Pd-P nanoparticles as active catalyst for the hydrogenation of acetylenic compounds

Belykh, L. B.; Skripov, N. I.; Sterenchuk, T. P.; Gvozdovskaya, K. L.; Sanzhieva, S. B.; Schmidt, Friedrich

doi:10.1007/s11051-019-4641-z

Cited by 17 publications

(14 citation statements)

References 74 publications

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“…Pd−P nanoparticles can also be obtained by the lowtemperature reduction of Pd(acac) 2 in the presence of P and H 2 , as reported by Belykh et al for the hydrogenation of mono-and disubstituted acetylenic compounds. 207 By varying the P:Pd ratio, the triple bond hydrogenation rate relative to the double bond hydrogenation rate increased, resulting in a significant boost in activity (8−9-fold), while maintaining high selectivity to the corresponding alkenes. The same group also studied 2-methyl-3-butyn-2-ol hydrogenation as a model substrate 208 and found that modification with P improved the activity and turnover number (relative to Pd catalyst) without any decrease in the selectivity to 2-methyl-3-butene-2ol at high conversion (95−98%).…”

Section: Catalytic Applications Of Metalmentioning

confidence: 93%

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Liu

McCue

2021

ACS Catal.

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The efficiency of a heterogeneous catalyst depends on the nature and the number of catalytically active sites, but these are often inhomogeneous. One possible solution is to construct site-isolated catalysts in which most, if not all, of the sites are structurally uniform and well-defined. Metal phosphides and sulfides form with distinct crystal structures based on a range of component stoichiometries. Hence, incorporating active components (i.e., the catalytically active metal) into this structure can regulate geometric arrangements in a more reproducible manner where nonmetal atoms act as spacers around metal atoms to create isolated sites. A d-metal/p-block element strategy can provide several advantages compared with other methods which generate discrete active sites, including convenient synthesis, good process economics, and improved catalyst stability. Interestingly, the metal atoms in these systems still show typical catalyst traits associated with the metal which opens up many possible catalytic applications. This Review presents several interesting synthesis methods for preparing metal phosphides and sulfides and aims to draw links between geometric structure/electronic properties and enhanced catalytic performance (i.e., enhanced activity, selectivity, and stability) for both petrochemical and fine chemical processes. With precise knowledge of metal phosphide and sulfide structures/active sites, we envision the development of practically useful d-metal/p-block element catalysts from powder formulations to more industrial type pellets. It should, however, be noted that these materials are not without additional complexities. For example, metal phosphides and sulfides can have complex surface chemistry and the operating environment can induce structural evolution. These factors also need to be carefully considered.

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Section: Catalytic Applications Of Metalmentioning

confidence: 93%

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Liu

McCue

2021

ACS Catal.

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“…It is noteworthy that similar catalytic systems made in situ from 3 or 4 and Pd(OAc) 2 (Table , entries 3,4) were found to be not so effective as corresponding complexes 13 or 14 , however, turned out to be better than “pure” Pd(OAc) 2 (Table , entry 5). Incomplete in situ complex formation of 3 or 4 and Pd(OAc) 2 may be a reason of lower activity of catalytic systems obtained in situ: partially unreacted Pd(OAc) 2 forms Pd‐black, which is usually less catalytically active than small metal NPs , . Indeed, according to microphotography of mixture of 4 with Pd(OAc) 2 , treated by NaBH 4 (see Supp.…”

Section: Study Of Catalytic Activities Of 13–22mentioning

confidence: 99%

Amphiphilic Pd^II‐NHC Complexes on 1,3‐Alternate p‐tert‐Butylthiacalix[4]arene Platform: Synthesis and Catalytic Activities in Coupling and Hydrogenation Reactions

et al. 2020

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Herein we report the first example of amphiphilic PdII–NHC complexes on the thiacalix[4]arene backbone in 1,3‐alternate configuration. Relative catalytic activity of synthesized PdII–NHC complexes in Suzuki–Miyaura coupling of haloarenes with phenylboronic acid was studied. A combination of micellar and metallocomplex catalysis was observed in Suzuki–Miyaura coupling upon going from pure DMF to water/DMF 3:1: the 2‐fold increase of conversion of 4‐bromoanisole unlike pure DMF was found. Interesting feature was found using chloroarene in DMF/water: the reaction selectivity changed from heterocoupling to homo coupling of phenylboronic acid. PdII–NHC complexes demonstrated a high activity in model hydrogenation reaction of p‐nitrophenol using sodium borohydride. The most lipophilic PdII–NHC complex was found to be most active, which can be attributed with additional p‐nitrophenol preconcentration in the aggregates due to larger hydrophobic capacity of macrocycle.

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“…Pd−P nanoparticles in the amorphous and crystalline state are new promising catalysts for hydrogenation [17–19] . Interest in the study of the nature and properties of transition metal nanophosphides has increased sharply since the beginning of the XXI century [20–22] .…”

Section: Introductionmentioning

confidence: 99%

“…PdÀ P nanoparticles in the amorphous and crystalline state are new promising catalysts for hydrogenation. [17][18][19] Interest in the study of the nature and properties of transition metal nanophosphides has increased sharply since the beginning of the XXI century. [20][21][22] In particular, we have previously shown [13] that the modification of palladium catalyst with elemental phosphorus at the stage of its formation increases the yield of H 2 O 2 from 69 % to 96 %-98 % while lowering its activity in the hydrogenation of eAQ by an order of magnitude.…”

Section: Introductionmentioning

confidence: 99%

Structurally Disordered Pd−P Nanoparticles as Effective Catalysts for the Production of Hydrogen Peroxide by the Anthraquinone Method

et al. 2021

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The properties of the catalyst based on structurally disordered PdÀ P nanoparticles supported on a carbon support (PdÀ P/C) in the preparation of hydrogen peroxide by the anthraquinone method have been studied. It is shown that a high yield of H 2 O 2 is observed upon sequential hydrogenation of 2000 mol of eAQ (mol Pd) À 1 . The H 2 O 2 yield reaches 96 %-97 %. PdÀ P nanoparticles are more active in the hydrogenation of 2-ethyl-9,10anthraquinone than Pd 6 P crystalline phosphide. In terms of H 2 O 2 yield, PdÀ P/C catalysts are superior to known catalysts: Pd/ C, Pd/Al 2 O 3 . Based on the data of X-ray powder diffraction, X-ray photoelectron spectroscopy, Inductively Coupled Plasma and thermogravimetry, the main reasons for the deactivation of PdÀ P/C catalysts have been established. Crystallization of the structurally disordered PdÀ P nanoparticles, poisoning by eAQ conversion products and leaching of the active component are considered to be possible reasons of the PdÀ P/C catalyst deactivation.

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Pd-P nanoparticles as active catalyst for the hydrogenation of acetylenic compounds

Cited by 17 publications

References 74 publications

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Amphiphilic Pd^II‐NHC Complexes on 1,3‐Alternate p‐tert‐Butylthiacalix[4]arene Platform: Synthesis and Catalytic Activities in Coupling and Hydrogenation Reactions

Structurally Disordered Pd−P Nanoparticles as Effective Catalysts for the Production of Hydrogen Peroxide by the Anthraquinone Method

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Pd-P nanoparticles as active catalyst for the hydrogenation of acetylenic compounds

Cited by 17 publications

References 74 publications

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Metal Phosphides and Sulfides in Heterogeneous Catalysis: Electronic and Geometric Effects

Amphiphilic PdII‐NHC Complexes on 1,3‐Alternate p‐tert‐Butylthiacalix[4]arene Platform: Synthesis and Catalytic Activities in Coupling and Hydrogenation Reactions

Structurally Disordered Pd−P Nanoparticles as Effective Catalysts for the Production of Hydrogen Peroxide by the Anthraquinone Method

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Amphiphilic Pd^II‐NHC Complexes on 1,3‐Alternate p‐tert‐Butylthiacalix[4]arene Platform: Synthesis and Catalytic Activities in Coupling and Hydrogenation Reactions