skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Catalytic oxidation of propane over palladium alloyed with gold: an assessment of the chemical and intermediate species
Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (Pd n Au 100−n ), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ∼ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified for the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. The implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed.  more » « less
Award ID(s):
1658990
PAR ID:
10088809
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Catalysis Science & Technology
Volume:
8
Issue:
23
ISSN:
2044-4753
Page Range / eLocation ID:
6228 to 6240
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; (, Nanoscale)
    null (Ed.)
    Palladium catalyzed cross-coupling reactions represent a significant advancement in contemporary organic synthesis as these reactions are of strategic importance in the area of pharmaceutical drug discovery and development. Supported palladium-based catalysts are highly sought-after in carbon–carbon bond forming catalytic processes to ensure catalyst recovery and reuse while preventing product contamination. This paper reports the development of heterogeneous Pd-based bimetallic catalysts supported on fumed silica that have high activity and selectivity matching those of homogeneous catalysts, eliminating the catalyst's leaching and sintering and allowing efficient recycling of the catalysts. Palladium and base metal (Cu, Ni or Co) contents of less than 1.0 wt% loading are deposited on a mesoporous fumed silica support (surface area SA BET = 350 m 2 g −1 ) using strong electrostatic adsorption (SEA) yielding homogeneously alloyed nanoparticles with an average size of 1.3 nm. All bimetallic catalysts were found to be highly active toward Suzuki cross-coupling (SCC) reactions with superior activity and stability for the CuPd/SiO 2 catalyst. A low CuPd/SiO 2 loading (Pd: 0.3 mol%) completes the conversion of bromobenzene and phenylboronic acid to biphenyl in 30 minutes under ambient conditions in water/ethanol solvent. In contrast, monometallic Pd/SiO 2 (Pd: 0.3 mol%) completes the same reaction in three hours under the same conditions. The combination of Pd with the base metals helps in retaining the Pd 0 status by charge donation from the base metals to Pd, thus lowering the activation energy of the aryl halide oxidative addition step. Along with its exceptional activity, CuPd/SiO 2 exhibits excellent recycling performance with a turnover frequency (TOF) of 280 000 h −1 under microwave reaction conditions at 60 °C. Our study demonstrates that SEA is an excellent synthetic strategy for depositing ultra-small Pd-based bimetallic nanoparticles on porous silica for SCC. This avenue not only provides highly active and sintering-resistant catalysts but also significantly lowers Pd contents in the catalysts without compromising catalytic activity, making the catalysts very practical for large-scale applications. 
    more » « less
  2. ; (, RSC Advances)
    In this work, a palladium binding peptide, Pd4, has been used for the synthesis of catalytically active palladium-decorated gold (Pd-on-Au) nanoparticles (NPs) and palladium–gold (Pd x Au 100− x ) alloy NPs exhibiting high nitrite degradation efficiency. Pd-on-Au NPs with 20% to 300% surface coverage (sc%) of Au showed catalytic activity commensurate with sc%. Additionally, the catalytic activity of Pd x Au 100− x alloy NPs varied based on palladium composition ( x = 6–59). The maximum nitrite removal efficiency of Pd-on-Au and Pd x Au 100− x alloy NPs was obtained at sc 100% and x = 59, respectively. The synthesized peptide-directed Pd-on-Au catalysts showed an increase in nitrite reduction three and a half times better than monometallic Pd and two and a half times better than Pd x Au 100− x NPs under comparable conditions. Furthermore, peptide-directed NPs showed high activity after five reuse cycles. Pd-on-Au NPs with more available activated palladium atoms showed high selectivity (98%) toward nitrogen gas production over ammonia. 
    more » « less
  3. ; ; ; ; ; ; ; ; ; ; et al (, Nature Communications)
    Abstract Direct ethanol fuel cells have been widely investigated as nontoxic and low-corrosive energy conversion devices with high energy and power densities. It is still challenging to develop high-activity and durable catalysts for a complete ethanol oxidation reaction on the anode and accelerated oxygen reduction reaction on the cathode. The materials’ physics and chemistry at the catalytic interface play a vital role in determining the overall performance of the catalysts. Herein, we propose a Pd/Co@N-C catalyst that can be used as a model system to study the synergism and engineering at the solid-solid interface. Particularly, the transformation of amorphous carbon to highly graphitic carbon promoted by cobalt nanoparticles helps achieve the spatial confinement effect, which prevents structural degradation of the catalysts. The strong catalyst-support and electronic effects at the interface between palladium and Co@N-C endow the electron-deficient state of palladium, which enhances the electron transfer and improved activity/durability. The Pd/Co@N-C delivers a maximum power density of 438 mW cm −2 in direct ethanol fuel cells and can be operated stably for more than 1000 hours. This work presents a strategy for the ingenious catalyst structural design that will promote the development of fuel cells and other sustainable energy-related technologies. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, Advanced Synthesis & Catalysis)
    Abstract The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system. 
    more » « less
  5. ; ; ; ; ; ; ; (, Synthesis)
    Abstract Catalytic oxidation of tricyclic endo-norbornene-fused tetrahydrofuran with the bimetallic nanocluster Cu/Au-PVP in the presence of H2O2 or t-BuOOH as the oxidant leads to C–H bond oxidation adjacent to the ether function to give 4-oxa-tricyclo[5.2.1.0]-8,9-exo-epoxydecane, however, oxidation with Pd/Au-PVP takes place at the C=C double bond to give the same epoxide and the oxidative three-bond forming dimeric product, dodecahydro-1,4:6,9-dimethanodibenzofurano[2,3-b:7,8-b′]bisoxolane. Formation of the latter product suggests the involvement of a reactive Pd–C intermediate. Similarly, oxidative C–C bond-forming reactions are observed in cycloaddition reactions of N2-Boc-1,2,3,4-tetrahydro-γ-carbolines and 2,3-dihydroxybenzoic acid with Cu/Au-PVP (2–5 mol%) and H2O2 at 25 °C, providing two-bond-forming [4+2] cycloadducts. Under similar reaction conditions, Pd/Au-PVP did not produce the corresponding cycloadduct, indicating a need for complexation between Cu and the carboxylic acid group of 2,3-dihydroxybenzoic acid and the allylic amine function of the γ-carbolines during the cyclization reaction. The reported intermolecular coupling reactions using Pd/Au-PVP or Cu/Au-PVP nanocluster catalysts under oxidative conditions at 25 °C are unprecedented. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email