Dynamic metal-polymer interaction for the design of chemoselective and long-lived hydrogenation catalysts

Lee, Songhyun; Shin, Seung‐Jae; Baek, Hoyong; Choi, Yeonwoo; Hyun, Kyunglim; Seo, Myungeun; Kim, Kyunam; Koh, Dong‐Yeun; Kim, Hyungjun; Choi, Minkee

doi:10.1126/sciadv.abb7369

Cited by 64 publications

(67 citation statements)

References 39 publications

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“… Stability (h) Refs. NHC–Cu C 2 H 2 /C 2 H 4 (1/99) 25 9.6 × 10 5 2.1 × 10− 2 >99 ~30 100 This work Cu 1 /ND@G C 2 H 2 /C 2 H 4 /H 2 /He (1/20/10/69) 200 3 × 10 3 1.7 × 10− 3 >98 500 60 48 Ni 3 Ga C 2 H 2 /C 2 H 4 /H 2 /He (0.5/50/10/39.5) 200 4 × 10 4 1.4 × 10 −6 77 500 50 49 Al 13 Fe C 2 H 2 /C 2 H 4 /H 2 /He (0.5/50/5/44.5) 200 9 × 10 4 / 82 1000 20 50 Pd/PPS C 2 H 2 /C 2 H 4 /H 2 /C 3 H 8 /N 2 (0.6/49.3/0.9/0.6/48.6) 100 3.26 × 10 2 / >65 60 200 51 Pd@SOD C 2 H 2 /H 2 /N 2 (0.6/6/93.4) 150 3 × 10 4 / 94.5 12 50 7 Single–atom Pd C 2 H 2 /C 2 H 4 /H 2 /He (0.5/50/5/44.5) 120 …”

Section: Resultsmentioning

confidence: 99%

Efficient electrocatalytic acetylene semihydrogenation by electron–rich metal sites in N–heterocyclic carbene metal complexes

et al. 2021

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Electrocatalytic acetylene semihydrogenation is a promising alternative to thermocatalytic acetylene hydrogenation due to its environmental benignity and economic efficiency, but its performance is far below that of the thermocatalytic reaction because of strong competition from side reactions, including hydrogen evolution, overhydrogenation and carbon–carbon coupling reactions. We develop N–heterocyclic carbene–metal complexes, with electron–rich metal centers owing to the strongly σ–donating N–heterocyclic carbene ligands, as electrocatalysts for selective acetylene semihydrogenation. Experimental and theoretical investigations reveal that the copper sites in N–heterocyclic carbene–copper facilitate the absorption of electrophilic acetylene and the desorption of nucleophilic ethylene, ultimately suppressing the side reactions during electrocatalytic acetylene semihydrogenation, and exhibit superior semihydrogenation performance, with faradaic efficiencies of ≥98 % under pure acetylene flow. Even in a crude ethylene feed containing 1 % acetylene (1 × 104 ppm), N–heterocyclic carbene–copper affords a specific selectivity of >99 % during a 100–h stability test, continuous ethylene production with only ~30 ppm acetylene, a large space velocity of up to 9.6 × 105 mL·gcat−1·h−1, and a turnover frequency of 2.1 × 10−2 s−1, dramatically outperforming currently reported thermocatalysts.

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Section: Resultsmentioning

confidence: 99%

Efficient electrocatalytic acetylene semihydrogenation by electron–rich metal sites in N–heterocyclic carbene metal complexes

et al. 2021

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“…[3] These materials may include hypercrosslinked polymers, [4] covalent organic frameworks (COFs), [5] conjugated microporous polymers (CMPs), [6] covalent triazine frameworks (CTFs), [7] and engineering plastics. [8] Being composed of mainly sp 2 carbons,t hese polymers exhibit remarkably improved thermochemical stabilities compared to typical organic polymers.S oft organic polymers with nanoscale framework mobility can have unique potentials as catalyst supports compared to hard inorganic materials.F or instance, we recently demonstrated that mobile polyphenylene sulfide (PPS) chains can coat the Pd catalyst surface via the phenomena denoted as dynamic metal-polymer interaction (DMPI). [8] DMPI indicates as trong interaction between metal catalysts and mobile polymer chains at relatively mild temperatures.T he PPS overlayer on the Pd surface formed via DMPI regulated the adsorption of reactants and their surface reactions,s ignificantly enhancing the selectivity and catalyst lifetime in partial hydrogenation reactions.…”

Section: Introductionmentioning

confidence: 99%

Tailoring a Dynamic Metal–Polymer Interaction to Improve Catalyst Selectivity and Longevity in Hydrogenation

et al. 2021

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Controlling metal–support interactions is important for tuning the catalytic properties of supported metal catalysts. Here, premade Pd particles are supported on stable polymers containing different ligating functionalities to control the metal–polymer interactions and their catalytic properties in industrially relevant acetylene partial hydrogenation. The polymers containing strongly ligating groups (e.g., Ar‐SH and Ar‐S‐Ar) can form a polymer overlayer on the Pd surface, which enables selective acetylene adsorption and partial hydrogenation to ethylene without deactivation. In contrast, polymers with weakly ligating groups (e.g., Ar‐O‐Ar) do not form an overlayer, resulting in non‐selective hydrogenation and fast deactivation, similar to Pd catalysts on conventional inorganic supports. The results imply that tuning the metal–polymer interactions via rational polymer design can provide an efficient way of synthesizing selective and stable catalysts for hydrogenation.

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“…Considering the characteristics of our new frameworks: high surface area, good dispersion of the metals and weak and reversible binding to the metal cations; we hypothesized that they could be used as supports for noble metal sites. Similar materials including carbon nitride 46,47 or even PPS 48 have been used as supports to stabilize and modify catalytic activity of Pd in catalysis. Gratifyingly, Pd 2+ @P1 showed good catalytic activity for classical Pd-catalysed reactions, i.e.…”

Section: Catalytic Application Of Pd@p1mentioning

confidence: 99%

Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

Rivero‐Crespo¹,

Toupalas²,

Morandi³

2021

Preprint

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Porous organic frameworks have shown a number of promising properties; however, their industrial application is usually hampered due to the lability of their linkages (imine, boroxine, etc.). Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulfide (PPS), we hypothesized that 2D and 3D poly-arylthioether frameworks would merge the attractive features common to porous frameworks and PPS in a single material. Herein, we report a Pd-catalysed C–S/C–S metathesis-based method to prepare new porous poly-arylthioether frameworks in good yields. The self-correcting nature of the process has enabled the synthesis of new, robust materials with high surface areas. Despite the frameworks’ extreme resistance to harsh chemicals, they can be fully recycled to recover the original building blocks using the same catalytic reaction. In addition, we demonstrate preliminary results showing that these materials have great potential in several environmentally relevant applications including metal capture, metal sensing and heterogeneous catalysis. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new materials.

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Dynamic metal-polymer interaction for the design of chemoselective and long-lived hydrogenation catalysts

Cited by 64 publications

References 39 publications

Efficient electrocatalytic acetylene semihydrogenation by electron–rich metal sites in N–heterocyclic carbene metal complexes

Efficient electrocatalytic acetylene semihydrogenation by electron–rich metal sites in N–heterocyclic carbene metal complexes

Tailoring a Dynamic Metal–Polymer Interaction to Improve Catalyst Selectivity and Longevity in Hydrogenation

Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

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