Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts

Searles, Keith; Siddiqi, Georges; Safonova, Оlga V.; Copéret, Christophe

doi:10.1039/c6sc05178b

Cited by 149 publications

(211 citation statements)

References 65 publications

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“…The reaction of SiO 2 ‐supported Ni II with H 2 likely occurs following the mechanism shown in Scheme –. Heterolytic cleavage of the H−H and Ni−O bonds generates O−H and Ni−H bonds.…”

Section: Methodsmentioning

confidence: 99%

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

2018

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Silica‐supported Ni catalysts usually show poor stability, low selectivity, and short lifetime in high‐temperature alkane dehydrogenation reactions owing to the reduction to Ni0 nanoparticles under the reaction conditions. The introduction of a phosphate ligand to silica‐supported NiII provided single‐site tetrahedral NiII phosphosilicate as a stable and selective propane dehydrogenation catalyst. The NiII−OSi bonds activate the C−H bonds of propane and make the NiII sites catalytically active, whereas the Ni−OP bonds prevent the reduction of NiII to Ni0 under the dehydrogenation conditions and help to achieve high stability and selectivity.

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Section: Methodsmentioning

confidence: 99%

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

2018

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“…We rst prepared well-dened Ga III sites on SiO 2 with ca. 1.0 Ga III nm À2 by graing and thermolysis of [Ga(OSi(O t Bu) 3 ) 3 (-THF)]: 41,42 Ga III @SiO 2 (ref. 42) (M x @SiO 2 denoted as isolated M surface sites in its x oxidation state) via an SOMC/TMP approach and then graed [Cu(O t Bu)] 4 on residual surface silanols present in Ga III @SiO 2 .…”

Section: Catalyst Synthesis and Characterizationmentioning

confidence: 99%

Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites

et al. 2020

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“…[22] Recent work from our group has demonstrated the ability to mitigatet he reducibility of Ga 2 O 3 by dispersing Ga III species on the surface of an insulating support (i.e.,S iO 2 ). [23] We therefore reasoned that the atomicd ispersal of Ti IV sites at the surfaceo fS iO 2 ,u pon which Cu nanoparticles were then supported, could promote the selective hydrogenation of CO 2 to CH 3 OH by generating isolated Lewis acid sites decoupled from the bulk properties of the native oxide. We demonstrate here that such sites can be generated through asurface organometallic chemistry (SOMC) approach [24,25] to form am aterial (Cu/Ti@SiO 2 ,i nw hich "M@SiO 2 "d enotes isolated metal centers Mo nS iO 2 )t hat selectively hydrogenates CO 2 to CH 3 OH.…”

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confidence: 99%

Selective Hydrogenation of CO₂ to CH₃OH on Supported Cu Nanoparticles Promoted by Isolated Ti^IV Surface Sites on SiO₂

et al. 2019

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Small and narrowly distributed Cu nanoparticles, supported on SiO 2 decorated with isolated Ti IV sites, prepared through surface organometallic chemistry,s howeds ignificantly improved CO 2 hydrogenationa ctivity and CH 3 OH selectivity compared to the corresponding Cu nanoparticles supportedo nS iO 2 .T hese isolated Lewis acid Ti IV sites, evidenced by UV/Vis spectroscopy, are proposed to stabilize surface intermediates at the interface between Cu nanoparticlesa nd the support.The selective hydrogenation of CO 2 to CH 3 OH, together with the production of H 2 from renewable energy sources (e.g.,i ntermittent excesse nergy generatedf rom wind or solarp ower) is essential to av irtuous sustainable closed-carbon fuel cycle. [1][2][3][4] Its practice, however,i sc omplicated by the parasitic reversew ater-gas-shift (RWGS) reaction, which forms CO instead. The most prominent catalysts for selective CO 2 hydrogenation to CH 3 OH are Cu-based, although their activity and CH 3 OH selectivityd ramatically depend on the oxide support. [5][6][7][8] Cu supportedo nZ rO 2 (Cu/ZrO 2 ,i nw hich "Cu/X"d enotes Cu nanoparticles dispersed on support X) has shown promising activity and high CH 3 OH selectivity compared to Cu/ SiO 2 . [9][10][11][12] Whereas SiO 2 can be considered as an inert support for the Cu nanoparticles that catalyzet he reaction, ZrO 2 provides Zr IV sites interfacing Cu nanoparticles that act as Lewis acid sites andp romote CH 3 OH synthesis. [9] In fact, Cu nanoparticles supported on SiO 2 decorated with isolated Zr IV sites show CO 2 hydrogenationa ctivity andC H 3 OH selectivity nearly identicalt ot hose for Cu/ZrO 2 , [13] underscoring the importance of these Lewis acid sites at the periphery of Cu nanoparticles for the selective hydrogenation of CO 2 to CH 3 OH.In contrast, Cu/TiO 2 has been observed to be av ery poor CO 2 hydrogenation catalystw ith low reaction rates and low CH 3 OH selectivity, [7,8,14] in spiteo ft he ability of Ti IV metal cen- [a] Dr.

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Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts

Cited by 149 publications

References 65 publications

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites

Selective Hydrogenation of CO₂ to CH₃OH on Supported Cu Nanoparticles Promoted by Isolated Ti^IV Surface Sites on SiO₂

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Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts

Cited by 149 publications

References 65 publications

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites

Selective Hydrogenation of CO2 to CH3OH on Supported Cu Nanoparticles Promoted by Isolated TiIV Surface Sites on SiO2

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Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites

Selective Hydrogenation of CO₂ to CH₃OH on Supported Cu Nanoparticles Promoted by Isolated Ti^IV Surface Sites on SiO₂