Enhancement of Alkyne Semi-Hydrogenation Selectivity by Electronic Modification of Platinum

Wang, Zhenshu; Garg, Aaron; Wang, Linxi; He, Haoran; Dasgupta, Anish; Zanchet, Daniela; Janik, Michael J.; Rioux, Robert M.; Román‐Leshkov, Yuriy

doi:10.1021/acscatal.9b04070

Cited by 31 publications

(29 citation statements)

References 56 publications

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“…This transformation is also a classical model reaction to evaluate the performance of a newly developed catalyst or hydrogenation method [1][2][3][4][5][6][7][8] . Although significant progress has been achieved, current reports are still mainly relying on the expensive noble-metal catalysts (e.g., Pt, Pd, Ru, or their related alloys) [9][10][11][12][13] or complicated metal complexes [14][15][16][17] with gaseous hydrogen (H 2 ) or expensive and/or toxic organic hydrogen sources, causing severe concerns on the cost, safety, and sustainability. To solve these problems, an electrochemical strategy has been recently developed by our group for selective semi-hydrogenation of alkynes over a Pd-P cathode by using H 2 O as the hydrogen source 18 .…”

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confidence: 99%

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

et al. 2021

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Electrocatalytic alkyne semi-hydrogenation to alkenes with water as the hydrogen source using a low-cost noble-metal-free catalyst is highly desirable but challenging because of their over-hydrogenation to undesired alkanes. Here, we propose that an ideal catalyst should have the appropriate binding energy with active atomic hydrogen (H*) from water electrolysis and a weaker adsorption with an alkene, thus promoting alkyne semi-hydrogenation and avoiding over-hydrogenation. So, surface sulfur-doped and -adsorbed low-coordinated copper nanowire sponges are designedly synthesized via in situ electroreduction of copper sulfide and enable electrocatalytic alkyne semi-hydrogenation with over 99% selectivity using water as the hydrogen source, outperforming a copper counterpart without surface sulfur. Sulfur anion-hydrated cation (S2−-K+(H2O)n) networks between the surface adsorbed S2− and K+ in the KOH electrolyte boost the production of active H* from water electrolysis. And the trace doping of sulfur weakens the alkene adsorption, avoiding over-hydrogenation. Our catalyst also shows wide substrate scopes, up to 99% alkenes selectivity, good reducible groups compatibility, and easily synthesized deuterated alkenes, highlighting the promising potential of this method.

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confidence: 99%

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

et al. 2021

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“…Overall, the catalytic property of the nanocrystals is directly linked to the position of their d-band center related to the Fermi level, which greatly affects the adsorption energies of the reactants as well as their activation barriers. After the surface engineering of Pt (or Ru) atoms on sub-5 nm Pd Ths, the change in electronic property for both the inner Pd core and surface Pt (or Ru) skin indicates a downshift of their d-band center, which plays a decisive role in determining their catalytic performance. , …”

Section: Resultsmentioning

confidence: 99%

“…After the surface engineering of Pt (or Ru) atoms on sub-5 nm Pd Ths, the change in electronic property for both the inner Pd core and surface Pt (or Ru) skin indicates a downshift of their d-band center, which plays a decisive role in determining their catalytic performance. 39,40 A set of control experiments were conducted to gain a deep understanding of the growth mechanism of Pt, Ru, and Rh atoms on sub-5 nm Pd Ths, aimed at achieving high quality and uniformity for the sub-10 nm core−shell structures. First, the role of the valence of Pt, Ru, and Rh precursors in determining the deposition behaviors have been investigated by TEM images (Figure S15).…”

Section: Resultsmentioning

confidence: 99%

“…Chronoamperometry tests for ORR were conducted in O 2 -saturated 0.1 M KOH solution at rotation rate of 1600 rpm for 12000 s at 0.7 V. The HER polarization curves of astested samples were performed in N 2 -saturated 0.5 M H 2 SO 4 electrolyte at a scan rate of 5 mV s −1 . The electrochemical doublelayer capacitance (C dl ) was employed to evaluate the ECSA for HER, which was tested by CVs prepared in the potential range without a redox process from 0.1 to 0.2 V (vs RHE) at different scan rates (20,40,60,80,100,120,140,160, and 180 mV s −1 ). Chronoamperometry tests for HER were performed in N 2 -saturated 0.5 M H 2 SO 4 solution for 17 h at a fixed potential of 0.07 V.…”

Section: Methodsmentioning

confidence: 99%

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Atomic Crystal Facet Engineering of Core–Shell Nanotetrahedrons Restricted under Sub-10 Nanometer Region

Zhang

Qian

et al. 2021

ACS Nano

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Simultaneously engineering the size and surface crystal facets of bimetallic core–shell nanocrystals offers an effective route to not only reduce the extravagance of innermost core metal and maximize the utilization efficiency of shell atoms but also strengthen the core-to-shell interaction via ligand and/or strain effects. Herein, we systematically study the architecture transition and crystal facet engineering at the atomic level on the surface of sub-5 nm Pd(111) tetrahedrons (Ths), aimed at embodying how the variations in the local facet and shape of a sub-10 nm core–shell structure affect its surface geometrical properties and electronic structures. Specifically, surface atomic replication is predominant when the shell metal deposits less than five atomic layers, thus forming a series of Pd@M (M = Pt, Ru, and Rh) core–shell Ths enclosed by (111) facets (∼6.8 nm), while over five atomic layers, spontaneous facets tropism of each metal is predominant, where Pt atoms still follow fcc-(111) packing, Ru atoms select hcp-phase stacking, and Rh atoms choose fcc-(100) crystallization, respectively. In particular, Pt atoms take a seamless geometrical transformation from Pd@Pt Ths into Pd@Pt truncated octahedrons (TOhs, ∼7.6 nm). As a proof-of-concept application, such sub-10 nm core–shell architectures with Pt skin show a component-dependent relationship toward oxygen reduction reaction (ORR), where the catalytic activity follows the order of Pd@Pt(111) TOhs (E 1/2 = 0.916 V, 1.632 A mgPt –1) > Pd@Pt(111) Ths > Pt black. Meanwhile the Ru skin show a facet-dependent relationship toward acidic hydrogen evolution reaction (HER) where the catalytic activity follows the order of Pd@Ru(111) Ths > Pd@Ru(hcp) Ths > Pd Ths.

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“…Alkyne functionalization is an atom-economic, green, and sustainable process for incorporating triple bonds into functional molecules. − How to control the product selectivity is the major challenge in catalytic alkyne hydrofunctionalization. − Compared to mononuclear metal complexes, dinuclear metal catalysts have the advantages of reactivity and selectivity. − Bimetallic catalysts that feature two closely associated metal sites and large perturbations in the electronic structure of metal–metal bonds have a correspondingly large impact on the active site of a catalyst. Thus, the catalytic activity and selectivity of bimetallic catalysts can be tuned by the nuclearity and bimetallic compatibility, and by ligand design. ,− …”

Section: Introductionmentioning

confidence: 99%

Control of the Regioselectivity of Alkyne Hydrostannylation by Tuning the Metal Pair of Heterobimetallic Catalysts: A Theoretical Study

Huo

Zeng

et al. 2021

Organometallics

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In this work, the detailed reaction mechanisms of two distinct Sn–H bond activation modes of the [Cu–Fe] and [Cu–Mn] heterobimetallic catalysts were computationally investigated using density functional theory calculations. Our calculation results show that the alkyne hydrostannylation catalyzed by the [Cu–Fe] and [Cu–Mn] catalysts involves three steps: Sn–H bond activation, alkyne insertion, and vinylstannane formation. The Sn–H bond activation step is an essential process during two distinct catalytic cycles, where two divergent Sn–H bond activation modes are produced by the [Cu–Fe] and [Cu–Mn] heterobimetallic catalysts. In the [Cu–Mn] catalytic process, the Sn–H bond is divided into (CH3)3Sn–Mn(CO)5 and MeCuH, whereas in the [Cu–Fe] catalytic process, HFe(CO)2 and MeCu–Sn(CH3)3 are obtained. The alkyne insertion process is the rate-determining step. Both our calculation and experimental results have shown that using a [Cu–Mn] heterobimetallic catalyst, only the (E)-β-product ((E)-β-Pro) can be easily obtained at about 60 °C. Using a [Cu–Fe] heterobimetallic catalyst, both α-Pro and (E)-β-Pro can be easily obtained at room temperature. The different regioselectivity of alkyne hydrostannylation catalyzed by different heterobimetallic catalysts is controlled by the Cu/M pair. Our calculation results are consistent with and provide an explanation for the experimental observations, which would be particularly helpful for the further development of alkyne hydrostannylation and the design of other heterobimetallic catalysts.

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Enhancement of Alkyne Semi-Hydrogenation Selectivity by Electronic Modification of Platinum

Cited by 31 publications

References 56 publications

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

Converting copper sulfide to copper with surface sulfur for electrocatalytic alkyne semi-hydrogenation with water

Atomic Crystal Facet Engineering of Core–Shell Nanotetrahedrons Restricted under Sub-10 Nanometer Region

Control of the Regioselectivity of Alkyne Hydrostannylation by Tuning the Metal Pair of Heterobimetallic Catalysts: A Theoretical Study

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