary rhodium-based intermetallics versus electrocatalytic oxidation of formic acid with rhodium monometallics.
Fig. 4 is a linear sweep voltammogram of carbon supported rhodium, binary rhodium iron, ternary rhodium platinum iron intermetallic compound electrocatalytic formic acid oxidation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention discloses a preparation method of a carbon-supported rhodium-based intermetallic compound for formic acid electrooxidation reaction, which comprises the following steps:
(1) Dispersing a carbon carrier in a solution of rhodium salt and non-noble metal (iron, zinc or bismuth) salt, or dispersing the carbon carrier in a solution of rhodium salt, other platinum group metal (platinum, iridium or ruthenium) salt and non-noble metal (iron, zinc or bismuth) salt, stirring, performing ultrasonic treatment, heating until the solvent is evaporated to dryness, and obtaining a solid;
(2) Grinding the solid powder obtained in the step (1), then carrying out low-temperature pre-reduction in a reducing atmosphere, and then carrying out high-temperature heat treatment to obtain the carbon-supported rhodium-based intermetallic compound nanoparticles.
In some embodiments, step (1), the heating temperature is 50 ℃ to 70 ℃; the solvent for dissolving the metal salt is at least one of water, ethanol and methanol.
In some embodiments, the reducing atmosphere comprises predominantly H in a volume fraction of 2 to 10% 2 /Ar。
In some embodiments, the rhodium salt is at least one of rhodium chloride, rhodium nitrate, rhodium acetate, and rhodium triacetylacetonate.
In some embodiments, the platinum salt in the other platinum group metal (platinum, iridium, ruthenium) salt is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinite, platinum acetylacetonate, platinum dichloride, and platinum tetrachloride, the iridium salt is at least one of iridium acetate, iridium chloride, sodium iridium chlorate, iridium tetrachloride hydrate, iridium acetylacetonate, and potassium hexachloroiridate, and the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate, ruthenium dicyclopentadienyl, potassium ruthenium, ammonium chlororuthenate, sodium chlororuthenate, and potassium chlororuthenate.
In some embodiments, the iron salt of the non-noble metal (iron, zinc, bismuth) salt is at least one of ferric chloride, ferrous chloride, ferric acetylacetonate, ferric acetate, ferric sulfate, and ferric nitrate, the zinc salt is at least one of zinc chloride, zinc acetate, zinc acetylacetonate hydrate, zinc sulfate, and zinc nitrate hydrate, and the bismuth salt is at least one of bismuth chloride, bismuth acetate, bismuth sulfate, and bismuth nitrate pentahydrate.
In some embodiments, the carbon support is at least one of carbon nanotubes, carbon nanofibers, carbon black, graphene oxide, reduced graphene oxide.
In some embodiments, the low temperature in the heating process in the step (2) is 150 ℃ to 300 ℃, and the temperature in the high temperature heat treatment process is 500 ℃ to 700 ℃.
In some embodiments, the atomic ratio of rhodium to other platinum group metal to non-noble metal is (0.9-1): (0-0.1): 1.
In some embodiments, the low-temperature reduction time is 1-3 h, the high-temperature heat treatment heating time is 2-10 h, and the heating rate is 5-10 ℃/min.
The carbon-supported rhodium-based intermetallic compound prepared by the invention has the mass fraction of rhodium element in the catalyst of 20-50%.
The carbon-supported rhodium-based intermetallic compound prepared by the invention is applied to a direct formic acid fuel cell anode catalyst.
Example 1
The first step is as follows: dissolving rhodium chloride, chloroplatinic acid and iron chloride in water, and then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium, platinum and iron to be 0.9;
the second step: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2 hours at 200 ℃ to room temperature, heating the sample to 700 ℃ from the room temperature for heat treatment for 4 hours at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded ternary rhodium-platinum-iron intermetallic compound nanoparticles.
Example 2
The first step is as follows: dissolving rhodium chloride and ferric chloride in water, then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium to iron to be 1;
the second step is that: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2h at 200 ℃ to room temperature, heating the sample to 700 ℃ from the room temperature for heat treatment for 4h at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded binary rhodium-iron intermetallic compound nano-particles.
Example 3
The first step is as follows: dissolving rhodium chloride, iridium chloride and ferric chloride in water, then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium to iridium to iron to be 0.9;
the second step: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2h at 200 ℃ to room temperature, heating the sample to 700 ℃ from the room temperature for heat treatment for 4h at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded ternary rhodium-iridium-iron intermetallic compound nano-particle.
Example 4
The first step is as follows: dissolving rhodium chloride and zinc chloride in water, then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium to zinc to be 1;
the second step is that: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2 hours at 200 ℃ to room temperature, heating the sample from the room temperature to 700 ℃ for heat treatment for 4 hours at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded binary rhodium-zinc intermetallic compound nanoparticles.
Example 5
The first step is as follows: dissolving rhodium chloride and bismuth chloride in water, then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium to bismuth to be 1;
the second step is that: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2h at 200 ℃ to room temperature, heating the sample to 700 ℃ from the room temperature for heat treatment for 4h at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded binary rhodium bismuth intermetallic compound nano-particles.
Example 6
The first step is as follows: dissolving rhodium chloride, ruthenium chloride and ferric chloride in water, and then dispersing Vulcan carbon in the solution, controlling the atomic ratio of rhodium to ruthenium to iron to be 0.9;
the second step: and further drying and grinding the sample in the first step, reducing the sample in argon-hydrogen mixed gas with the volume fraction of 10% of hydrogen for 2h at 200 ℃ to room temperature, heating the sample to 700 ℃ from the room temperature for heat treatment for 4h at the heating rate of 10 ℃/min, and naturally cooling the sample to the room temperature to obtain the carbon-loaded ternary rhodium ruthenium-iron intermetallic compound nano-particles.
Example 7
Dispersing 5mg of catalyst powder in 1mL of Nafion/isopropanol mixed solution with the Nafion mass fraction of 0.1%, performing ultrasonic treatment for 5-10 min to uniformly disperse the catalyst, absorbing 10 mu L of dispersion liquid, dripping the dispersion liquid on a glassy carbon electrode, and naturally drying to form a uniform and compact thin layer. A polarization curve of the catalyzed formic acid oxidation reaction was measured at a scanning speed of 5mV/s in a nitrogen-saturated formic acid solution containing 0.5mol/L sulfuric acid and 0.5mol/L formic acid using a glassy carbon electrode coated with a catalyst layer as a working electrode, a reversible hydrogen electrode as a reference electrode, and a carbon rod as a counter electrode.
FIG. 1 is X-ray diffraction (XRD) patterns of carbon-supported (a) rhodium bismuth, (b) rhodium zinc, (c) rhodium iron, (d) in examples 1-6, which are consistent with corresponding standard card comparisons and illustrate the formation of binary and ternary rhodium-based ordered intermetallic structures.
FIG. 2 is an X-ray diffraction (XRD) pattern of the carbon-supported rhodium iron of example 2 after the initial heat reduction treatment (200 ℃) and the subsequent heat treatment (700 ℃ or 400 ℃), wherein the shift of the strongest diffraction peak and the change of the number of the diffraction peaks indicate that the crystal phase is changed from face-centered cubic to body-centered cubic by comparing the sample treated at 400 ℃ with the sample treated at 200 ℃. The diffraction peak increases as compared to the 400 ℃ and 700 ℃ treated samples, indicating a higher shift in atomic arrangement to order.
Fig. 3 is a linear sweep voltammogram of the catalyzed formic acid oxidation of the carbon-supported (a) binary rhodium-based intermetallic compounds with (b) ternary rhodium-based intermetallic compounds and rhodium of examples 1-7, and the results show that the initial potential of the prepared rhodium-based intermetallic compounds for catalyzing the formic acid oxidation reaction decreases, indicating that the overpotential decreases, which is beneficial for increasing the output voltage of the direct acid addition fuel cell. The current density of the ternary rhodium-based intermetallic compound electrocatalytic formic acid oxidation was greater than that of the binary rhodium-based intermetallic compound, indicating that the catalytic performance was further improved by introducing a second active noble metal.
Fig. 4 is a linear sweep voltammogram of carbon-supported binary rhodium iron, ternary rhodium platinum iron intermetallic compound and rhodium electrocatalytic formic acid oxidation in examples 1,2,7, and the results show that the formation of isolated rhodium active sites of the binary rhodium iron intermetallic compound can reduce the overpotential for formic acid oxidation reactions relative to single metal rhodium. The ternary rhodium-platinum-iron intermetallic compound with the same crystal form is prepared by replacing part of rhodium with platinum, and the catalytic activity is further improved while the advantage of lowering overpotential is kept.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a carbon-supported rhodium-based ordered intermetallic compound is characterized by comprising the following steps:
(1) Dispersing a carbon carrier in a metal salt solution, wherein the metal salt solution contains rhodium salt and non-noble metal salt, fully and uniformly mixing, and evaporating the solvent to dryness to enable the metal salt to be adsorbed on the carbon carrier;
(2) Grinding the intermediate product obtained in the step (1), placing the ground intermediate product in a reducing atmosphere, and heating the ground intermediate product at a low temperature of between 150 and 300 ℃ to reduce the metal salt into disordered nano particles; then heating at the high temperature of 500-700 ℃ to obtain the carbon-supported rhodium-based ordered intermetallic compound.
2. The method of claim 1, wherein the metal salt solution further comprises a platinum group metal salt other than rhodium.
3. The process for producing a carbon-supported rhodium-based ordered intermetallic compound according to claim 1 or 2, wherein the rhodium salt is at least one of rhodium chloride, rhodium nitrate, rhodium acetate and rhodium triacetylacetonate.
4. The process for producing the carbon-supported rhodium-based ordered intermetallic compound according to claim 1, wherein in the step (2), the heating time under the low temperature condition is 1 to 3 hours, and the heating time under the high temperature condition is 2 to 10 hours; the heating rate of heating under the low temperature condition and the heating rate of heating under the high temperature condition are both 5-10 ℃/min.
5. The process for producing a carbon-supported rhodium-based ordered intermetallic compound according to claim 1 or 2, characterized in that the platinum group metal salt other than rhodium is a platinum salt, an iridium salt or a ruthenium salt;
preferably, the platinum salt is at least one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum acetylacetonate, platinum dichloride and platinum tetrachloride; the iridium salt is at least one of iridium acetate, iridium chloride, iridium sodium chlorate, iridium tetrachloride hydrate, iridium acetylacetonate and potassium hexachloroiridate; the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate, ruthenate, potassium ruthenate, ammonium ruthenate chloride, sodium ruthenate chloride and potassium ruthenate chloride.
6. The process of claim 1 or 2, wherein the non-noble metal salt is an iron, zinc or bismuth salt;
preferably, the iron salt is at least one of ferric chloride, ferrous chloride, ferric acetylacetonate, ferric acetate, ferric sulfate and ferric nitrate; the zinc salt is at least one of zinc chloride, zinc acetate, zinc acetylacetonate hydrate, zinc sulfate and zinc nitrate hydrate; the bismuth salt is at least one of bismuth chloride, bismuth acetate, bismuth sulfate and bismuth nitrate pentahydrate.
7. The method of claim 1, wherein the carbon support is at least one of carbon nanotubes, carbon nanofibers, carbon black, graphene oxide, and reduced graphene oxide.
8. The carbon-supported rhodium-based ordered intermetallic compound prepared by the method of any one of claims 1 to 7.
9. The carbon-supported rhodium-based ordered intermetallic compound of claim 8, wherein the mass fraction of rhodium element in the carbon-supported rhodium-based ordered intermetallic compound is between 20% and 50%.
10. Use of the carbon-supported rhodium-based ordered intermetallic compound according to claim 8 or 9 in anode catalysts for formic acid fuel cells.
CN202211035137.1A 2022-08-26 2022-08-26 Carbon-supported rhodium-based ordered intermetallic compound, preparation and application as catalyst Pending CN115472846A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210299749A1 (en) * 2018-07-31 2021-09-30 Northwestern University Tetrahexahedra nanoparticles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210299749A1 (en) * 2018-07-31 2021-09-30 Northwestern University Tetrahexahedra nanoparticles
US11673197B2 (en) * 2018-07-31 2023-06-13 Northwestern University Tetrahexahedra nanoparticles

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