METHOD FOR SYNTHESIZING AMORPHOUS Pd-BASED NANOPARTICLES

Abstract

A general and controlled method for synthesizing amorphous Pd-based nanoparticles is provided. The provided method comprises: dissolving a Pd precursor in a first solvent to form a first solution; mixing the first solution with a second solvent to form a first mixture; adding surfactant into the first mixture to form a second mixture; heating the second mixture to render a second solution; adding other metal precursor into the second solution to form a third mixture; heating the third mixture to render a third solution; naturally cooling down the third solution; adding ethanol to the third solution to form a fourth solution; and collecting the amorphous Pd-based nanoparticles from the fourth solution. The provided method allows tuning of the phase of Pd-based nanoparticles to obtain amorphous Pd-based nanocatalysts to efficiently switch the ring-opening route of epoxides for the synthesis of distinct targeted chemicals and modulating of the catalytic performance thereof in electrochemical hydrogen emission reactions.

Description

FIELD OF THE INVENTION

The present invention generally relates to synthesis of noble metal nanomaterials and catalytic applications of the same. More specifically, the present invention relates to synthesis of amorphous palladium (Pd)-based nanoparticles and catalytic applications of the same.

BACKGROUND OF THE INVENTION

Noble metal nanomaterials normally serve as efficient catalysts for various important reactions in pharmaceutical, chemical industries, such as ring-opening reactions of epoxides. Linear and/or branched alcohols in epoxides can be formed via the selective hydrogenation route, which is normally catalyzed by metals under hydrogen (H₂) atmosphere; when alcohols exist as nucleophiles, the alcoholysis reaction of epoxides could occur to predominantly obtain the branched β-alkoxy alcohols, which is mainly catalyzed by homogeneous catalysts, in general suffering from the inherent drawbacks such as catalyst recycling and production purification. As illustrated in FIG. 1, the alcoholysis reaction and hydrogenation reaction could compete against each other in the ring-opening reaction of SO in ethanol under H₂ atmosphere. It still remains a key challenge to efficiently switch the ring-opening route of SO for the highly selective synthesis of distinct targeted chemicals.

Among the noble metals, Pd-based nanomaterials have drawn particular attention and been extensively studied for decades due to their high intrinsic activities towards diverse catalytic applications. Previous research results also indicated that Pd-based nanoalloy materials with multi-metal components could exhibit significantly improved catalytic performance compared with single metals due to the synergistic effect between different metal atoms. However, most of the previous works on Pd-based catalysts only focused on the thermodynamically stable conventional crystalline phase, i.e., face-centered cubic (fcc) phase. Recently, the rapid progress made in the field of phase engineering of nanomaterials (PEN) has revealed that the phase structure, i.e., atomic arrangement, of nanomaterials plays a vital role in determining their properties and functions. Some studies have demonstrated that noble metal nanomaterials with unconventional phases, in comparison with their counterpart with conventional phase structures, could exhibit distinct physicochemical properties and catalytic performance.

In particular, nanomaterials with amorphous phase, i.e., long-range disordered structure, have emerged as new, highly efficient catalysts due to the abundant uncoordinated sites and dangling bonds. To date, several synthetic approaches have been developed to prepare amorphous noble metal nanomaterials, which exhibited excellent performance towards various catalytic reactions, e.g., thermal annealing synthesis of amorphous Ir nanosheets for electrochemical oxygen evolution, template-assistant synthesis of amorphous Au nanoclusters for electrocatalytic carbon dioxide reduction.

However, the rational preparation of amorphous noble metal nanomaterials still remains difficult due to the strong metallic bonds existed between atoms of noble metals. Therefore, it is of importance to develop controllable and general strategies to realize the controlled synthesis of amorphous noble metal and their alloy nanomaterials with tunable compositions for development of high performance catalysts.

SUMMARY OF THE INVENTION

It is an objective of the present invention to provide a robust and controlled approach for synthesizing amorphous Pd-based nanomaterials which can be used as catalysts with high efficiency, high selectivity, low overpotential and high turnover frequency in various catalytic reactions.

In accordance with a first aspect of the present invention, a method for synthesizing amorphous Pd-based nanoparticles is provided. The provided method comprises: a) dissolving a Pd precursor in a first solvent to form a first solution; b) mixing the first solution with a second solvent to form a first mixture; c) adding surfactant into the first mixture to form a second mixture; d) heating the second mixture at a first heating temperature for a first heating time to render a second solution; e) adding other metal precursor into the second solution to form a third mixture; f) heating the third mixture at a second heating temperature for a second heating time to render a third solution; g) naturally cooling down the third solution to a room temperature; h) adding ethanol to the third solution to form a fourth solution; and i) collecting the amorphous Pd-based nanoparticles from the fourth solution by centrifugation.

The Pd precursor is Pd(II) acetylacetonate, Pd(II) acetate, PdBr₂ or combinations thereof.

The Pd precursor has a purity of greater than or equal to 98%; the first solvent is a toluene having a purity of greater than or equal to 99.5%; and a concentration of Pd precursor in the toluene is in a range from 1 to 20 mg/ml. Preferably, the concentration of Pd precursor in the toluene is 10 mg/ml.

The second solvent is an oleylamine having a purity greater than or equal to 70%; and a volume ratio of the oleylamine to the first solution is in a range from 20:1 to 3:1. Preferably, the volume ratio of the oleylamine to the first solution is 9:1.

The surfactant is a C₃-C₂₀ alkanethiol, an organophosphorus compound or the combination thereof. The amorphous Pd-based nanoparticles synthesized using alkanethiol as surfactant have a particle size of 4 nm to 8 nm. The amorphous Pd-based nanoparticles synthesized using organophosphorus compound as surfactant have a particle size of 8 nm to 12 nm.

The surfactant is 1-propanethiol, 1-octanethiol, 2-ethylhexanethiol, 1-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, triphenylphosphine, trioctylphosphine, or combinations thereof.

The surfactant has a purity greater than or equal to 98%; and a molar ratio of the surfactant to Pd precursor is in a range from 1:2 to 2:1. Preferably, the molar ratio of the surfactant to Pd precursor is 1:1.

The first heating temperature is in a range from 140° C. to 200° C.; and the first heating time is in a range from 15 to 25 minutes. Preferably, the first heating temperature is 155° C.; and the first heating time is 20 minutes.

The other metal precursor is a ruthenium (Ru) precursor, a rhodium (Rh) precursor, an silver (Ag) precursor, an iridium (Ir) precursor, a nickel (Ni) precursor or combinations thereof.

The other metal precursor has a purity greater than or equal to 99.98%; and a molar ratio of the other metal precursor to the Pd precursor is in a range from 1:10 to 5:1.

The molar ratio of the other metal precursor to the Pd precursor is 1:2.

The step e) further comprising dissolving the other metal precursor in a solvent before adding the other metal precursor into the second solution.

The second heating temperature is in a range from 140° C. to 200° C.; and the second heating time is in a range from 45 to 75 minutes.

The second heating temperature is 155° C.; and the second heating time is 60 minutes.

The volume ratio of the ethanol to the third solution is in a range from 1:1 to 10:1.

In accordance with a second aspect of the present invention, a method of preparing a catalyst using amorphous Pd-based nanoparticles is provided. The method comprises: synthesizing amorphous Pd-based nanoparticles with the method in accordance with the first aspect of the present invention; dispersing carbon powder in ethanol to obtain a fourth mixture; sonicating the fourth mixture in an ice bath for one hour to form a carbon suspension; adding the synthesized amorphous Pd-based nanoparticles into the carbon suspension to obtain a fifth mixture; sonicating the fifth mixture in an ice bath for one hour to form a catalyst-loaded carbon suspension; collecting the catalyst-loaded carbon from the catalyst-loaded carbon suspension by centrifugation; washing the catalyst-loaded carbon with a mixture solution composing of chloroform and ethanol; re-dispersing the catalyst-loaded carbon in a mixture solution containing isopropanol and water to form a sixth mixture; adding Nafion solution into the sixth mixture to form a seventh mixture; and sonicating the seventh mixture in an ice bath for one hour to form a catalyst.

In accordance with a third aspect of the present invention, a method of using amorphous Pd-based nanoparticles as catalysts for electrochemical hydrogen evolution reaction or ring-opening reaction of an epoxide is provided.

The provided synthesis method allows tuning of the phase of Pd-based nanocatalysts for efficiently switching the ring-opening route of SO for the synthesis of distinct targeted chemicals and also modulating of catalytic performance thereof towards electrochemical HER. Specifically, the usage of amorphous Pd-based alloy nanocatalyst (e.g., Pd, PdRu alloy nanoparticles) induces the alcoholysis reaction of SO towards the highly selective production of 2-ethoxy-2-phenylethanol (EPE), while the conventional crystalline Pd-based catalyst (e.g., fcc-Pd, fcc-PdRu alloy nanoparticles) mainly catalyzes the hydrogenation reaction of SO to form 2-phenylethanol (PE) with high selectivity..

Pd-based catalysts can also be applied in various electrochemical reactions such as HER. In present invention, the amorphous PdRh nanocatalyst (e.g., Pd, PdRu alloy nanoparticles) exhibits significantly superior HER performance with lower overpotential and higher turnover frequency (TOF) values compared to the counterpart crystalline fcc-Pd-based catalyst. The conventional crystalline fcc-Pd-based catalyst, in which binding between Pd and hydrogen during the HER process is normally too strong, the amorphous Pd-based nanomaterials could exhibit weakened binding towards hydrogen due to the modified electronic structure, which leads to the enhanced HER performance. Besides, the amorphous structures could possess abundant dangling bonds and uncoordinated atoms, which provide more active sites for catalytic reactions, facilitating the HER process. In addition, the excellent HER activity of binary amorphous PdRh catalyst could also be attributed to the alloying effect of Pd and Rh. Specifically, the synergistic effect between

Rh and Pd atoms could efficiently modify the electronic structure of Pd and weaken the adsorption of hydrogen on Pd, thus boosting the HER performance.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention are described in more details hereinafter with reference to the drawings, in which:

FIG. 1 illustrates two typical ring-opening reaction routes of SO via an alcoholysis reaction and hydrogenation reaction to produce EPE and PE, respectively.

FIG. 2 illustrates the preparation process of amorphous Pd-based nanoparticles (NPs) through a one-pot reduction method by adding other metal precursors.

FIG. 3A is the transmission electron microscopy (TEM) image of synthesized amorphous PdRu (a-PdRu) NPs (Inset: toluene dispersion of a-PdRu NPs in a 250-mL vial).

FIG. 3B is the size distribution histogram of the synthesized a-PdRu NPs.

FIG. 3C is the high-resolution TEM (HRTEM) image of the synthesized a-PdRu NPs (Inset: the FFT pattern taken from the selected dashed square area).

FIG. 3D is the selected area electron diffraction (SAED) pattern of the synthesized a-PdRu NPs.

FIG. 3E is the X-ray diffraction (XRD) pattern of the synthesized a-PdRu NPs.

FIG. 3F is the energy disperse X-ray spectroscopy (EDS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) characterizations of the synthesized a-PdRu NPs.

FIG. 3G is the scanning transmission electron microscope (STEM) image of the synthesized a-PdRu NPs and the corresponding EDS elemental mappings.

FIG. 3H is the EDS elemental line scan along the dotted white line in FIG. 3G.

FIG. 3I is the Pd 3d X-ray photoelectron spectroscopy (XPS) spectrum of the synthesized a-PdRu NPs.

FIG. 3J is the Pd K-edge X-ray absorption near edge structure (XANES) spectra of the synthesized a-PdRu NPs and commercial Pd foil.

FIG. 3K is the Pd K-edge Fourier-transformed extended X-ray absorption fine structure (EXAFS) spectra of the synthesized a-PdRu NPs and commercial Pd foil.

FIG. 3L is the Ru 3d XPS spectrum of the synthesized a-PdRu NPs.

FIG. 3M is the Ru K-edge XANES spectra of the synthesized a-PdRu NPs and commercial Ru foil.

FIG. 3N is the Ru K-edge Fourier-transformed EXAFS spectra of the synthesized a-PdRu NPs and commercial Ru foil.

FIG. 4A is the TEM image of synthesized amorphous PdRh (a-PdRh) NPs.

FIG. 4B is the size distribution histogram of synthesized a-PdRh NPs.

FIG. 4C is the HRTEM image of synthesized a-PdRh NPs (Inset: the corresponding FFT pattern taken from the selected dashed square area).

FIG. 4D is the SAED pattern of the synthesized a-PdRh NPs.

FIG. 4E is the XRD pattern of the synthesized a-PdRh NPs.

FIG. 4F is the EDS and ICP-OES characterizations of the synthesized a-PdRh NPs.

FIG. 4G is the STEM image of the synthesized a-PdRh NPs and the corresponding EDS elemental mappings.

FIG. 4H is the EDS elemental line scan along the dotted white line in FIG. 4G.

FIG. 4I is the Pd 3d XPS spectrum of the synthesized a-PdRh NPs.

FIG. 4J is the Rh 3d XPS spectrum of the synthesized a-PdRh NPs.

FIG. 5A is the TEM image of the synthesized amorphous PdRuRh (a-PdRuRh) NPs.

FIG. 5B is the size distribution histogram of the synthesized a-PdRuRh NPs.

FIG. 5C is the HRTEM image of the synthesized a-PdRuRh NPs (Inset: the corresponding FFT pattern taken from the selected dashed square area).

FIG. 5D is the SAED pattern of the synthesized a-PdRuRh NPs.

FIG. 5E is the XRD pattern of the synthesized a-PdRuRh NPs.

FIG. 5F is the EDS and ICP-OES characterizations of the synthesized a-PdRuRh NPs.

FIG. 5G is the STEM image and the corresponding EDS elemental mappings of the synthesized a-PdRuRh NPs.

FIG. 5H is the corresponding EDS elemental line scan along the dotted white line in FIG. 5G.

FIG. 6 is the gas chromatography-mass spectrometry (GC-MS) spectrum of ring-opening reaction of SO catalyzed by a-PdRu NPs.

FIG. 7 is the GC-MS spectrum of ring-opening reaction of SO without any catalyst.

FIG. 8 are conversion rate curves of SO in the ring-opening reaction of a-Pd NPs, a-PdRu NPs, fcc-Pd NPs, and fcc-PdRu NPs.

FIG. 9 are histograms of selectivity of EPE and PE products in ring-opening reaction of SO catalyzed by a-Pd NPs, a-PdRu NPs, fcc-Pd NPs, and fcc-PdRu NPs.

FIG. 10 is the total ion chromatogram (TIC) for detecting EPE (at ˜7.85 min) in the ring-opening reaction of SO catalyzed by a-PdRu NPs.

FIG. 11 is the ¹H nuclear magnetic resonance (NMR) spectrum of EPE.

FIG. 12 is the ¹³C NMR spectrum of EPE.

FIG. 13A illustrates conversion of SO and selectivity of EPE after using a-PdRu catalyst to catalyze the alcoholysis reaction of SO for 5 cycles.

FIG. 13B illustrates the GC-MS spectrum of ring-opening reaction of SO catalyzed by the a-PdRu catalyst in different catalytic cycles.

FIG. 13C illustrates the HRTEM image of a-PdRu catalyst after 5 catalytic cycles (Inset: the corresponding FFT pattern taken from the selected dashed square area).

FIG. 13D illustrates the SAED pattern of a-PdRu catalyst after 5 catalytic cycles.

FIG. 14 illustrates GC-MS spectra of the ring-opening reaction of SO catalyzed by a-Pd NPs under H₂ atmosphere at room temperature.

FIG. 15 illustrates GC-MS spectra of the ring-opening reaction of SO catalyzed by fcc-Pd NPs under H₂ atmosphere at room temperature.

FIG. 16 illustrates GC-MS spectra of the ring-opening reaction of SO catalyzed by fcc-PdRu NPs under H₂ atmosphere at room temperature.

FIG. 17A illustrates the polarization curves of a-Pd NPs, a-PdRh NPs, fcc-Pd NPs, fcc-PdRh NPs and commercial Pt/C in electrocatalytic HER.

FIG. 17B illustrates the Tafel plots of a-Pd NPs, a-PdRh NPs, fcc-Pd NPs, fcc-PdRh NPs, and commercial Pt/C obtained from the corresponding polarization curves in FIG. 17A.

FIG. 17C illustrates the overpotentials at the current density of 10 mA cm⁻² for distinct catalysts and some previously reported Pd-based electrocatalysts (see Table 2 for more details).

FIGS. 18A to 18C illustrate cyclic voltammetry (CV) curves of a-PdRh, fcc-PdRh and a-Pd catalysts measured at a scan rate of 10 mV s⁻¹ in N₂-saturated 0.5 M H₂SO₄ aqueous solution in the presence and absence of 10 mM CuSO4, respectively.

FIG. 19 shows TOF values of a-PdRh, fcc-PdRh, and a-Pd catalysts measured in 0.5 M H₂SO₄ aqueous solution.

FIGS. 20A to 20C illustrate the electrochemical impedance spectroscopy (EIS) measurement results of a-PdRh, fcc-PdRh, and a-Pd catalysts, respectively.

DETAILED DESCRIPTION

In the following description, a method for synthesizing amorphous Pd-based nanoparticles and the likes are set forth as preferred examples. It will be apparent to those skilled in the art that modifications, including additions and/or substitutions may be made without departing from the scope and spirit of the invention. Specific details may be omitted so as not to obscure the invention; however, the disclosure is written to enable one skilled in the art to practice the teachings herein without undue experimentation.

Referring to FIG. 2, in accordance with some embodiments of the present invention, a series of amorphous Pd-based nanoparticles may be synthesized via a facile one-pot wet-chemical approach. In particular, a Pd precursor is dissolved in a first solvent, to form a first solution; the first solution is mixed with a second solvent to form a first mixture; surfactant is added into the first mixture to form a second mixture; the second mixture is undergone a first heat treatment to render a second solution; other metal precursor is then added into the second solution to form a third mixture; the third mixture is undergone a second heat treatment to render a third solution; the third solution is naturally cooled down to a room temperature; ethanol is added to the third solution to form a fourth solution; and the amorphous Pd-based nanoparticles are collected from the fourth solution by centrifugation.

In some embodiments, the amorphous Pd-based nanoparticles are washed after being precipitated from the fourth solution. Particularly, the washing step includes dispersing the amorphous Pd-based nanoparticles into a third solvent and sonicating the solution, adding a fourth solvent and sonicating the mixture, and collecting the solid product by centrifugation. The third solvent is different from the fourth solvent. Preferably, the third solvent is selected from the group consisting of chloroform, hexane and toluene, and the fourth solvent is selected from the group consisting of ethanol, methanol and acetone.

The amorphous Pd-based nanoparticles may be, but are not limited to, binary, ternary, quaternary or quinary amorphous Pd-based nanoparticles. More particularly, the amorphous Pd-based nanoparticles may be, but not limited to, amorphous Pd—Ru, Pd—Ag, Pd—Rh, Pd—Ir, Pd—Ni, Pd—Ag—Ru, Pd—Ag—Rh, Pd—Ru—Rh, Pd—Ag—Ru—Rh or Pd—Ag—Ru—Rh—Ir nanoparticles.

The first solvent may be, but not limited to, a toluene, an ethanol, a methanol, a chloroform or combinations thereof.

The second solvent may be, but not limited to, an amine, an alkene or combinations thereof.

EXAMPLES

Synthesis of a-PdRu NPs

In a typical synthesis, 40.5 mg of Pd(OAc)₂ were dissolved in 4.05 mL of toluene and then mixed with 36 mL of oleylamine in a 50-mL vial under magnetic stirring. After 45 μL of 1-dodecanethiol were added, the mixture was stirred for another 15 min at room temperature. The vial was then immersed into an oil bath at 155° C. and kept for 20 min. Subsequently, 27.9 mg of RuCl₃·_χH₂O (dissolved in 2.79 mL of ethanol) were added into the reaction solution. After holding at 155° C. for another 60 min, the vial was taken out, followed by naturally cooling down to room temperature. After adding 70 mL of ethanol, the product was collected by centrifugation at 10,000 rpm for 10 min. After the as-obtained a-PdRu NPs were dispersed into 15 mL of chloroform and sonicated for 5 min, 90 mL of acetone were added to precipitate the NPs. The a-PdRu NPs were then collected by centrifugation at 10,000 rpm for 10 min. The aforementioned washing process was repeated for three times. Finally, the a-PdRu NPs were re-dispersed in toluene for further usage.

Synthesis of a-PdRh NPs

The synthesis protocol of a-PdRh NPs is basically the same as the aforesaid protocol for the preparation of a-PdRu NPs except changing the added metal precursor from 27.9 mg of RuCl₃·_χH₂O to 25.2 mg of RhCl₃·_χH₂O (dissolved in 2.52 mL of ethanol). After washing by following the same protocol for three times, the obtained a-PdRh NPs were finally re-dispersed in toluene for further usage.

Synthesis a-PdRuRh NPs

The synthesis protocol of a-PdRuRh NPs is basically the same protocol for the preparation of a-PdRu NPs except changing the added metal precursor from 27.9 mg of RuCl₃·_χH₂O to the mixture of 27.9 mg of RuCl₃·_χH₂O (dissolved in 2.79 mL of ethanol) and 25.2 mg of RhCl₃·_χH₂O (dissolved in 2.52 mL of ethanol). After washing by following the same protocol for three times, the obtained a-PdRuRh NPs were finally re-dispersed in toluene for further usage.

Characterization Methodologies

TEM images, SAED patterns, and EDS data were obtained on a JEOL JEM-2100F (JEOL, Tokyo, Japan) transmission electron microscope. XRD patterns were recorded with a Siemens D500 X-ray diffractometer (Bruker AXS), using CuKa radiation (λ=1.5406 Å). The samples used for XRD characterization were prepared by drop-casting the corresponding solutions on clean glass substrates and drying under ambient conditions. XPS measurements were conducted on the ESCALAB 250Xi (Thermo Fisher Scientific) instrument. The C 1s peak with a binding energy of 284.8 eV was used as the reference. The samples used for XPS characterization were prepared by drop-casting the corresponding solutions on clean Si substrates and then drying under ambient conditions. Inductively coupled plasma optical emission spectroscopy (ICP-OES) measurements were performed on a Dual-view Optima 5300 DV ICP-OES system. The XANES and EXAFS spectra of Pd K-edge and Ru K-edge were performed at the 7-BM/QAS beamline of the National Synchrotron Light Source II (NSLS-II).

Characterization of a-PdRu NPs

As shown in the TEM image in FIG. 3A and the size distribution histogram in FIG. 3B, the obtained a-PdRu NPs are quasi-spherical with a size of 5.9±1.0 nm. The HRTEM image (FIG. 3C) clearly shows the long-range disordered atomic arrangement in a-PdRu NPs. The diffuse rings in the corresponding selected-area fast Fourier transform (FFT) pattern (inset of FIG. 3C) and SAED pattern (FIG. 3D) further confirm the amorphous structure of obtained a-PdRu NPs. XRD was also used to characterize the crystallinity of as-synthesized NPs. As shown in FIG. 3E, no obvious diffraction peak is observed in the XRD pattern of a-PdRu NPs, corroborating their amorphous phase. EDS analysis (FIG. 3F) reveals that the atomic percentage of Ru in a-PdRu NPs is determined to be 13.2 at %, which is consistent with the value of 13.6 at % based on the ICP-OES result. EDS elemental mappings (FIG. 3G) and line scan (FIG. 3H) corroborate the distribution of Pd and Ru elements, verifying the alloy structure of a-PdRu NPs.

XPS and XAFS characterizations were carried out to study the chemical states and electronic structures of Pd and Ru in the synthesized a-PdRu NPs. As shown in FIG. 3I, two main fitted peaks in the Pd 3d spectrum of a-PdRu NPs correspond to Pd⁰, while two weak peaks corresponding to Pd²⁺ can also be observed, demonstrating the mixed chemical states of Pd element. The presence of Pd²⁺ 3d peaks could be ascribed to the formation of Pd—S bond on the surface of a-PdRu NPs due to the strong interaction between Pd atoms and S atoms in thiol molecules. The XANES spectrum (FIG. 3J) and the corresponding Fourier-transformed EXAFS spectrum (FIG. 3K) of the Pd K-edge confirm the presence of both Pd—Pd and Pd—S bonds in the a-PdRu NPs, further corroborating the mixed chemical states of Pd element, which shows good agreement with the XPS result (FIG. 3I). It is worth mentioning that the formation of strong Pd—S bond on the surface of Pd could facilitate the formation of amorphous structure. Moreover, the Ru 3d XPS profile (FIG. 3L), the Ru K-edge XANES spectrum (FIG. 3M), and the corresponding EXAFS spectrum (FIG. 3N) reveal the formation of Ru-S bond in the a-PdRu NPs which are mainly due to the interaction between thiol molecules and Ru atoms. In the Ru 3d XPS spectrum (FIG. 3L), the signals of Ru 3d peaks are overlapped with that of C 1s, making it difficult to clearly distinguish the chemical state of Ru solely based on the XPS characterization. The X-ray absorption fine structure (XAFS) characterizations of Ru K-edge (FIGS. 3M and 3N) affirm the formation of Ru—S bond and Ru-Ru bond in the as-synthesized a-PdRu NPs. In the EXAFS spectrum of a-PdRu NPs (FIG. 3N), two obvious peaks can be observed and assigned to the Ru—S bond length and Ru—Ru bond length, respectively.

Characterization of a-PdRh NPs

The TEM image in FIG. 4A and the size distribution histogram in FIG. 4B show that the synthesized a-PdRh NPs are quasi-spherical with a size of 6.2±1.0 nm. The HRTEM image and corresponding FFT pattern (FIG. 4C and inset) demonstrate the lack of long-range ordered atomic ordering in the a-PdRh NPs. The diffuse ring in the SAED pattern (FIG. 4D) and the absence of diffraction peak in XRD profile (FIG. 4E) further affirm the amorphous phase. EDS spectrum shows that the atomic percentage of Rh in a-PdRh NPs is estimated to be 16.6 at %, similar to the value of 15.4 at % according to the ICP-OES result (FIG. 4F). The EDS elemental mappings (FIG. 4G) and line scan (FIG. 4H) reveal that Pd and Rh are evenly distributed in the obtained NPs. The XPS spectra of Pd 3d (FIG. 41) and Rh 3d (FIG. 4J) confirm that both the Pd and Rh elements possess mixed chemical states. The existence of weak peaks corresponding to Pd²⁺ and Rh²⁺ could mainly be attributed to the formation of Pd—S and Rh—S bonds.

Characterization of a-PdRuRh NPs

The TEM image in FIG. 5A and the size distribution histogram in FIG. 5B shows that the synthesized amorphous ternary PdRuRh NPs, as referred to a-PdRuRh, possess a sphere-like morphology with a size of 6.8±1.2 nm. The disordered atomic arrangement as revealed by the HRTEM image (FIG. 5C) clearly corroborates the amorphous nature of a-PdRuRh NPs, which can be further affirmed by the diffuse rings in the FFT pattern (inset of FIG. 5C) and SAED pattern (FIG. 5D) as well as the absence of diffraction peak in the XRD spectrum (FIG. 5E). The atomic ratio of Pd/Ru/Rh verified by EDS characterization is ˜79.0/10.1/10.9, which is consistent with the result (˜77.2/12.0/10.8) determined by ICP-OES (FIG. 5F). The EDS elemental mappings (FIG. 5G) and line scan (FIG. 5H) further corroborate the ternary alloy structure of synthesized a-PdRuRh NPs.

For comparison, monometallic amorphous Pd NPs (as referred to a-Pd NPs), and crystalline Pd and PdRu NPs with conventional fee phase, denoted as fcc-Pd and fcc-PdRu, respectively, were also prepared for catalytic performance comparison.

Preparation of Catalyst Slurry for Catalytic Ring-Opening Reaction of SO

An exemplary process of prepartion of catalyst slurry for catalytic ring-opening reaction of SO is described as follows. First, after 7 mg of Vulcan XC-72R carbon black were dispersed in 7 mL of ethanol in a vial, the as-obtained mixture was sonicated in an ice bath for 1 h to ensure the formation of the homogeneous suspension. Then, 3 mL of a catalyst solution, containing 3 mg of as-synthesized amorphous Pd-based NPs (e.g. a-PdRu NPs) (determined by ICP-OES), were dropwise added into the carbon suspension. The obtained mixture was then sonicated for another 1 h in an ice bath. After that, the catalyst loaded on carbon (catalyst/carbon) with an amorphous Pd-based NPs amount of 30 wt % was collected by centrifugation at 10,000 rpm for 10 min, followed by washing for six times with a mixture of chloroform (5 mL) and ethanol (5 mL). Subsequently, the catalyst/carbon was re-dispersed in 10 mL of ethanol for further usage.

Catalytic Ring-Opening Reaction of SO

All the catalytic ring-opening reactions of SO were conducted in the 25-mL Schlenk glass vessel tubes under H₂ (1 atm) atmosphere at room temperature (˜25° C.). Specifically, 0.2 mmol of SO, 0.2 mmol of mesitylene used as an internal standard, and 1 mol % of catalyst/carbon (based on the ratio of noble metal/SO) were dispersed in 1 mL of ethanol under H₂ atmosphere. Composition of liquid samples taken during the ring-opening reaction were analyzed by GC-MS (Agilent 6890N GC system and Waters Quattro micro mass spectrometer with triple quadrupole detector) characterization. Samples of reaction at different reaction time were taken out and diluted with acetone, and then filtered by a filter membrane (with of pore size of 0.22 μm) to remove the catalysts. The samples were analyzed by GC-MS to monitor the conversion of SO and meanwhile to determine the selectivity of different products, including EPE and PE. Analysis times for products were typically on the order of 4.5-9.1 min depending upon the composition. Helium was used as the carrier gas at a constant flow rate of 1 mL/min. The column oven temperature was programmed from 70 to 200° C. at the rate of 20° C./min, and then raised to 280° C. at the rate of 30° C./min. The NMR (Bruker 500 MHz spectrometer) was used to analyze the formation of EPE product.

Catalytic Performance of the Ring-Opening Reaction of SO

Referring to FIG. 6, the GC-MS spectra used for detecting the ring-opening reaction of SO catalyzed by a-PdRu NPs under H₂ atmosphere at room temperature shows that the ring-opening reaction of SO on the a-PdRu catalyst could be completed within 420 min. It can be seen that the ring-opening reaction of SO cannot occur without any catalyst since no product except the original SO was detected (FIG. 7).

Referring to FIGS. 8 and 9, when the synthesized a-PdRu NPs are used as a catalyst, the alcoholysis reaction of SO occurs with a high SO conversion of >99% and the main product is EPE with a high selectivity of ˜94% as analyzed by the GC-MS (FIG. 10) and the NMR spectra (FIGS. 11 and 12).

Furthermore, the recyclability of the a-PuRu catalyst towards the alcoholysis reaction of SO was studied. Referring to FIG. 13A, after 5 cycles of alcoholysis reaction, the conversion of SO and selectivity of EPE on the a-PdRu catalyst can be maintained as >99% and ˜89%, respectively. In the GC-MS spectra (FIG. 13B) recorded during the recycling test, peaks appearing at ˜5.77, 6.79, and 7.85 min correspond to mesitylene (used as an internal standard), PE, and EPE, respectively. After the recycling test, HRTEM image of the a-PdRu NPs (FIG. 13C) and the corresponding FFT pattern (Inset of FIG. 13C) verify that the disordered atomic arrangement can be maintained. The diffuse diffraction rings in the SAED pattern (FIG. 13D) further confirm that the a-PdRu NPs preserve their amorphous phase, indicating their good structural stability.

As shown in FIGS. 8, 9 and 14, compared to binary metallic a-Pd NPs the monometallic a-Pd NPs exhibit a slightly lower EPE selectivity of ˜92% and slower conversion rate in the alcoholysis reaction of SO, which indicates that the alloying effect arising from the incorporation of Ru into Pd could boost the catalytic performance of the binary a-PdRu catalyst. As shown in Table 1, excellent catalytic performance of the amorphous Pd-based nanomaterials for the alcoholysis reaction of SO towards the production of EPE places them among the best of the state-of-art heterogeneous catalysts.

TABLE 1
Comparison of the catalytic performances of heterogeneous catalysts
for the alcoholysis reaction of SO towards the synthesis of EPE
		Reaction
	Amount	temperature	Conversion	Selectivity
Catalysts	(/1 mmol SO)	(° C.)	of SO (%)	of EPE (%)
α-PdRu	0.01	mmol	r.t. (~25)	>99	~94
	(~1	mg)
α-Pd	0.01	mmol	r.t. (~25)	>99	~92
	(~1	mg)
Ti3C2Tx MXenes	1	mg	60	99	50
Gd-based MOF	50	mg	35	100	100
La-based MOF	41.8	mg	70	77	100
Fe-based MOF	25	mg	40	N.A.	35
Functionalized MIL-	35	mg	r.t.	84	100
101(Cr) MOF
Sulfonic acid	0.02	mmol	r.t.	94	99
functionalized MOF
Lanthanide-organic	50	mg	35	99	100
coordination polymer
Graphite oxide	1	mg	r.t.	N.A.	72
Polyoxometalate-	40	mg	r.t.	96	90
modified rGO
Acidic activated carbon	100	mg	r.t.	N.A.	84
Acid treated carbon	66.7	mg	r.t.	99	97
Nanoporous	50	mg	r.t.	92	86
aluminosilicate
Mesoporous	50	mg	r.t.	N.A.	86
aluminosilicate
Sulphated yttria-zirconia	12	mg	32	N.A.	96
S, Fe-doped	50	mg	r.t.	N.A.	99
titanoniobate
CuO/SiO2	125	mg	60	99	90
Pd/strontium hydroxyl	12	mg	r.t.	73	100
fluoride
SiO2-supported Fe(III)	22.2	mg	r.t.	N.A.	100
catalyst

Referring to FIGS. 8, 9, 15 and 16, the usage of crystalline fcc-Pd and fcc-PdRu NPs as catalysts would switch the ring-opening route of SO to a hydrogenation route, thus predominately forming PE product with high selectivity of ˜97% and ˜95%, respectively.

The aforementioned results unambiguously demonstrate that the phase structure of Pd-based nanocatalyst plays a significant role in controlling the ring-opening route of SO towards synthesis of different targeted products with high selectivity.

Preparation of Catalyst Slurry for Electrochemical HER

An exemplary process of prepartion of catalyst slurry for electrochemical HER is described as follows. First, 540 μg of Vulcan XC-72R carbon black were dispersed in 540 μL of ethanol and the obtained mixture was sonicated in an ice bath for 1 h to make sure the formation of the homogeneous suspension. Then, 60 μL of catalyst solution, containing 60 μg of amorphous Pd-based NPs (e.g., a-PdRu NPs) (determined by ICP-OES), were dropwise added into the aforementioned carbon suspension, which was then sonicated for another 1 h in ice bath. After that, the as-obtained catalyst/carbon with amorphous Pd-based NPs amount of 10 wt % was collected by centrifugation at 14,800 rpm for 5 min, followed by washing six times with 1 mL of mixture solution composing of chloroform and ethanol (volume ratio of 1:1). After the catalyst/carbon was re-dispersed in a mixture solution containing 139 μL of isopropanol and 59 μL of water, 2 μL of Nafion solution were added and the mixed solution was sonicated for another 1 h in an ice bath to obtain the uniformly distributed catalyst slurry.

Electrochemical HER Measurements

The HER measurements were conducted on a CHI 760E electrochemical workstation at room temperature with the assistance of a glassy carbon electrode mounted on a rotator (glassy carbon rotating disk electrode (RDE)). A three-electrode system was used in the measurements. The glassy carbon RDE coated with catalyst, the graphite rod, and the Ag/AgCl (saturated KCl) electrode were employed as working electrode, counter electrode, and reference electrode, respectively. The Ag/AgCl electrode was calibrated with respect to a reversible hydrogen electrode (RHE)

Before drop-casting, the glassy carbon electrode (with diameter of 5 mm and area of 0.196 cm²) is pre-polished with by Al₂O₃ slurry, then cleaned with deionized water and ethanol respectively. The working electrode was prepared by drop-casting 10 μL of the as-obtained catalyst slurry (containing 3.0 μg of amorphous Pd-based NPs) onto the glassy carbon electrode. The obtained electrode was dried under ambient conditions until the solvent was completely evaporated.

The phase-dependent catalysis of as-synthesized Pd-based nanomaterials toward electrochemical HER was investigated. Polarization curves were measured at room temperature with a scan rate of 5 mV s⁻¹ and a rotation rate of 1,600 revolutions per minute (rpm) in 0.5 M H₂SO₄ aqueous solution. EIS measurements were carried out in the frequency range of 0.1 Hz-100 kHz with 10 mV amplitude to obtain the solution resistance (R_s) and the charge transfer resistance (K_ct). All the polarization curves were corrected by iR_s compensation.

For comparison, the HER measurements for the a-PdRh NPs, fcc-PdRh, a-Pd NPs, fcc-Pd NPs, and commercial Pt/C catalyst were conducted under the same conditions in 0.5 M H₂SO₄ aqueous solution.

As demonstrated in the HER polarization curves in FIG. 17A, the a-PdRh and a-Pd catalysts exhibit significantly superior HER activities compared to their crystalline counterparts, i.e., fcc-PdRh and fcc-Pd, demonstrating the vital role of amorphous phase in boosting the HER performance. Moreover, when compared with the monometallic a-Pd and fcc-Pd NPs, the binary a-PdRh and fcc-PdRh catalysts show remarkably excellent HER activity, indicating that the incorporation of Rh into Pd could improve the HER catalytic performance. Referring to FIG. 17B, only a small overpotential of 20.6 mV is needed for the a-PdRh catalyst to achieve a current density of 10 mA cm⁻², which is comparable to that of commercial Pt/C (15.7 mV) and much lower than those of fcc-PdRh (46.8 mV), monometallic a-Pd (55.0 mV), and fcc-Pd (122.0 mV). Such low overpotential also places a-PdRh catalyst among the best of the reported Pd-based acidic HER electrocatalysts (Table 2).

Reaction kinetics distinct catalysts during the HER process can be evaluated by analyzing their Tafel slopes. As shown in FIG. 17C and Table 2, the Tafel slope of a-PdRh catalyst (41.9 mV dec⁻¹) is much lower than those of crystalline fcc-PdRh (60.6 mV dec⁻¹) and monometallic a-Pd (66.7 mV dec⁻¹), demonstrating the faster reaction kinetics of a-PdRh in HER.

TABLE 2
Summary of electrocatalytic HER performances
of Pd-based catalysts in acidic media
		Overpotential
		(mV) at 10 mA	Tafel slope (mV
Catalyst	Electrolyte	cm−2	dec−1)
α-PdRh NPs	0.5M H2SO4	20.6	41.9
fcc-PdRh NPs	0.5M H2SO4	46.8	60.6
α-Pd NPs	0.5M H2SO4	55.0	66.7
fcc-Pd NPs	0.5M H2SO4	122.0	103.8
Pt/C	0.5M H2SO4	15.7	25.3
Pd2B nanosheets	0.5M H2SO4	15.3	22.5
Intermetallic PdCu nanowires	0.5M H2SO4	19.7	27
Pd/Cu—Pt nanorings	0.5M H2SO4	22.8	25
Au@PdAg nanoribbons	0.5M H2SO4	26.2	30
PdP2 NPs/C	0.5M H2SO4	27.5	29.5
PdCu0.2H0.43 NPs	0.5M H2SO4	28	23
Twinned PtPdRuTe structures	0.5M H2SO4	39	32
PdTe nanowires/rGO	0.5M H2SO4	48	63
Porous PdCuNi—S catalyst	0.5M H2SO4	48	35
Porous Pd—CNx composite	0.5M H2SO4	55	35
Pd NPs@Bis	0.5M H2SO4	62	30
PdCu@Pd nanocubes	0.5M H2SO4	68	35
PdCo@N-doped C	0.5M H2SO4	80	31
Pd3P2S8 nanodots	0.5M H2SO4	91	29
Ag@PdAg nanocubes	0.5M H2SO4	93	70
Pd/Bi/Cu hierarchical structures	0.5M H2SO4	79	61
Pd NPs/TiO2 nanospheres	0.5M H2SO4	108	64

FIGS. 18A to 18C illustrates CV curves of a-PdRh, fcc-PdRh and a-Pd catalysts measured at a scan rate of 10 mV s⁻¹ in N₂-saturated 0.5 M H₂SO₄ aqueous solution in the presence and absence of 10 mM CuSO₄, respectively. In order to further investigate the intrinsic activities of these catalysts, the TOF values of a-PdRh, fcc-PdRh, and a-Pd catalysts were determined based on the numbers of active sites which were estimated through copper (Cu) underpotential deposition (UPD) method. In detail, the number of active sites (n) is calculated according to the Cu UPD stripping charge (Qcu) based on the following equation:

n=Q _Cu/(2Fm)

where F is the Faraday constant (96485 C mol⁻¹), m is the loading mass of noble metals (3×10⁻⁶ g in this work), and the constant 2 means two electrons transferred in the process of Cu UPD stripping (Cu_upd→Cu²⁺+2e⁻).

FIG. 19 shows TOF values of a-PdRh, fcc-PdRh, and a-Pd catalysts measured in 0.5 M H₂SO₄ aqueous solution. The TOF value (H₂ s⁻¹) is calculated on the basis of the following equation: TOF=I/(2Fnm), where I is the current (A) during polarization curve test. The constant 2 indicates the number of electrons transferred in the HER process, as two electrons are required to form one H₂ molecule.

As shown in FIG. 19, the a-PdRh catalyst exhibits remarkably higher TOF values compared with those of crystalline fcc-PdRh and monometallic a-Pd. Specifically, at the overpotentials of 25, 50, 75, and 100 mV, the TOF values of a-PdRh catalyst are 4.6, 10.2, 18.1, and 29.3 H₂ s⁻¹, respectively, surpassing many reported metal-based electrocatalysts in the same electrolyte (Table 3), which verifies the excellent HER activity of the as-synthesized a-PdRh catalyst in acidic media.

TABLE 3
Comparison of the TOF values of α-PdRh catalyst with some
reported metal-based electrocatalysts toward HER in acidic media.
		Overpotential	TOF
Catalyst	Electrolyte	(mV)	(H2 s−1)
α-PdRh	0.5M H2SO4	25	4.6
		50	10.2
		75	18.1
		100	29.3
Ir NPs/hollow carbon	0.5M H2SO4	25	4.21
Ru on nitrogenated carbon	0.5M H2SO4	25	0.67
PdP2 NPs/C	0.5M H2SO4	27.5	0.32
Nanoporous Ag@Pd—Pt	0.5M H2SO4	75	3.26
Pd NPs@Bis	0.5M H2SO4	80	2.33
PdCu0.2H0.43 NPs	0.5M H2SO4	100	1.34
Porous PdCuNi—S catalyst	0.5M H2SO4	100	0.032
W—Mo dual-atom catalyst	0.5M H2SO4	100	2.36
Pt single atoms on graphene	0.5M H2SO4	100	26.41
Pd3P2S8 nanodots	0.5M H2SO4	140	1.6
Pt clusters/MXene	0.5M H2SO4	200	10.66

Furthermore, the EIS measurement results of a-PdRh, fcc-PdRh, and a-Pd catalysts (FIGS. 20A to 20C) unravel that the a-PdRh catalyst obviously possesses a smaller charge transfer resistance compared to the crystalline fcc-PdRh and monometallic a-Pd, affirming the fast charge transfer and favorable HER kinetics on a-PdRh. The aforementioned results demonstrate that the amorphous phase and the doping of Rh into Pd both contribute to the superior HER performance of the synthesized a-PdRh catalyst.

The embodiments may be chosen and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention for various embodiments and with various modifications that are suited to the particular use contemplated. While the methods disclosed herein have been described with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or re-ordered to form an equivalent method without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations are not limitations. While the apparatuses disclosed herein have been described with reference to particular structures, shapes, materials, composition of matter and relationships . . . etc., these descriptions and illustrations are not limiting. Modifications may be made to adapt a particular situation to the objective, spirit and scope of the present disclosure. All such modifications are intended to be within the scope of the claims appended hereto.

Claims

1. A method for synthesizing amorphous Pd-based nanoparticles, comprising: a) dissolving a Pd precursor in a first solvent to form a first solution;b) mixing the first solution with a second solvent to form a first mixture;c) adding surfactant into the first mixture to form a second mixture;d) heating the second mixture at a first heating temperature for a first heating time to render a second solution;e) adding other metal precursor into the second solution to form a third mixture;f) heating the third mixture at a second heating temperature for a second heating time to render a third solution;g) naturally cooling down the third solution to a room temperature;h) adding ethanol to the third solution to form a fourth solution; andi) collecting the amorphous Pd-based nanoparticles from the fourth solution by centrifugation.

2. The method of claim 1, wherein the Pd precursor is Pd(II) acetylacetonate, Pd(II) acetate, PdBr2 or combinations thereof.

3. The method of claim 2, wherein the Pd precursor has a purity of greater than or equal to 98%; the first solvent is a toluene having a purity of greater than or equal to 99.5%; and a concentration of Pd precursor to the toluene is in a range from 1 to 20 mg/ml.

4. The method of claim 3, where in the concentration of Pd precursor to the toluene is 10 mg/ml.

5. The method of claim 1, wherein the second solvent is an oleylamine having a purity greater than or equal to 70%; and a volume ratio of the oleylamine to the first solution is in a range from 20:1 to 3:1.

6. The method of claim 5, wherein the surfactant is a C3-C20 alkanethiol, an organophosphorus compound or the combination thereof.

7. The method of claim 1, wherein the surfactant is 1-propanethiol, 1-octanethiol, 2-ethylhexanethiol, 1-dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, triphenylphosphine, trioctylphosphine, or combinations thereof.

8. The method of claim 7, wherein the surfactant has a purity greater than or equal to 98%; and a molar ratio of the surfactant to Pd precursor is in a range from 1:2 to 2:1.

9. The method of claim 8, wherein the molar ratio of the surfactant to Pd precursor is 1:1.

10. The method of claim 1, wherein the first heating temperature is in a range from 140° C. to 200° C.; and the first heating time is in a range from 15 to 25 minutes.

11. The method of claim 10, wherein the first heating temperature is 155° C.; and the first heating time is 20 minutes.

12. The method of claim 1, wherein the other metal precursor is a Ru precursor, a Rh precursor, an Ag precursor, an Ir precursor, a Ni precursor or combinations thereof.

13. The method of claim 12, wherein the other metal precursor has a purity greater than or equal to 99.98%; and a molar ratio of the other metal precursor to the Pd precursor is in a range from 1:10 to 5:1.

14. The method of claim 13, wherein the molar ratio of the other metal precursor to the Pd precursor is 1:2.

15. The method of claim 14, wherein the step e) further comprising dissolving the other metal precursor in a solvent before adding the other metal precursor into the second solution.

16. The method of claim 1, wherein the second heating temperature is in a range from 140° C. to 200° C.; and the second heating time is in a range from 45 to 75 minutes.

17. The method of claim 16, wherein the second heating temperature is 155° C.; and the second heating time is 60 minutes.

18. The method of claim 1, wherein a volume ratio of the ethanol to the third solution is in a range from 1:1 to 10:1.

19. A method of preparing a catalyst, comprising: synthesizing amorphous Pd-based nanoparticles with the method of claim 1;dispersing carbon powder in ethanol to obtain a fourth mixture;sonicating the fourth mixture in an ice bath for one hour to form a carbon suspension;adding the synthesized amorphous Pd-based nanoparticles into the carbon suspension to obtain a fifth mixture;sonicating the fifth mixture in an ice bath for one hour to form a catalyst-loaded carbon suspension;collecting the catalyst-loaded carbon from the suspension by centrifugation;washing the catalyst-loaded carbon with a mixture solution composing of chloroform and ethanol;re-dispersing the catalyst-loaded carbon in a mixture solution containing isopropanol and water to form a sixth mixture;adding Nafion solution into the sixth mixture to form a seventh mixture; andsonicating the seventh mixture in an ice bath for one hour to form a catalyst.

20. A method of using the catalyst prepared with the method of claim 19 for an epoxide ring-opening reaction or an electrochemical hydrogen evolution reaction.