Atomically Precise Strategy to a PtZn Alloy Nanocluster Catalyst for the Deep Dehydrogenation of <i>n</i>-Butane to 1,3-Butadiene

Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae; Kropf, A. Jeremy; Yang, Ce; Wen, Jianguo; Hackler, Ryan A.; Liu, Cong; Çelik, Gökhan; Marshall, Christopher L.; Stair, Peter C.; Delferro, Massimiliano

doi:10.1021/acscatal.8b02794

Cited by 77 publications

(71 citation statements)

References 47 publications

(77 reference statements)

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“…Recently,s everal silicasupported Pt-Zn alloy catalysts were investigated for the dehydrogenation of ethane and n-butane,s howing enhanced catalytic activity and the selectivity of corresponding alkene as compared with monometallic Pt catalysts. [10] However, these catalysts possessed larger sizes of MNPs and suffered from the sintering of MNPs during the reaction and/or regeneration process,which restricted their practical application. Until now,s upported Pt-Zn catalysts with excellent catalytic performance and stability have been rarely reported for PDH conversions.…”

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confidence: 99%

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

et al. 2020

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Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt‐based catalysts usually suffer from short‐term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand‐protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt–Zn clusters inside silicalite‐1 (S‐1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6–54 h−1 and specific activity of propylene formation of 65.5 molnormalC3normalH6 gPt−1 h−1 (WHSV=108 h−1) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S‐1‐H catalyst even after 13000 min on stream (WHSV=3.6 h−1), affording an extremely low deactivation constant of 0.001 h−1, which is 200 times lower than that of the PtZn4/Al2O3 counterpart under the same conditions. We also show that the introduction of Cs+ ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.

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Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

et al. 2020

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“…[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. In fact, the CH 3 OH formation rates and CH 3 OH selectivity are higher for Cu/Ti@SiO 2 than those fort he reportedC u/Zr@SiO 2 materials.…”

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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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“…[4] The physical and chemical behavior of nanoparticles and nanoclusters is generally size-and composition-dependent. [5] The ability to tailor the nanoparticles at an atomic level is of crucial importance for uncovering promising candidates for the assembly of new materials with specific functionalities.T o date,a tomically precise metallic nanoparticles have been synthesized in solution and in the gas phase, [5,6] allowing for the accurate determination of their structure-property correlations.I nc ontrast, the information about atomically precise metal oxide nanoparticles is rather limited [7] despite the widespread use of metal oxides owing to their catalytic, magnetic, and other properties.Titanium dioxide (TiO 2 )i so ne of the most widely used metal oxide catalysts and catalyst supports for diverse reactions including CO oxidation, [8] water splitting, [9] and pollutants degradation. [10] In the past years,the development of solution procedures has contributed significantly to the synthesis of titania nanoclusters.…”

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Activity of Atomically Precise Titania Nanoparticles in CO Oxidation

et al. 2019

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Understanding the property evolution of atomically precise nanoparticles atom by atom along the sizecontinuum is critical for selecting potential candidates to assemble nanomaterials with desired functionality,b ut it is very challenging experimentally especially for systems having mixtures of elements such as metal oxides.I nt his work, the capability to oxidize carbon monoxide has been measured experimentally for titania nanocluster anions of (TiO 2 ) n O m À (À3 m 3) across ab road size range in the gas phase.S toichiometric (TiO 2 ) n O À exhibits superior oxidative activity over other clusters of (TiO 2 ) n O m À (m ¼ 6 1) even when the cluster dimensions are scaled up to n = 60, indicating that each atom still influences the chemical behavior of titania nanoparticles composed of % 180 atoms.T he fascinating result not only identifies ap romising building blocko fT i n O 2n+1 for devising new nanoscale titania materials with desirable oxidative activity,but also provides compelling molecular-level evidence for the Mars-van Krevelen mechanism of CO oxidation over titania supports.Nanostructured materials have drawn increasing interest due to their potential applications in various fields such as catalysis, [1] sensors, [2] plasmonics, [3] and biomedicine. [4] The physical and chemical behavior of nanoparticles and nanoclusters is generally size-and composition-dependent. [5] The ability to tailor the nanoparticles at an atomic level is of crucial importance for uncovering promising candidates for the assembly of new materials with specific functionalities.T o date,a tomically precise metallic nanoparticles have been synthesized in solution and in the gas phase, [5,6] allowing for the accurate determination of their structure-property correlations.I nc ontrast, the information about atomically precise metal oxide nanoparticles is rather limited [7] despite the widespread use of metal oxides owing to their catalytic, magnetic, and other properties.Titanium dioxide (TiO 2 )i so ne of the most widely used metal oxide catalysts and catalyst supports for diverse reactions including CO oxidation, [8] water splitting, [9] and pollutants degradation. [10] In the past years,the development of solution procedures has contributed significantly to the synthesis of titania nanoclusters. [11] So far, the largest atomically precise cluster reported is [Ti 52 O 74 ]protected by surface organic ligands. [12] Theh ydrogen evolution activity tests demonstrated that it exhibits higher photocatalytic performance than the small cluster of [Ti 6 O 4 ]. It should be noted that the atomically precise titania nanoclusters synthesized via solution methods were usually scattered over ar ange of discrete sizes and stoichiometric compositions. [11] Moreover, the introduction of various distinct types of ligands to stabilize the specific clusters inevitably influences the related properties. [13] It is very difficult to generalize the correlations of property evolution with cluster size and stoichiometric compositions under comparable condi...

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Atomically Precise Strategy to a PtZn Alloy Nanocluster Catalyst for the Deep Dehydrogenation of n-Butane to 1,3-Butadiene

Cited by 77 publications

References 47 publications

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

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

Activity of Atomically Precise Titania Nanoparticles in CO Oxidation

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Atomically Precise Strategy to a PtZn Alloy Nanocluster Catalyst for the Deep Dehydrogenation of n-Butane to 1,3-Butadiene

Cited by 77 publications

References 47 publications

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

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

Activity of Atomically Precise Titania Nanoparticles in CO Oxidation

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