Structure Sensitivity of Acrolein Hydrogenation by Platinum Nanoparticles on BaxSr1−xTiO3Nanocuboids

Engelhardt, Christopher M.; Kennedy, Robert M.; Enterkin, James A.; Poeppelmeier, Kenneth R.; Ellis, Donald E; Marshall, Christopher L.; Stair, Peter C.

doi:10.1002/cctc.201701505

Cited by 8 publications

(7 citation statements)

References 94 publications

(180 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Stable adsorption modes of acrolein (Fig. 5), as reported by 22 DFT studies, 32,103,104,165,166,[174][175][176][177]190,[193][194][195][196][197][198][199][200][201][202][203][204] organized by host metal (Group 10 vs. 11). Nanoclusters are indicated as "NC," with the number of atoms in parentheses.…”

Section: Adsorption and Reactivitysupporting

confidence: 57%

“…Figure 4. A summary of the adsorption energies (eV) of acrolein (unsaturated aldehyde; red), allyl alcohol (unsaturated alcohol; blue), and propanal (saturated aldehyde; green), on transition metal surfaces as reported by 19 DFT studies, 32,103,104,165,166,176,190,[192][193][194][195][196][197][198][199][200][201][202][203] selecting the most negative value in a given study (see Table S1 for full tabulation of the data). Data from 5 vdW-DFT studies [174][175][176][177]204 The adsorption energies of acrolein and its partially hydrogenated products, allyl alcohol and propanal, from DFT calculations indicate that the selectivity is controlled by the adsorption thermodynamics on Group 10 metals but not on Group 11 metals (Fig.…”

Section: Adsorption and Reactivitymentioning

confidence: 99%

“…x TiO 3 nanocuboids (x = 0, 0.5, 1). 201 The effect of strain on acrolein adsorption was modeled using…”

Section: Pt and Pt Alloysmentioning

confidence: 99%

See 2 more Smart Citations

Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review

et al. 2020

View full text Add to dashboard Cite

Selective hydrogenation of α,ß-unsaturated aldehydes to unsaturated alcohols is a challenging class of reactions, yielding valuable intermediates for the production of pharmaceuticals, perfumes, and flavorings. On monometallic heterogeneous catalysts, the formation of the unsaturated alcohols is thermodynamically disfavored over the saturated aldehydes. Hence, new catalysts are required to achieve the desired selectivity. Herein, the literature of three major research areas in catalysis is integrated as a step toward establishing the guidelines for enhancing the selectivity: reactor studies of complex catalyst materials at operating temperature and pressure; surface science studies of crystalline surfaces in ultrahigh vacuum; and first-principles modeling using density functional theory calculations. Aggregate analysis shows that bimetallic and dilute alloy catalysts significantly enhance the selectivity to the unsaturated alcohols compared to monometallic catalysts. This comprehensive review focuses primarily on the role of different metal surfaces as well as the factors that promote the adsorption of the unsaturated aldehyde via its C=O bond, most notably by electronic modification of the surface and formation of the electrophilic sites. Furthermore, challenges, gaps, and opportunities are identified to advance the rational design of efficient catalysts for this class of reactions, including the need for systematic studies of catalytic processes, theoretical modeling of complex materials, and model studies under ambient pressure and temperature.

show abstract

Section: Adsorption and Reactivitysupporting

confidence: 57%

Section: Adsorption and Reactivitymentioning

confidence: 99%

See 1 more Smart Citation

Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Here, Pt NPs of different metal loading, size, and edge to facet ratio were synthesized by varying the number of ALD cycles. 54−56 For 1 cycle (1c-), 5 cycles (5c-), and 10 cycles (10c-) Pt/SrTiO 3 , the loading of Pt and the volume of the Pt NPs increase linearly with the number of ALD cycles (Figure S10 and Table S2). Average particle sizes of Pt NPs on 1c-Pt/SrTiO 3 , 5c-Pt/SrTiO 3 , and 10c-Pt/SrTiO 3 are found to be 1.2 ± 0.2 nm, 2.3 ± 0.7 nm, and 2.9 ± 1.1 nm, respectively (Figure S11).…”

Section: Results and Discussionmentioning

confidence: 99%

Upcycling Single-Use Polyethylene into High-Quality Liquid Products

et al. 2019

Self Cite

View full text Add to dashboard Cite

Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO3 completely converts PE (Mn = 8000–158,000 Da) or a single-use plastic bag (Mn = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (Mn) and the narrow polydispersity (Đ) of the final liquid product. Solid-state nuclear magnetic resonance of 13C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons.

show abstract

“…216,217 The energy profiles of hydrogenation pathways over typical alloy bimetallic surfaces were also investigated by DFT calculations to interpret the effect of the second metal. Yang et al 165 reported that the optimal reaction pathway over Co (111) was the hydrogenation of CC while CoGa 3 (221) favored the hydrogenation of CO (Figure 16b). The DFT calculation results indicated that the added In or Ga served as the active sites for adsorption and activation of the CO bond, and thus enhanced the selectivity to UOL.…”

Section: Theoretical Calculations For the Hydrogenation Of Ualmentioning

confidence: 99%

Highly Selective Catalysts for the Hydrogenation of Unsaturated Aldehydes: A Review

2020

View full text Add to dashboard Cite

The selective hydrogenation of unsaturated aldehydes (UAL) to saturated aldehydes (SAL) and unsaturated alcohols (UOL) is an important industrial process for producing fine chemicals. More efforts were made on the selective hydrogenation of CO to UOL, because CC hydrogenation is thermodynamically favored over CO hydrogenation. A crucial step toward high selectivity is the rational design of heterogeneous catalysts. In this Review, the catalyst design for the hydrogenation of UAL to UOL are catalogued into three major strategies, namely, modifying electronic properties, forming electrophilic sites, and involving confinement/steric effect. Research works accomplished in the past decade on the catalyst design for UAL hydrogenation are systematically reviewed using the above strategies. The focus is on the selectivity-enhancing mechanism, methods to perform the chosen strategy, and the factors that influence the mechanism. Density functional theory calculations and catalyst stability are discussed to appreciate the challenges in designing catalysts. In addition, recent advances in the selective hydrogenation of CC of cinnamaldehyde to hydrocinnamaldehyde are briefly reviewed.

show abstract

Structure Sensitivity of Acrolein Hydrogenation by Platinum Nanoparticles on Ba_xSr_1−xTiO₃Nanocuboids

Cited by 8 publications

References 94 publications

Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review

Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review

Upcycling Single-Use Polyethylene into High-Quality Liquid Products

Highly Selective Catalysts for the Hydrogenation of Unsaturated Aldehydes: A Review

Contact Info

Product

Resources

About