Selective hydrogenation of mixed alkyne/alkene streams at elevated pressure over a palladium sulfide catalyst

McCue, Alan J.; Guerrero-Ruı́z, A.; Ramirez-Barria, Carolina; Rodrı́guez-Ramos, I.; Anderson, James A.

doi:10.1016/j.jcat.2017.09.004

Cited by 67 publications

(65 citation statements)

References 82 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More importantly, the catalytic performance of R350 sample maps on well to that previously reported for a nano-sized Pd4S supported on carbon nanofibers. [49,50] This report therefore suggests that detailed characterisation of bulk phase materials can be useful for establishing links with analogous nano-sized particles which are challenging to characterise given their extremely small size.…”

Section: Implications Of the Phase Transformation On Selectivitymentioning

confidence: 93%

“…[46] Recently, metal sulfides, or more specifically, supported palladium sulfide nanoparticles have been shown to be an excellent hydrogenation catalyst [47,48] with performance attributed to the formation of the Pd4S phase and isolation of the active Pd sites. [49,50] Whilst these reports focused on a supported Pd4S phase, it was hinted that similar results could be obtained with a bulk phase palladium sulfide powder. [49] Reports of sulfur being beneficial in heterogeneous catalysis are still somewhat limited [ 51 ] Herein, results are presented which demonstrate how a PdS powder evolves and changes with thermal pre-treatment to yield a highly…”

Section: Introductionmentioning

confidence: 89%

“…At low te pe atu e ≈ °C , it is lea that h d oge i te a ts ith the palladiu sulfide, perhaps by forming a hydride type phase as previously reported. [50] However, this results in only a minor change in crystallinity and composition. Increasing the reduction temperature to 150°C sees the onset of sulfur loss as H2S or SO2 (Figure 2A) from the surface, consistent with a shift in the composition measured by EDX ( Table 2).…”

Section: Evolution Of the Palladium Sulfide Phasementioning

confidence: 99%

See 2 more Smart Citations

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Liu

McCue

Feng

et al. 2018

Journal of Catalysis

Self Cite

View full text Add to dashboard Cite

Unsupported, bulk phase palladium sulfide has been studied for the selective hydrogenation of acetylene. The sample underwent significant change during thermal pretreatments, the extent of which depends on temperature. Exposure to hydrogen at temperatures of 150°C or above results in the loss of sulfur from the sample, primarily as hydrogen sulfide. As sulfur is lost, the sample is progressively transformed from a sulfur rich phase (PdS) to a sulfur lean phase (Pd4S) via an intermediate phase (Pd16S7). Reduction at 250°C produces a material, which contains simultaneously these three phases mentioned above with some Pd4S phase is located at the surface, whereas reduction at 350°C results in a largely pure Pd4S phase. Thermal treatments which produce a Pd4S surface display excellent catalytic properties. At complete acetylene conversion at 250°C, ethylene selectivites of 82.8% and 90.0% were obtained under non-competitive and competitive conditions, respectively. Beneficial catalytic properties arise from the uniformity of Pd sites due to the crystal structure of Pd4S along with electronic influences on the adsorption/desorption processes arising from sulfur neighbours. No indications of deactivation or obvious deposition of carbon were observed over Pd4S sample after 50 h on stream.

show abstract

Section: Implications Of the Phase Transformation On Selectivitymentioning

confidence: 93%

Section: Introductionmentioning

confidence: 89%

Section: Evolution Of the Palladium Sulfide Phasementioning

confidence: 99%

See 1 more Smart Citation

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Liu

McCue

Feng

et al. 2018

Journal of Catalysis

Self Cite

View full text Add to dashboard Cite

show abstract

“…To reduce the ecological footprint of hydrogenation processes, new materials have been investigated including other metals, alloys and intermetallic compounds, metal oxides, hybrid nanoparticles, supported single atoms, and p ‐block modified noble metals ,. As lately shown by an integrated experimental and theoretical work that classified prominent families of hydrogenation catalysts, the modification of palladium‐based catalysts with sulfur‐containing molecules, which yields nanostructured palladium sulfide ( i. e ., Pd 3 S and Pd 4 S) emerged as one of the most effective ways of tuning the ensemble properties to obtain a robust catalyst ,. To benefit from this design strategy, we have explored if the approach applies to other p ‐block elements.…”

Section: Introductionmentioning

confidence: 99%

“…[6,13] As lately shown by an integrated experimental and theoretical work that classified prominent families of hydrogenation catalysts, the modification of palladiumbased catalysts with sulfur-containing molecules, which yields nanostructured palladium sulfide (i. e., Pd 3 S and Pd 4 S) emerged as one of the most effective ways of tuning the ensemble properties to obtain a robust catalyst. [13,14] To benefit from this design strategy, we have explored if the approach applies to other pblock elements.…”

Section: Introductionmentioning

confidence: 99%

Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi‐Hydrogenation

et al. 2018

View full text Add to dashboard Cite

Modification of transition metals with p‐block elements is known to be effective to tune the ensemble characteristics of catalysts for the semi‐hydrogenation of alkynes. To further explore this approach, here we prepare two nickel phosphides, namely Ni2P and Ni5P4. Assessment in the semi‐hydrogenation of 1‐hexyne and 2‐methyl‐3‐butyn‐2‐ol shows that the phosphides present higher rate and selectivity than unmodified nickel catalysts. While no activity and selectivity differences are displayed in the semi‐hydrogenation of 1‐hexyne over Ni2P and Ni5P4, in the case of 2‐methyl‐3‐butyn‐2‐ol a higher rate and lower selectivity to 2‐methyl‐3‐buten‐2‐ol are observed over Ni2P. Density functional theory reveals that the hydroxyl group facilitates the reaction, but also increases the barrier for product desorption. Detailed analyses of the ensemble show the potential of phosphorus to create spatially‐isolated nickel trimers that surpass the performance of unmodified nickel, but also its limited ability to modulate the electronic properties and related binding energies of organic intermediates, which is key to preventing undesired side reactions.

show abstract

Creation of Redox‐Active PdS_x Nanoparticles Inside the Defect Pores of MOF UiO‐66 with Unique Semihydrogenation Catalytic Properties

Dong

Wang

2019

Adv Funct Materials

View full text Add to dashboard Cite

Semihydrogenation of alkynes to produce alkenes is very important in the industry; however, over‐hydrogenation heavily complicates the postprocesses, which are highly energy consuming and not environmentally friendly. One of the most efficient pathways to solve this challenging issue is to develop highly selective catalysts that could only hydrogenate alkynes and are inactive in hydrogenation of alkenes. This work presents herein an efficient catalyst, consisting of in situ created PdS0.53 nanoparticles as the redox‐active sites inside the defect pores of metal–organic framework UiO‐66, which demonstrates very high alkene selectivity (up to 99.5%) in semihydrogenation of easily over‐hydrogenated terminal alkynes. In contrast to the traditional catalysts, strict control over the reaction time becomes the nonessential condition because the catalyst system is almost inactive in hydrogenation of alkenes. Therefore, this paradigm work provides a practically applicable pathway for the development of efficient catalysts with unique catalytic properties for selective semihydrogenation reactions.

show abstract

Selective hydrogenation of mixed alkyne/alkene streams at elevated pressure over a palladium sulfide catalyst

Cited by 67 publications

References 82 publications

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi‐Hydrogenation

Creation of Redox‐Active PdS_x Nanoparticles Inside the Defect Pores of MOF UiO‐66 with Unique Semihydrogenation Catalytic Properties

Contact Info

Product

Resources

About

Selective hydrogenation of mixed alkyne/alkene streams at elevated pressure over a palladium sulfide catalyst

Cited by 67 publications

References 82 publications

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Evolution of palladium sulfide phases during thermal treatments and consequences for acetylene hydrogenation

Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi‐Hydrogenation

Creation of Redox‐Active PdSx Nanoparticles Inside the Defect Pores of MOF UiO‐66 with Unique Semihydrogenation Catalytic Properties

Contact Info

Product

Resources

About

Creation of Redox‐Active PdS_x Nanoparticles Inside the Defect Pores of MOF UiO‐66 with Unique Semihydrogenation Catalytic Properties