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as) United States a2) Patent Application Publication co) Pub. No.: US 2025/0281915 Al US 20250281915A1 TOUR et al. (43) Pub. Date: Sep. 11, 2025 (54) SYNTHESIS OF METALLIC GLASS BOLT 35/45 (2024.01) NANOPARTICLES BY FLASH BOLT 37/02 (2006.01) CARBOTHERMIC REACTIONS AND BOIS 37/04 (2006.01) COMPOSITIONS THEREOF BOIS 37/08 (2006.01) . CO7B 37/02 (2006.01) (71) Applicant: WILLIAM MARSH RICE CO7F 5/02 (2006.01) UNIVERSITY, Houston, TX (US) C25B 1/054 (2021.01) (72) Inventors: James M. TOUR, Houston, TX (US); C25B 11/061 (2021.01) Bing DENG, Houston, TX (US) (52) ww. BOLJ 27/1856 (2013.01), BOLT 21/18 (73) Assignee: WILLIAM MARSH RICE (2013.01); BOLJ 35/45 (2024.01); BOLT UNIVERSITY, Houston, TX (US) 37/0203 (2013.01); BOLT 37/0213 (2013.01); BOLJ 37/04 (2013.01); BOLT 37/088 (21) Appl. No.: 18/735,513 (2013.01); CO7B 37/02 (2013.01); CO7F 5/025 oad (2013.01); C25B 11/054 (2021.01); C25B (22) Filed: Jun. 6, 2024 1061 (2021.01) Related U.S. Application Data (60) Provisional application No. 63/506,410, filed on Jun. (67) ABSTRACT 6, 2023. Publication Classification Synthesis of metallic glass nanoparticles and compositions (51) Int. Cl. thereof, including, particularly, the kinetically controlled BOLT 27/185 (2006.01) synthesis of glass nanoparticles by flash carbothermic reac- BOIS 21/18 (2006.01) tions and compositions thereof.
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Patent Application Publication Sep. 11,2025 Sheet 1 of 22 US 2025/0281915 Al FIG. 1A
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Patent Application Publication Sep. 11,2025 Sheet 2 of 22 US 2025/0281915 Al Ni/Cu/Fe/Co/Sn A @ Pd/Pt FIG. 1B ae
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Patent Application Publication Sep. 11,2025 Sheet 22 of 22 US 2025/0281915 Al TABLE VIII “a . Fafet Catabyst fon ‘eva comespoting) pa TOP Gbws | References Grd oe) bn} ects Amorpinnus PaSey a 23 Bs ig He 2022 PeOLe as ew % as | PERO re 209 Pregeaghene ast 1 38 _ rewind | Lie 2nee Minti st Ph 18 He 38 Bi Bhang BLE Rag a288 10 2 Re . Uahimeost 2027 OsONS ~ 48 x 4g tye We RENAME Q2k2 ety ag at ACTS ~ it a 23 Py 2082 PRACeCaNe O82 #® 28 an ~ baa 202) BOs O83 pei ¥ 268 Baa m¥ Lanse Pie: oa pt B 22 ESOPGAGR mV | Dat 2S BuGMWCNTs ay 3 iss pea NBS mY | Kiweor 2000 PHEMeS; - se 4 3 Sly 2028 PB De ~ Bt 2 29.8 Foe 20g PHANERC. $102 # eS 34 FSP Bong HEY BNC 19 it 2ESL Ban 2039 WGARSC * ue 38 4852 You 262¢ Pec Octo at 3h es Hereix Pili NE O.204 bee 3S as Hives Pole MONE a:204 0 4 ig | STG aN Heveis Note: Al the nmasurements were conducted ip OS M HSO¢ using « three-clectrade configuration. FIG. 9
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US 2025/0281915 Al SYNTHESIS OF METALLIC GLASS NANOPARTICLES BY FLASH CARBOTHERMIC REACTIONS AND COMPOSITIONS THEREOF CROSS-REFERENCED TO RELATED PATENT APPLICATIONS [0001] The application claims priority to U.S. Patent Appl. Ser. No. 63/506,410, to James M. Tour, et al., entitled “Synthesis Of Metallic Glass Nanoparticles By Flash Car- bothermic Reactions And Compositions Thereof,” filed Jun. 6, 2023, which patent application is commonly owned by the owner of the present invention and is incorporated herein in its entirety. GOVERNMENT INTEREST [0002] This invention was made with government support under Grant No. FA9550-19-1-0296 and No. FA9550-22-1- 0526, awarded by the United States Air Force Office of Scientific Research. The United States government has certain rights in the invention. TECHNICAL FIELD [0003] The present invention relates to the synthesis of metallic glass nanoparticles and compositions thereof, including, particularly, the kinetically controlled synthesis of glass nanoparticles by flash carbothermic reactions and compositions thereof. BACKGROUND [0004] Nanoscale metallic glasses offer opportunities for investigating fundamental properties of amorphous solids [Yang 2021] and technological applications in biomedicine, microengineering, and catalysis [Kumar 2009; Glasscott 2019; Gao 2022]. The top-down fabrication of metallic glass nanostructure is restricted by the availability of bulk metallic glass [Chen 2011; Yan 2020]; in contrast, the bottom-up synthesis remains rarely explored due to the rigorous for- mation conditions, especially the extreme cooling rate [Zhong 2014]. [0005] Metallic glasses (MG), first discovered by melt quenching of the Au—Si alloy [Klement 1960], are a broad class of solid metallic materials with amorphous atomic structures [Greer 2009]. Depending on the glass forming ability (GFA) that is quantitatively described by the critical cooling rate (R.), MG exhibit many dimensional forms. For example, MG ribbons, typically <100 uum, are made by rapid quenching of alloy melts [Klement 1960], MG thin films are fabricated by physical vapor deposition [Li M 2019; Ding 2014], and bulk MG with very low Rg are afforded by casting [Chen 2011; Kui 1984]. [0006] Recently, MG nanostructures have received con- siderable interests due to their unique atomic structures [Yang 2021], intriguing size-dependent mechanics [Kiani 2020; Sha 2019; Jang 2010], and the potential application in unconventional areas including additive manufacturing [Shen 2017], nanoimprinting [Kumar 2009], and catalysis [Glasscott 2019; Gao 2022; Li J 2019; Hu 2016; Carmo 2011; Pang 2021]. The present top-down fabrication of MG nanostructures involves thermoplastic forming [Kumar 2009; Carmo 2011; Kumar 2011], thermal drawing tech- niques [Yan 2020], selective etching [Wada 2007], and laser ablation [Liang 2021]. However, the top-down approaches Sep. 11, 2025 rely on bulk MG counterpart availability, which heavily restricts the materials and composition choice. [0007] However, the top-down approaches rely on bulk MG counterpart availability, which restricts the material and composition choice. The bottom-up nanoscale MG synthesis such as chemical reduction [Kiani 2020; Ma 2015; Zhao 2014; Wang 2021], electrochemical synthesis [Glasscott 2019; Zeeshan 2016], and physical vapor deposition [Liu 2015] affords better size, morphology, and compositional tunability. However, wet chemistry-based processes often lead to contaminated by surfactants [Wang 2021], while physical deposition methods require a substrate that hinders intrinsic property studies and wide-range applications. [0008] It is highly desired but still very challenging to develop a bottom-up method for synthesis of nanoscale MG with pure and tunable compositions, small size, and good morphology. SUMMARY OF THE INVENTION [0009] The present invention relates to the synthesis of metallic glass nanoparticles and compositions thereof, including, particularly, the kinetically controlled synthesis of glassy nanoparticles by flash carbothermic reactions (FCR) and compositions thereof. [0010] In general, in one embodiment, the invention fea- tures a method for synthesizing metallic glass nanoparticles. The method includes mixing a metal/metalloid precursor with a material comprising carbon. The method further includes performing a flash Joule heating process using the material mixed with the metal/metalloid precursor in which the metal/metalloid precursors are decomposed and fused into alloy melts. The method further includes rapidly cooling the alloy melts to vitrify the alloy melts into the metallic glass nanoparticles. [0011] Implementations of the invention can include one or more of the following features: [0012] The method can include a kinetically controlled synthesis of the metallic glass nanoparticles. [0013] The step of mixing can include dissolving the metal/metalloid precursor in a solvent to forma solution and wetting the material comprising the carbon with the solu- tion. [0014] A phosphorous source can be dissolved in the solvent when forming the solution. [0015] The phosphorous source can be PPh. [0016] The step of wetting can include impregnating the metal/metalloid precursor on the material comprising the carbon. [0017] The solvent can be selected from the group con- sisting of alcohols, water, and mixtures thereof. [0018] The solvent can include ethanol. [0019] The carbon in the material can serve as a conduc- tive additive and a supporting substrate in the flash Joule heating process. [0020] The material can include carbon black. [0021] The metallic glass nanoparticles can be Pd- and/or Pt-based metallic glass nanoparticles. [0022] The metallic glass nanoparticles can be selected from the group consisting of PdNiP, PdCuP, PdCuNiP, PtNiP, PtCuP, PtCuNiP, and PdCuFeNiP metallic glass nan- oparticles and combinations thereof. [0023] The metallic glass nanoparticles can have the chemical formula M,—M.—P. M, can be selected from the
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US 2025/0281915 Al
group consisting of Pt, Pd, and combinations thereof. M, can
be selected from the group consisting of Cu, Ni, Fe. Co, Sn,
and combinations thereof.
[0024] The flash Joule heating process can include pro-
viding millisecond current pulses through the metal/metal-
loid precursor at a heating rate of at least 10° K/s.
[0025] The heating rate can be at least 10* K/s.
[0026] The flash Joule heating process can raise the tem-
perature of the metal/metalloid precursors to at least 1800 K.
[0027] The rapidly cooling can be performed at an ultra-
fast rate of cooling of at least 10? K/s.
[0028] The ultrafast rate of cooling be at least 10° K/s.
[0029] The ultrafast rate of cooling can be by thermal
radiation.
[0030] The metal/metalloid precursors can be selected
from the group consisting of H,PtCl,, PdCl,, CuCl, NiCl,
FeCl,, PPh;, P,O,, and combinations thereof.
[0031] The metal/metalloid precursor can include a metal
salt.
[0032] The metal salt can be selected from the group
consisting of H,PtCl,, PdCl,, CuCl,, NiCl,, FeCl, and
combinations thereof.
[0033] In general, in another embodiment, the invention
features a composition including metallic glass nanopar-
ticles made by any of the above-described methods.
[0034] In general, in another embodiment, the invention
features a method that includes using any of the above-
described compositions a catalyst. The catalyst includes the
metallic glass nanoparticles.
[0035] Implementations of the invention can include one
or more of the following features:
[0036] The metallic glass nanoparticles can be used as
catalysts for a hydrogen evolution reaction.
[0037] The metallic glass nanoparticles can be used as
catalysts for clean H, production via water electrolysis.
[0038] The metallic glass nanoparticles can be used as
catalysts for catalytic coupling.
[0039] The catalytic coupling can be of a boronic acid and
an aryl halide.
[0040] The catalytic coupling can be Suzuki-Miyaura cou-
pling or Miyaura-Heck coupling.
[0041] The metallic glass nanoparticles can include Pt{NiP
metallic glass nanoparticles.
[0042] The metallic glass nanoparticles can include PaNiP
metallic glass nanoparticles.
[0043] The metallic glass nanoparticles can be used as
catalysts for a reaction selected from the group consisting of
electrochemical reactions, hydrogen evolution reactions,
oxygen reduction reactions, carbon dioxide reduction reac-
tions, reactions used in fuel cells, carbon-carbon bond
forming reactions, carbon hydrogen bond forming reactions,
hydroformylation reactions, carbon monoxide insertion
reactions, and reductive elimination reactions.
[0044] The metallic glass nanoparticles can be used as
catalysts for a hydrogenation reaction.
[0045] The hydrogenation reaction can be hydrogenation
of one or more alkenes and/or alkynes. The metallic glass
nanoparticles can include a metal selected from the group
consisting of Pd, Pt, Ni, and Rh.
[0046] The hydrogenation reaction can be hydrogenation
of one or more nitriles. The metallic glass nanoparticles can
include a metal selected from the group consisting of Pd, Pt,
Ni, and Rh.
Sep. 11, 2025
[0047] The hydrogenation reaction can be hydrogenation
one or more aromatic compounds. The metallic glass nan-
oparticles can include a metal selected from the group
consisting of Pd, Pt, and Ru.
[0048] The metallic glass nanoparticles can be used as
catalysts for an oxidation reaction.
[0049] The oxidation reaction can be oxidation of one or
more alcohols. The metallic glass nanoparticles can include
a metal selected from the group consisting of Pd, Pt, and Ru.
[0050] The oxidation reaction can be oxidation of one or
more olefins. The metallic glass nanoparticles can include a
metal selected from the group consisting of Pd, Mn, and Co.
[0051] The oxidation reaction can be oxidation of one or
more hydrocarbons. The metallic glass nanoparticles can
include a metal selected from the group consisting of V and
Mo.
[0052] The metallic glass nanoparticles can be used as
catalysts for a carbon-carbon bond forming reaction.
[0053] The carbon-carbon bond forming reaction can be a
Heck reaction. The metallic glass nanoparticles can include
Pd.
[0054] The carbon-carbon bond forming reaction can be a
Suzuki coupling. The metallic glass nanoparticles can
include Pd.
[0055] The carbon-carbon bond forming reaction can be a
Sonogashira coupling. The metallic glass nanoparticles can
include a metal selected from the group consisting of Pd and
Cu.
[0056] The carbon-carbon bond forming reaction can be a
Stille coupling. The metallic glass nanoparticles can include
[0057] The carbon-carbon bond forming reaction can be a
Negishi coupling: The metallic glass nanoparticles can
include a metal selected from the group consisting of Pd and
Ni.
[0058] The metallic glass nanoparticles can be used as
catalysts for a polymerization reaction.
[0059] The polymerization can be a Ziegler-Natta polym-
erization. The metallic glass nanoparticles can include a
metal selected from the group consisting of Ti and Al.
[0060] The polymerization can be a Metallocene polym-
erization. The metallic glass nanoparticles can include a
metal selected from the group consisting of Zr and Ti.
[0061] The metallic glass nanoparticles can be used as
catalysts for a reduction reaction.
[0062] The reduction reaction can be a Birch reduction.
The metallic glass nanoparticles can include (a) Na and/or Li
and (b) Fe.
[0063] The reduction reaction can be a catalytic transfer
hydrogenation. The metallic glass nanoparticles can include
a metal selected from the group consisting of Pd and Pt.
[0064] The metallic glass nanoparticles can be used as
catalysts for a cross-coupling reaction.
[0065] The cross-coupling reaction can be a Buchwald-
Hartwig amination. The metallic glass nanoparticles can
include Pd.
[0066] The cross-coupling reaction can be a Kumada
coupling. The metallic glass nanoparticles can include a
metal selected from the group consisting of Ni and Pd.
[0067] The metallic glass nanoparticles can be used as
catalysts for a metathesis reaction.
[0068] The metathesis reaction can be an olefin metath-
esis. The metallic glass nanoparticles can include a metal
selected from the group consisting of Ru and Mo.Page 26
US 2025/0281915 Al [0069] The metathesis reaction can be an alkyne metath- esis. The metallic glass nanoparticles can include a metal selected from the group consisting of W and Mo. [0070] The metallic glass nanoparticles can be used as catalysts for a C—H activation. [0071] The C—H activation can be a C—H functional- ization. The metallic glass nanoparticles can include a metal selected from the group consisting of Pd, Rh, and Ru. [0072] The metallic glass nanoparticles can be used as catalysts for a water-gas shift reaction: Iron (Fe) and copper (Cu) catalysts. [0073] The metallic glass nanoparticles can be used as catalysts for a Fischer-Tropsch synthesis. The metallic glass nanoparticles can include a metal selected from the group consisting of Fe and Co. [0074] The metallic glass nanoparticles can be used as catalysts for an ammonia synthesis (Haber Process). The metallic glass nanoparticles can include Fe. [0075] The metallic glass nanoparticles can be used as catalysts for a methanol synthesis. The metallic glass nan- oparticles can include a metal selected from the group consisting of Cu and Zn. [0076] The metallic glass nanoparticles can be used as catalysts for a Wacker process. The metallic glass nanopar- ticles can include a metal selected from the group consisting of Pd and Cu. BRIEF DESCRIPTION OF THE DRAWINGS [0077] FIGS. 1A-1E show synthesis of MGNP by flash carbothermic reaction. FIG. 1A is a schematic of the FCR process for MGNP synthesis. FIG. 1B shows molecular dynamics simulated atomic model of a ternary MGNP. FIG. 1C is a pulsed current curve under the FCR conditions of 100 V and 50 ms. Inset of FIG. 1C are pictures of the sample before (top) and during (bottom) the FCR reaction (scale bar, 1 cm). FIG. 1D is a real-time temperature curve recording using an infrared thermometer. T,,,,,, and T, are the maxi- mum temperature of the FCR process and the glass transi- tion temperature of PdNiP, respectively. FIG. 1E is a sche- matic of the time-temperature transformation diagram showing the kinetic formation of MG. T,,, and T, are the melting temperature and the glass transition temperature of PdNiP, respectively. [0078] FIGS. 2A-21 show characterization of PdNiP MCNP. FIG. 2A is a XRD pattern of the PANiP MGNP supported on carbon black. The PDF reference card is graphite (PDF #41-1487). FIG. 2B is a bright-field trans- mission electron microscopy (BF-TEM) image of the PdNiP MGNP supported on carbon black. Inset of FIG. 2B is SAED pattern of the MGNP supported on carbon black. The scale bar is 50 nm for the TEM image, and 5 nm”! for the SAED pattern. FIG. 2C is a HRTEM image of the PdNiP MGNP and corresponding FFT image (inset of FIG. 2C). Scale bar, 5 nm. FIG, 2D is a nanobeam diffraction pattern of the PANiP MGNP, and the intensity profile derived from the electron diffraction. k, and k, are the first and second diffraction vectors, respectively. Scale bar, 5 nm™'. FIG. 2B shows size distribution of the PANiP MGNP. The average size is 10.6#1.6 nm. FIG. 2F shows elemental composition of the PANiP MGNP determined by EDS. Three points were collected with the average composition of Pd,;Ni,¢P3,. FIG. 2G is XPS fine spectrum of Pd. FIG. 2H is XPS fine spectrum of Ni. FIG. 21 is XPS fine spectrum of P. Sep. 11, 2025 [0079] FIGS. 3A-3F show general synthesis of MGNP by the FCR process with HRTEM images, corresponding FFT patterns, HAADF-STEM images, elemental maps, and EDS spectra for (a) FIG. 3A: ternary PANiP MGNP; (b) FIG. 3B: ternary PdCuP MGNP; (c) FIG. 3C: ternary PtCuP MGNP; (d) FIG. 3D: quaternary PdCuNiP MGNP; (e) FIG. 3E: quaternary PtCuNiP MGNP; and (f) FIG. 3F: quinary, high-entropy PtPdCuNiP MGNP. All scale bars in the HRTEM images and STEM images are 10 nm. [0080] FIGS. 4A-4N show nanoscale effect enhanced glass forming ability. FIG. 4A is the phase diagram of the ternary Pd—Ni—P system. The compositions of bulk MG and ribbon MG were from literatures values. [He 1996; Schluckebier 1983]. FIG. 4B is calculated R, of the ternary Pd—Ni—P system. The dash line denotes the composition of P=20 at %. FIG. 4C shows molecular dynamics simulated 3D atomic model of MG nanoparticle with composition of PdysgNijo7P6o (P at %~19%). FIG. 4D shows molecular dynamics simulated 3D atomic model of MG bulk with composition of Pd,;)Ni,j9P so (P at %~19%). FIGS. 4E-4F are local bond orientational order parameters of all the atoms in, respectively, (E) the MG nanoparticle and (F) the MG bulk. The dashed curves denote the normalized bond orien- tational order parameter at 0.5, which serves as the criterion differentiating disordered and ordered structures. FIG. 4G shows the ten most abundant Ni/Pd-centered Voronoi poly- hedra in the MG nanoparticle. FIG. 4H shows four repre- sentative Ni/Pd-centered Voronoi polyhedra. FIG. 41 shows the ten most abundant P-centered Voronoi polyhedra in the MG nanoparticle. FIG. 4J shows four representative P-cen- tered Voronoi polyhedra. FIG. 4K is the coordination num- ber distribution of Ni/Pd and P for MG nanoparticle. The average coordination number of Ni/Pd and P are 11.5 and 7.9, respectively. FIG. 4L is the coordination number dis- tribution of Ni/Pd and P for MG bulk. The average coordi- nation number of Ni/Pd and P are 11.1 and 8.8, respectively. [0081] FIGS. 5A-5H show nanoscale effect enhanced glass forming ability. FIG. 54 shows calculated R. of the ternary Pd—Co—P system. The black line denotes R-=10* Ks“. FIG. 5B shows a HRTEM image of PdCoP MGNP. Scale bars, 10 nm. The inset of FIG. 5B shows the corre- sponding FFT pattern. FIG. 5C shows EDS spectrum of PdCoP MGNP. FIG. 5D shows calculated R, of the ternary Pd—Sn—P system. The black line denotes R-=10* Ks“. 5E shows a HRTEM image of PdSnP MGNP. Scale bars, 10 nm. The inset of FIG. 5E shows the corresponding FFT pattern. FIG. 5F shows EDS spectrum of PdSnP MGNP. FIG. 5G shows a HRTEM image, the corresponding FFT pattern, HAADF-STEM image, and EDS maps of PdCuFeNiP MGNP. Scale bars, 10 nm. FIG. 5H shows EDS spectrum of PdCuFeNiP MGNP. [0082] FIG. 6 shows TABLE III, which is a table reflecting the chemical state analysis of MGNP by XPS. [0083] FIG. 7 shows TABLE V, which is a table reflecting some PdNiP catalyzed Suzuki-Muyara reactions. [0084] FIG. 8 shows TABLE VI, which is a table reflect- ing some PdNiP MGNP catalyzed Miyaura-Heck reactions. [0085] FIG. 9 shows TABLE VIII, which is a table reflect- ing some recently reported previous metal-based HER elec- trocatalytsts in acid solution, as well as the use of ternary PtNiP MGNP as the high-performance electrocatalyst.
Page 27
US 2025/0281915 Al DETAILED DESCRIPTION [0086] The present invention relates to the synthesis of metallic glass nanoparticles and compositions thereof, including, particularly, the kinetically controlled synthesis of glass nanoparticles by flash carbothermic reactions and compositions thereof. [0087] A kinetically controlled flash carbothermic reaction featuring ultrafast heating (>10° K s~') and cooling (>10* K s-') has been discovered for the synthesis of metallic glass nanoparticles (MGNP) within milliseconds. Various permu- tations of noble metals, base metals, and metalloid (M,— M,—P, M,=Pt/Pd, M.=Cu/Ni/Fe/Co/Sn) have been synthe- sized with widely tunable particle sizes and supportive substrates. Through combinatorial development, a substan- tially larger phase space of nanoscale metallic glass has been discovered compared to the bulk counterpart, revealing that the nanosize effect enhanced glass forming ability. Guided by this, several nanoscale metallic glasses with elemental compositions have been synthesized that have never, to Applicant’s knowledge, been synthesized in bulk. The metallic glass nanoparticles show high activity in heteroge- neous catalysis, outperforming crystalline metal alloy nan- oparticles. [0088] A thermal process for nanoscale MG synthesis necessitates certain features. First, a high temperature is necessary to ensure the intimate mixing of multiple metal elements with diverse miscibility, as MGs are typically composed of three or more elements. [Greer 2009]. Second, a short reaction duration is required to minimize particle agglomeration and achieve uniform, nanoscale particle dis- persion. Finally, an ultrafast cooling rate is needed to vitrify the alloy melt and avoid crystallization. Recently, several unconventional thermal processes [Chen 2016; Liu 2022; Deng 2021] have been reported for synthesizing alloy nan- oparticles with single-phase crystal structures, such as the electrothermal-based shock synthesis of high-entropy alloy nanoparticle [Yao 2018; Yao 2020: Cui 2022; Yao 2022], the photothermal -based laser ablation synthesis of high-entropy alloy and ceramic nanoparticles [Wang 2022], and the flash Joule heating synthesis of metastable nanocrystals [Chen 2021; Deng I 2022; Deng II 2022]. It is believed that by rational composition design, nonequilibrium thermal pro- cesses can kinetically suppress crystallization and produce metastable glassy materials. [0089] The present invention relates to the flash carboth- ermic reaction (FCR) for the general synthesis of metallic glass nanoparticles (MGNP). Metal precursors loaded on a carbon substrate are subjected to millisecond current pulses, rapidly raising the temperature to ~1800 K through Joule heating (10° K s“!). The resulting ally melts then cool at an ultrafast rate (>10* K s“') through thermal radiation, vitri- fying into glassy nanoparticles. FCR is feasible for the synthesis of various Pd- and Pt-based MGNP, including palladium-nickel-phosphorous (PdNiP), PdCuP, PdCuNiP, PtNiP, PtCuP, PtCuNiP, and the high-entropy PtPdCuNiP. [0090] By constructing the phase diagram of PdNiP nan- oparticles through combinational development, it was dis- covered that the composition space of MG at the nanoscale is substantially expanded than that of the bulk counterpart, showing that the nanosize effect enhances the GFA. Strue- tural simulations further revealed delicate short-range order differences between nanoscale and bulk MG. The enhanced GFA allows for the synthesis of nanoscale MG with com- positions that have never been achieved in bulk, exemplified Sep. 11, 2025 by PdCoP, PdSnP, and high-entropy PdCuFeNiP. Further- more, applications of MGNP in heterogenous catalysis have been performed, which outperform the crystalline counter- parts. Synthesis of PUNiP MGNP by Flash Carbothermic Reaction [0091] In embodiments, the flash carbothermic reaction (FCR) for MGNP synthesis involves three steps (FIG. 1A): [0092] First, the metal/metalloid precursors are dissolved (such as in ethanol) and homogeneously wet impregnated onto a support (such as a carbon black support), which simultaneously served as the conductive additive and sup- porting substrate. (Structurally, the carbon black is com- posed of amorphous carbon nanospheres.) [0093] Then, pulsed direct current input rapidly ramps up the sample to a high temperature [Yao 2018; Johnson 2011], leading to the decomposition of the metal precursors and elemental liquid metals. See FIG. 1A. Since these metals do not wet carbon, the liquid metals diffuse to reduce their surface energy at high temperature, and subsequently fuse into alloy melts driven by the negative enthalpy of mixing (AH,,;,)- [Takeuchi 2001]. [0094] The sample was then rapidly cooled due to the intensive thermal radiation and low heat capacity of carbon substrate (<0.033 J K~') [Butland 1973] (FIG. 1A), resulting in the vitrification of the alloy melt into glassy nanoparticles (FIG. 1B). [0095] Due to the good GFA of ternary palladium-nickel- phosphorous (PdNiP), it was chosen and synthesized as a representative example [Chen 2011]. In a typical trial, a pulsed current of ~90 A within 50 ms was applied to the precursor mixture in an Ar-filled chamber (FIG. 1C). With strong light emission (FIG. 1C, inset), the sample tempera- ture rapidly reached its maximum at T,,,,.~1760 K (FIG. 1D) beyond the decomposition temperature of metal precursors. See TABLE I. TABLE I Physical properties of the metal precursors and corresponding metals/metalloids Decomposition Metal/ Melting Boiling Precursoxs temp. (K) Metalloid point (K) point (K) PdCl, 863-1013 Pd 1828 3236 HPtCl, >783 Pt 2041 4098 CuCl, 1273 Cu 1358 3200 Nich, 1073 Ni 1728 3186 FeCh, 713, Fe 1811 3134 PPh, Crack? P 860 893 (sublimation) Note: The thermal homolysis temperature of organics is usually well below 1270K. In the FCR process, the maximum temperature is ~1760K, which is enough for the decomposition of PPh. [0096] Based on T,,,,, and the glass transition temperature (T,) of PdNiP (~600 K) [Chen 1973], the cooling rate was calculated to be ~1.5x10* K s“*, which is higher than the Rc of PdNiP bulk MG [He 1996]. [0097] Deviating from thermodynamically equilibrium crystal phases, metallic glass is typically trapped by a kinetic barrier. According to the temperature-time transformation diagram, as schematically shown in FIG. 1E, the cooling rate determines the formation of glassy or crystal phases. In the scenario of FCR, the rapid cooling enables the glassy phase
Page 28
US 2025/0281915 Al formation. As a control, the synthesis using a tube furnace with a slow cooling rate (~10 K min“’) led to the formation of crystalline PdNiP nanoparticles. Characterization of PaNiP MGNP [0098] The amorphous structure of the as-obtained PdNiP NP was confirmed by X-ray diffraction (XRD) and trans- mission electron microscopy (TEM). The XRD pattern did not show any peaks from crystalline components, except for the broad diffraction peaks from the amorphous carbon support (FIG. 2A). The synthesized nanoparticles (NPs) were supported on the carbon black (FIG. 2B). The selected- area electron diffraction (SAED) showed diffusive diffrac- tion halos without discrete spot (FIG. 2B, inset). [0099] The amorphous structure was further confirmed by high-resolution TEM (HRTEM) and the corresponding fast Fourier transformation (FFT) pattern (FIG, 2C). HRTEM. images with tilt range from 0° to 5° were acquired, and all are characterized of an amorphous structure. [0100] To exclude the effect of the carbon support, nano- beam diffraction was performed on a single NP that showed similar diffuse halos (FIG. 2D, inset). The normalized inten- sity of the nanobeam diffraction pattern showed the main peak positions at 4.12 nm7! and 6.96 nm7’, which corre- sponds to k,/k,~1.69 (FIG. 2D), in agreement with previous experimental results on PdNiP bulk MG [Lan 2017]. [0101] The particle size was calculated based on the data from the TEM images, showing an average size of ~10.6 nm. and a narrow size distribution (FIG. 2E). The average composition was determined to be Pd,,Ni,,P3, by energy- dispersive X-ray spectroscopy (EDS) (FIG. 2F). [0102] The element composition of the MGNP were deter- mined by statistics using EDS. Taking PANiP MGNP as an example, the EDS spectrum shows the appearance of Pd, Ni, P, and C peaks. The C peak is from the carbon support. Three points were tested and obtained the elemental ratios of Pd (43.120.8 at %), Ni (26.3#1.8 at %), and P (30.7+1.0 at %), so the composition of the MGNP could be estimated as Pd43Ni26P31. The small standard deviation showed the compositional uniformity of the MGNP. Based on the same method, TABLE II shows the elemental compositions of particular MGNP. Sep. 11, 2025 TABLE II Elemental composition of MGNP MGNP Average composition PdNiP MGNP PaysNizagP ay PdCuP MGNP PdygCuzoP22 PdCuNP MGNP PdagCuy3NisP30 PtNiP MGNP Pty4NiggP22 PtCuP MGNP PtgyCuggP og PtCuNiP MGNP PtygCurgNin Poy PtPdCuNiP MGNP Pty Pdg9Cuy NijoPo7 PdCoP MGNP Pd3pCoy9Pao PdSnP MGNP PdoSiysPsq PdCuNiFeP MGNP Pdg3Cuy NitsFe iP, [0103] Due to the short duration of the FCR process and the temperatures being <2500 K, the carbon substrates remain unchanged. The high temperature of the FCR process resulted in the complete reaction, leaving no chloride resi- due in the product. [0104] The electronic structures of the PANiP MGNP were investigated by X-ray photoemission spectroscopy (XPS). (See FIGS. 2G-21; FIG. 6 (showing TABLE IID). [0105] Various chemical bonds, including Pd—Pd, Ni— Ni, P—P, Pd—Ni, Pd—P and Ni—P, were found, resulting from its amorphous feature. The Pd 3d is split into two peaks of Pd 3d,,. and 3d, (FIG. 2G). The Pd 3d,,. peak at 335.4 eV is assigned to PA—M (including Pd—Pd [Kohiki 1990] and Pd—Ni [Hillebrecht 1982]). The Pd 3d,,. peak at 337.0 eV is assigned to Pd—P. [Nefedov 1980]. The minor Pd 3d,,5 peak at 338.3 eV could be assigned to be Pd—O [Kim 1974] due to the surface oxidation. The Ni 2p,,, peak at 852.9 eV is assigned to Ni—P, and the peak at 857.0 eV is its satellite peak [Jin 2020] (FIG. 2H). The minor Ni 2p,,5 peak at 854.3 eV can be assigned to Ni—O due to surface oxidation. The P 2p is split into two peaks of P 2p,,. and 2p, 2. For P 2p3)., the peak at 130.5 eV is assigned to P—M. [Wang 1988], and the peak at 132.5 eV could be assigned to M—? (FIG. 21). General Synthesis of Pd- and Pt-Based Metallic Glass Nanoparticles [0106] To demonstrate the versatility of the FCR method utilized in embodiments of the present invention, a series of Pd- and Pt-based MGNP were synthesized using different precursors (FIGS. 3A-3F; FIG. 6 (TABLE III); and TABLE IV). TABLE IV Precursors and FCR conditions for MGNP synthesis Mass FCR FCR Precursor Molar Ratios loading voltage time Product Swt% 100 50 ms PdNiP MGNP Swt% 100V 30 ms PdCuP MGNP Swt% 100 50 ms PdCuNiP MGNP Swt% —100V 50 ms PINiP MGNP Swt% 100V 50. ms PtCuP MGNP Swi% 100V 50 ms P1CuNiP MGNP Swt% 100V 50. ms PtPdCuNiP MGNP swi% 100 50 ms PdCoP MGNP. Swt% 100V 30 ms PdSaP MGNP swi% 100 50. ms PdCuFeNiP MGNP Swt% —100V 50 ms Pt crystal NP S wt % 100 V 50 ms PtNi crystal NP
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US 2025/0281915 Al TABLE IV-continued Sep. 11, 2025 Precursors and FCR conditions for MGNP synthesis Mass FCR FCR Precursor Molar Ratios loading voltage time Product Pt:Ni:P = 1:1:2 S wt % 100 V 100 ms — crystal NP Pi S wt % 100 V 150 ms crystal NP Pt:Ni:P = 1:1:2 S wt % 100 V 100 ms — Crystal NP Note: The precursors are PCH, NiCh, CuCh, HyPtClg, FeCl, and PPh, The mass loading denotes the mass ratio of Pd or Pt with respeet to earbon black. [0107] Generally, the GFA of an alloy was susceptible to its composition, where the difference of a few atomic ratio percentages could induce a change of R¢ by several orders of magnitude [Bordeenithikasem 2017]. Nevertheless, due to the presence of deep eutectics in the Pd—P and Pt—P systems, the Pd- and Pt-based MG can be synthesized over a wide compositional range [Schwartz 1997]. To control product composition, an excessive supply of P was employed given its high volatility compared to other metal components. (See TABLE I and TABLE IV). [0108] The amorphous features of the as-synthesized nan- oparticles were confirmed through multiscale characteriza- tion methods including XRD, SAED, and HRTEM. The average compositions were Pd,;Ni,,P3, (FIG. 3A), PdygCtyoP3. (FIG. 3B), PtyyCusgP,g (FIG. 30), PdgoCu, sNigP3 (FIG. 3D), PtygCu,4Ni, ;P>7 (FIG. 3E), and the quinary Pt,,Pd,,Cu, ,Ni,P,, (FIG. 3F) which is consid- ered as high-entropy MG [Glasscott 2019; Takeuchi 2011; Duan 2022]. High-angle annular dark-field scanning trans- mission electron microscopy (HAADF-STEM) image and element maps demonstrated uniform distributions of ele- ments. The nanoparticles exhibited structural and elemental uniformity, regardless of their compositions. The EDS spec- tra of individual nanoparticles of all compositions show the absence of carbon or oxygen peaks (FIGS. 3A-3F), proving that the as-synthesized nanoparticle is metallic glass, instead of oxide glass or carbide phase. The carbon black served as the conductive additive and substrate and did not participate in the reaction. [0109] The FCR method for MGNP synthesis provides wide tunability in terms of the particle size, dispersity, compositions, and the substrates. The MGNP showed a narrow size distribution with coefficient of variation <10%. The particle size can be tuned by varying precursor loadings from 5 to 100 nm is tunable, such as by changing precursor loading or the FCR time durations; but particle size gener- ally cannot be adjusted independently from loading. The synthesized MGNP were uniformly dispersed on the carbon black support, and other conductive carbons like carbon nanotubes can be used, expanding the range of substrate applicability. [0110] The MPNPs remained stable in atmospheric con- ditions and preserve their structure, size, and morphology even after six months of storage. [0111] The FCR process for MGNP synthesis also dem- onstrated good scalability. By simply increasing the FCR voltage, a 0.2 g per batch was achieved. Considering the time used to charge the FCR system and the loading of the sample, we conclude that the time required for the 200 mg batch synthesis is ~10 s, corresponding to a production rate of 72 g hv’, higher than other reported methods like chemi- cal reduction, electrochemical synthesis, and physical vapor deposition. Nanosize Effect Enhanced Glass Forming Ability [0112] Combining easily tunable precursor loading and ultrafast synthesis, the FCR provides access to a broad compositional space of MG. Exemplified by the ternary Pd—Ni—P alloy, a large library of PdNiP nanoparticles were synthesized by combinatorial development. Their phases (crystalline or glassy) and compositions were deter- mined by TEM and EDS, respectively (FIG. 4A). The ternary Pd—Ni—P phase diagram revealed that ~54% of the nanoparticles formed a glassy phase, covering about 10 to 55 at % of P. As a comparison, the compositions of ribbon MG [Schluckebier 1983] and bulk MG [He 1996] appear to lie close to P ~20 at % (FIG. 4A), which is rooted in the deep eutectic points at approximately NigoP., and PdgoP.9. Therefore, the composition space of PdNiP MG at the nanoscale is substantially larger than the bulk counterpart, ie., the nanosize effect can enhance the glass forming ability. [0113] The R,. determines whether the phase is crystalline or glassy under a specific cooling rate. The composition- dependent R,. was calculated using an empirical model [Takeuchi 2001] and a recently developed algorithm [Gabski 2020]. (FIG. 4B). The R, strongly correlate to the P content, with compositions of 20 to 70 at % of P having R-<100 K s”! (FIG. 4B). For P content <10 at % or >80 at %, R,. surges to >10* K s~!. As the cooling rate of the present FCR is in the order of 10* K s“! (FIG. 1D), it affords the synthesis of PdNiP MGNP with P content down to ~10 at % (FIG. 4B). This is consistent with experimental results, where crystal- line phases form at P <10 at % (FIG. 4A). [0114] To further explain the dimension dependent GFA, ab initio molecular dynamics was implemented to explore the MG structure in both the nanoparticulate and bulk forms. A PdNiP nanoparticle surrounded by a vacuum layer (FIG. 4C) and a PdNiP supercell under periodic boundary condi- tions (FIG. 4D), with the same composition ratio (Pd:Ni: P~2:2:1) were modeled. While both ensembles had amor- phous atomic structures, the local bond orientational order was employed to quantitatively describe the degree of disorder. [Yang 2021; Lechner 2008]. [0115] 100% atoms in the MG nanoparticle are disordered under the normalized bond orientational order parameters criterion (FIG. 4E). By contrast, while most atoms (~96.4%) in the MG bulk are disordered, some have crystal features approaching hexagonal close packed (hep) or face cubic center (fcc) structures (FIG. 4F). These results demonstrated that, even with the same composition, the MG nanoparticle
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US 2025/0281915 Al was more disordered than its bulk counterpart, echoing the experimental observation that the nanosize effect enhanced GFA. [0116] A series of MG with P content of ~11, ~19, ~33, ~40, and ~52 at % were modeled, where all nanoparticles are more disordered than the bulk counterparts, regardless of the composition. [0117] Furthermore, the subtle differences in short-range order between nanoscale and bulk MG were analyzed based on Voronoi tessellation [Yang 2021; Guan 2012; Sheng 2006]. In metal-metalloid MG, the metals (Ni, Pd) and metalloid (P) have distinct local orders [Guan 2012]. The ten most abundant Ni/Pd-centered Voronoi polyhedra of MG nanoparticle are shown in FIG. 4G. Common motifs observed in MG, such as distorted icosahedra with indices of <0, 1, 10, 2>, <0, 2, 8, 2> and <0, 2, 8, 1>, and <0, 3, 6, 3> are identified (FIG. 4H). For the P-centered cases (FIG. 41), frequently encountered polyhedra include tricapped trigonal prisms with index of <0, 3, 6, 0>, and distorted tricapped trigonal prisms with index of <0, 4, 4, 0>, <0, 5, 2, 0>, and <0, 3, 6, I> (FIG. 4). [0118] The Voronoi polyhedra of the MG bulk are mostly the same with those in the nanoparticle. The polyhedral face distribution of all the Voronoi polyhedra showed the most abundant 5-edged Ni/Pd-centered faces in both MG nan- oparticle and bulk. By contrast, the 4-edged P-centered polyhedral faces were the most abundant for MG nanopar- ticle and 5-edged ones for MG bulk. Moreover, the coordi- nation numbers of all the atoms in the MG were determined based on the Voronoi index, from 2,n, (FIGS. 4K-4L). The average first-neighbor coordination numbers of Ni/Pd in MG nanoparticle (~11.5) was very similar with that of MG bulk (~11.1). However, the average coordination numbers of P in MG nanoparticle (7.9) are smaller than that of MG bulk at 8.8, clearly revealing the more disordered local structure of MG in nanoparticle form. Synthesis of MGNP with Expanded Composition Space [0119] The conclusion of nanosize effect enhanced GFA has at least two implications. First, for a given alloy system, a composition ratio that cannot form bulk MG may form glassy material at the nanoscale. The strict composition requirement for bulk MG formation would be lessened for bottom-up nanoscale MG synthesis, as demonstrated by the synthesis of Pd—Ni—P MGNP with wide tunable compo- sition. FIG. 4A. [0120] Second, an alloy system that is inaccessible for bulk MG may form MG at the nanoscale. Based on this, the composition space of Pd-based MG was expanded. Com- bined with the composition-dependent R,. calculation, the MGNP synthesis could be rationally designed. As examples, the choice of base metals was expanded and the synthesis of PdCoP (FIGS. 5A-5C) and PdSnP MGNPs (FIGS. 5D-5F) were achieved. Due to the similar property of Co and Ni, the composition-dependent R.. for Pd —Co—P system (FIG. 5A) resembles to that of Pd—Ni—P (FIG. 4B), where P content can be critical. By contrast, the calculated R. of Pd—Sn—P (FIG. 5D) showed that all three elements can be critical for the glassy formation. Furthermore, Fe was incor- porated and the high-entropy PdCuNiFeP MGNP (FIGS. 5G-5H) was synthesized. To Applicant’s knowledge, these MGNP compositions have not yet been reported in bulk form, so it is unknown whether they can be synthesized in Sep. 11, 2025 bulk. The present invention thus provides a process for a wide range of glassy materials and high entropy materials. Catalytic Applications of the Metallic Glass Nanoparticles [0121] Due to the versatility of the FCR method, the synthesized MGNP can find wide applications in various fields. Le., the FCR enables the scalable and rapid produc- tion of uniformly dispersed MGNP with diverse elemental compositions, which are promising in wide-range applica- tions. [0122] As a representative example, the application of MGNP in heterogeneous catalysis, exemplified by Suzuki- Miyaura coupling of a boronic acid and an aryl halide has been shown. PdNiP MGNP Catalyzed Suzuki-Miyaura Coupling Reactions [0123] As shown in FIG. 7 (TABLE V), the PANiP MGNP was used for catalyzing the Suzuki-Miyaura reaction. Experimentally, a reaction flask was charged with freshly prepared catalyst (5 mg of the as-prepared PdNiP/carbon black with Pd at ~5 wt %, corresponding to 0.2 mol % of Pd), water/ethanol (v/v=3 mL/5 mL), the aryl boronic acid (1.2 mmol), K,CO, (2.0 mmol), and the aryl halide (1.0 mmol). The mixture was stirred and heated at 70° C. for 30 min. The reaction progress was monitored by thin layer chromatography (TLC). After complete reaction, the prod- uct was analyzed by nuclear magnetic resonance (NMR). The yield, turnover number (TON), and turnover frequency (TOF) were calculated by: Yield=n(product, mol)/n(precur- sor, mol), TON=n(product, mol)/n(Pd, mol), and TOF=TON(t, where t is the reaction time in h. [0124] The results were shown in FIG. 7 (TABLE V). High yields (+99%) for different coupled biaryl products were obtained with the PANiP MGNP catalyst under mild reaction conditions. These results were compared with lit- erature reports of bimetallic catalysts of Nip sPd, , nanopar- ticles [Rai 2015], and Pd,Ni,/CNF [Bao 2019]. (FIG. 7 (TABLE V)). The yields from the PANiP MGNP were higher than those of the bimetallic PdNi catalysts. To assess the intrinsic catalytic performance of these Pd-based catalysts, the TOF was calculated. The TOF of the PaNiP MGNP was significantly higher than the bimetallic Ni, Pd,, and Pd,Ni,, demonstrating the high intrinsic activity of the PdNiP MGNP. This could be due to the optimized electronic structure by the synergic Pd —Ni—? interactions, as well as the geometric effect through which the amorphous structure has more actives sites for catalysis. PdNiP MGNP Catalyzed Miyaura-Heck Coupling Reaction [0125] As shown in FIG, 8 (TABLE VD, the PdNiP MGNP was used for catalyzing the Miyaura-Heck reaction. The catalyst (5 mg of the as-prepared PdNiP/carbon black with Pd of ~5 wt %, corresponding to 0.2 mol % of Pd based on aryl Jodide) in DMF (2.5 mL) and DI water (2.5 mL) was sonicated for 5 min. K,CO, (2 mmol), aryl iodide (1.0 mmol), and styrene (1.5 mmol) were added. After 17 h, the product was purified by silica gel chromatography and analyzed by ‘H NMR. The yield, turnover number (TON), and turnover frequency (TOF) were calculated by:
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US 2025/0281915 Al
Yield = n{produet, mol) / n(precursor, mol);
TON = n(product, mol) /n(Pd, mol); and
TOF = TON]t,
where t is the reaction time in h.
[0126] The results were shown in FIG. 8 (TABLE VI).
High yields (>92%) for different coupled products were
obtained with the PANiP MGNP catalyst under mild reaction
conditions.
[0127] These results were compared with the bimetallic
NigosPdo,95 nanoparticle reported in literature [Rai 2016].
FIG. 8 (TABLE VI). The yields catalyzed by the PdNiP
MGNP are higher than that by the bimetallic PdNi catalyst,
and a comparable TOF is obtained.
Results
[0128] Again, in this representative example, the applica-
tion of MGNP in heterogeneous catalysis has been shown,
exemplified by Suzuki-Miyaura coupling of a boronic acid
and an aryl halide. TABLE VII shows the Pt content in
various catalysts.
TABLE VIL
Pt content in various catalysts
Materials PtNiP MGNP/CB PtNi NP/CB Puc
PL wt % 5.88 6.84 17.2
[0129] High yields (>99%) for different coupled biaryl
products were obtained with the PdNiP MGNP catalyst
under mild reaction conditions. The yields were higher than
those of the bimetallic PdNi catalyst nanoparticles. [Yan
2019]. To assess the intrinsic catalytic performance of these
Pd-based catalysts, the turnover frequency (TOF) was cal-
culated. The TOF of the PdNiP MGNP is significantly higher
than the bimetallic Nig. .Pdy, and Pd,Ni,, demonstrating the
high intrinsic activity of the PANiP MGNP. This could be
due to the optimized electronic structure by the synergic
Pd—Ni—P inter-actions, as well as the geometric effect
through which the amorphous structure has more active sites
for catalysis. In addition, the PA—Ni—P MGNP also exhib-
ited high yields for catalytic coupling of aryl halides and
styrene by Miyaura-Heck coupling. FIG. 8 (TABLE VI).
[0130] Other representative examples of use as a catalyst
includes use of the ternary PtNiP MGNP as a high-perfor-
mance electrocatalyst for the hydrogen evolution reaction
(HER). FIG. 9 (TABLE VIII (showing some recently
reported previous metals-based HER electrocatalysts in acid
solution, as well as the use of ternary PtNiP MGNP as the
high-performance electrocatalyst).
[0131] Again, due to the versatility of the FCR method,
the synthesized MGNP provide wide applications in various
fields.
[0132] The methods and systems of the present invention
are also related to PCT Patent Appl. Serial Nos. PCT/US21/
52030, PCT/US21/52043, PCT/US21/52057, and PCT/
US21/52070, to James M. Tour et al., each entitled “Ultra-
fast Flash Joule Heating Synthesis Methods And Systems
For Performing Same,” each filed Sep. 24, 2021, and each
Sep. 11, 2025
claiming priority to U.S. Patent Appl. Ser. No. 63/082,592,
filed Sep. 24, 2020. These applications are incorporated
herein in their entirety.
[0133] While embodiments of the invention have been
shown and described, modifications thereof can be made by
one skilled in the art without departing from the spirit and
teachings of the invention. The embodiments described and
the examples provided herein are exemplary only, and are
not intended to be limiting. Many variations and modifica-
tions of the invention disclosed herein are possible and are
within the scope of the invention. The scope of protection is
not limited by the description set out above, but is only
limited by the claims which follow, that scope including all
equivalents of the subject matter of the claims.
[0134] The disclosures of all patents, patent applications,
and publications cited herein are hereby incorporated herein
by reference in their entirety, to the extent that they provide
exemplary, procedural, or other details supplementary to
those set forth herein.
[0135] Amounts and other numerical data may be pre-
sented herein in a range format. It is to be understood that
such range format is used merely for convenience and
brevity and should be interpreted flexibly to include not only
the numerical values explicitly recited as the limits of the
range, but also to include all the individual numerical values
or sub-ranges encompassed within that range as if each
numerical value and sub-range is explicitly recited. For
example, a numerical range of approximately 1 to approxi-
mately 4.5 should be interpreted to include not only the
explicitly recited limits of 1 to approximately 4.5, but also
to include individual numerals such as 2, 3, 4, and sub-
ranges such as | to 3, 2 to 4, etc. The same principle applies
to ranges reciting only one numerical value, such as “less
than approximately 4.5,” which should be interpreted to
include all of the above-recited values and ranges. Further,
such an interpretation should apply regardless of the breadth
of the range or the characteristic being described.
[0136] Unless defined otherwise, all technical and scien-
tific terms used herein have the same meaning as commonly
understood to one of ordinary skill in the art to which the
presently disclosed subject matter belongs. Although any
methods, devices, and materials similar or equivalent to
those described herein can be used in the practice or testing
of the presently disclosed subject matter, representative
methods, devices, and materials are now described.
[0137] Following long-standing patent law convention,
the terms “a” and “an” mean “one or more” when used in
this application, including the claims.
[0138] Unless otherwise indicated, all numbers expressing
quantities of ingredients, reaction conditions, and so forth
used in the specification and claims are to be understood as
being modified in all instances by the term “about.” Accord-
ingly, unless indicated to the contrary, the numerical param-
eters set forth in this specification and attached claims are
approximations that can vary depending upon the desired
properties sought to be obtained by the presently disclosed
subject matter.
[0139] As used herein, the term “about” and “substan-
tially” when referring to a value or to an amount of mass,
weight, time, volume, concentration or percentage is meant
to encompass variations of in some embodiments +20%, in
some embodiments +10%, in some embodiments +5%, in
some embodiments +1%, in some embodiments +0.5%, andPage 32
US 2025/0281915 Al in some embodiments +0.1% from the specified amount, as such variations are appropriate to perform the disclosed method. [0140] As used herein, the term “substantially perpendicu- lar” and “substantially parallel” is meant to encompass variations of in some embodiments within +10° of the perpendicular and parallel directions, respectively, in some embodiments within +5° of the perpendicular and parallel directions, respectively, in some embodiments within +1° of the perpendicular and parallel directions, respectively, and in some embodiments within +0.5° of the perpendicular and parallel directions, respectively. [0141] As used herein, the term “and/or” when used in the context of a listing of entities, refers to the entities being present singly or in combination. Thus, for example, the phrase “A, B, C, and/or D” includes A, B, C, and D individually, but also includes any and all combinations and subcombinations of A, B, C, and D. 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US 2025/0281915 Al highly durable catalysts in methanol electro-oxida- tion,” Chem. Mater, 2014, 26, 1056-1061 (“Zhao 2014”). [0240] Zhong, L., et al. “Formation of monatomic metallic glasses through ultrafast liquid quenching,” Nature, 2014, 512, 177-180 (“Zhong 2014”). What is claimed is: 1. A method for synthesizing metallic glass nanoparticles, wherein the method comprises: (a) mixing a metal/metalloid precursor with a material comprising carbon; (b) performing a flash Joule heating process using the material mixed with the metal/metalloid precursor, wherein the metal/metalloid precursors are decom- posed and fused into alloy melts; and (c) rapidly cooling the alloy melts to vitrify the alloy melts into the metallic glass nanoparticles. 2. The method of claim 1, wherein the method comprises a kinetically controlled synthesis of the metallic glass nan- oparticles. 3. The method of claim 1, wherein the step of mixing comprises dissolving the metal/metalloid precursor in a solvent to form a solution and wetting the material com- prising the carbon with the solution. 4. The method of claim 3, wherein a phosphorous source is dissolved in the solvent when forming the solution. 5. The method of claim 4, wherein the phosphorous source is PPh. 6. The method of claim 3, wherein the step of wetting comprises impregnating the metal/metalloid precursor on the material comprising the carbon. 7. The method of claim 3, wherein the solvent is selected from the group consisting of alcohol, water, and mixtures thereof. 8. The method of claim 3, wherein the solvent comprises ethanol. 9. The method of claim 1, wherein the carbon in the material serves as a conductive additive and a supporting substrate in the flash Joule heating process. 10. The method of claim 1, wherein the material com- prises carbon black. 11. The method of claim 1, wherein the metallic glass nanoparticles are Pd- and/or Pt-based metallic glass nan- oparticles. 12. The method of claim 1, wherein the metallic glass nanoparticles are selected from the group consisting of PdNiP, PdCuP, PdCuNiP, PtNiP, PtCuP, PtCuNiP, and PdCuFeNiP metallic glass nanoparticles and combinations thereof. 13. The method of claim 1, wherein (a) the metallic glass nanoparticles have the chemical formula M,—M,—P; (b) M, is selected from the group consisting of Pt, Pd, and combinations thereof; and Sep. 11, 2025 (c) M, is selected from the group consisting of Cu, Ni, Fe. Co, Sn, and combinations thereof. 14. The method of claim 1, wherein the flash Joule heating process comprises providing millisecond current pulses through the metal/metalloid precursor at a heating rate of at least 107 K/s. 15. The method of claim 1, wherein the flash Joule heating process raises the temperature of the metal/metalloid pre- cursors to at least 1800 K. 16. The method of claim 1, wherein the rapidly cooling is performed at an ultrafast rate of cooling of at least 10° K/s. 17. The method of claim 16, wherein the ultrafast rate of cooling is by thermal radiation. 18. The method of claim 1, wherein the metal/metalloid precursors are selected from the group consisting of H,PtCl,, PdCl,, CuCl, NiCl, FeCl,, PPh, P,O;, and combinations thereof. 19. The method of claim 1, wherein the metal/metalloid precursor comprises a metal salt. 20. The method of claim 19, wherein the metal salt is selected from the group consisting of H,PtCl;, PdCl,, CuCl,, NiCl,, FeCl, and combinations thereof. 21. A composition comprising metallic glass nanopar- ticles made by the method of claim 1. 22. A method comprising using the composition of claim 21. as a catalyst, wherein the catalyst comprises the metallic glass nanoparticles. 23. The method of claim 22, wherein the metallic glass nanoparticles are used as catalysts for a hydrogen evolution reaction. 24. The method of claim 22, wherein the metallic glass nanoparticles are used as catalysts for clean H, production via water electrolysis. 25. The method of claim 22, wherein the metallic glass nanoparticles are used as catalysts for catalytic coupling. 26. The method of claim 25, wherein the catalytic cou- pling is of a boronic acid and an ary] halide. 27. The method of claim 25, wherein the catalytic cou- pling is Suzuki-Miyaura coupling or Miyaura-Heck cou- pling. 28. The method of claim 22, wherein the metallic glass nanoparticles comprise PtNiP metallic glass nanoparticles. 29. The method of claim 22, wherein the metallic glass nanoparticles comprise PdNiP metallic glass nanoparticles. 30. The method of claim 22, wherein the metallic glass nanoparticles are used as catalysts for a reaction selected from the group consisting of electrochemical reactions, hydrogen evolution reactions, oxygen reduction reactions, carbon dioxide reduction reactions, reactions used in fuel cells, carbon-carbon bond forming reactions, carbon hydro- gen bond forming reactions, hydroformylation reactions, carbon monoxide insertion reactions, and reductive elimi- nation reactions.
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