Remarkable Carbon Dioxide Hydrogenation to Ethanol on a Palladium/Iron Oxide Single‐Atom Catalyst

Caparrós, Francisco J.; Soler, Lluís; Rossell, Marta D.; Angurell, Inmaculada; Piccolo, L.; Rossell, Oriol; Llorca, Jordi

doi:10.1002/cctc.201800362

Cited by 105 publications

(56 citation statements)

References 25 publications

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“…Furthermore, comparative studies on the catalysis of different aggregation states, e.g., single atoms (SAs), nanoclusters (NCs), and nanoparticles (NPs), like the work by Zhang et al on the Ru catalysts for CO 2 methanation 24 , received extensive attention. But, most of these studies rely on tuning the aggregation states by changing the metal loadings 25,26 , which did not conform to the single-factor-variable research method. Thus, a facile approach to regulate the aggregation states of metal species other than altering metal loading is desired.…”

Section: Introductionmentioning

confidence: 99%

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

et al. 2019

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Preparation of single atom catalysts (SACs) is of broad interest to materials scientists and chemists but remains a formidable challenge. Herein, we develop an efficient approach to synthesize SACs via a precursor-dilution strategy, in which metalloporphyrin (MTPP) with target metals are co-polymerized with diluents (tetraphenylporphyrin, TPP), followed by pyrolysis to N-doped porous carbon supported SACs (M 1 /N-C). Twenty-four different SACs, including noble metals and non-noble metals, are successfully prepared. In addition, the synthesis of a series of catalysts with different surface atom densities, bi-metallic sites, and metal aggregation states are achieved. This approach shows remarkable adjustability and generality, providing sufficient freedom to design catalysts at atomic-scale and explore the unique catalytic properties of SACs. As an example, we show that the prepared Pt 1 /N-C exhibits superior chemoselectivity and regioselectivity in hydrogenation. It only converts terminal alkynes to alkenes while keeping other reducible functional groups such as alkenyl, nitro group, and even internal alkyne intact.

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Section: Introductionmentioning

confidence: 99%

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

et al. 2019

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“…Moreover, CO as a gas byproduct was also detected. Comparing to the literatures, in which the CoAlOx‐600, [20] Ru 3 (CO) 12 /Rh 2 (CO) 4 Cl 2 , [42] Au‐a‐TiO 2 [15] and 0.1Pd/Fe 3 O 4 [16] were used as catalysts, the CoMoC x ‐800 showed the highest selectivity for ethanol. As contrast catalysts, Co‐800 and β‐Mo 2 C‐800 were prepared (Figure S5 and S6) and used to catalyze the CO 2 hydrogenation.…”

Section: Resultsmentioning

confidence: 69%

“…Under the conditions of 200 °C and total pressure of 6 MPa, Au/TiO 2 gave a high ethanol yield of 869.3 mmolg Au −1 h −1 with a high stability [15] . Pd/Fe 3 O 4 single‐atom catalyst was also showed the high space‐time yield (413 mmolg Pd −1 h −1 ) of ethanol at 300 °C and 1 bar [16] . Recently, Huang et al.…”

Section: Introductionmentioning

confidence: 96%

“…[15] Pd/Fe 3 O 4 single-atom catalyst was also showed the high space-time yield (413 mmolg Pd À 1 h À 1 ) of ethanol at 300°C and 1 bar. [16] Recently, Huang et al reported the ordered PdÀ Cu nanoparticles were employed as catalysts for synthesizing ethanol from the CO 2 hydrogenation, and 41.5 mmolg À 1 h À 1 ethanol was yielded when the reaction was carried out at 3.2 MPa and 200°C for 5 h. [17] Due to the higher cost and scarcity of precious metals, it is a better choice to replace precious metal catalysts with cheap and abundant non-noble metal catalysts. It was reported that K/CuÀ Zn catalyst showed a C 2 + OH selectivity of 11.8 % under the reaction conditions of 350°C and 3 MPa.…”

Section: Introductionmentioning

confidence: 99%

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Highly Selective Synthesis of Ethanol via CO₂ Hydrogenation over CoMoC_x Catalysts

et al. 2021

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Hydrogenation of CO 2 to ethanol is one of the promising and emerging routes for the transformation of CO 2 into value-added chemicals. In the present work, series of CoMoCx catalysts were prepared by using ionic liquids as all-in-one precursors and adjusted the proportional and electronic properties of CoMoC x catalysts by modifying carburization temperature, the efficiency of CO 2 to ethanol hydrogenation was optimized. Under the optimal reaction conditions (180°C and 2 MPa), the selectivity of ethanol reached 97.4 %, and the yield of ethanol arrived at 0.528 mmolg cat. À 1 h À 1 . In situ DRIFTS results revealed that a nucleophilic attack on the carbon of CH 3 O* by a formyl to form ethanol.

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“…Furthermore, the interaction between the anchored single metal atoms and support is possible to create a particular architecture for the subsequent CC coupling reaction. Thus, Pd 1 /Fe 3 O 4 SAC shows remarkable catalytic performance for the hydrogenation of CO 2 to ethanol with a selectivity of 97.5% at 300 °C, which is much higher than that of Pd 1 /Al 2 O 3 , Pd 1 /CeO 2 , and Pd 1 /ZrO 2 …”

Section: Applicationsmentioning

confidence: 94%

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

et al. 2019

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metal atoms are highly desirable for supported noble-metal (NM) catalysts. [2] Single-atom catalyst (SAC), defined as a catalyst composing only isolated singleatom active sites on supports, was first introduced by Zhang and co-workers in 2011. [3] Owing to the single-atom feature of active sites, SACs provide great advantages in minimizing the usage of precious metal with a 100% atom-utilization efficiency, which thus result in an improved catalytic reactivity, and have aroused extensive attention in the field of catalysis over the past few years. [4] Meanwhile, since the electronic properties of active sites greatly depend on the size and shape of metal particles, which then governs the performance of a catalyst, [5] downsizing metal nanoparticles (NPs) to single atom with the decreased low coordination and the quantized orbital of active sites, is recognized as the other important factor in tuning the catalytic performance of SACs. [5,6] However, due to the tendency of aggregation of single atoms during preactivation and under reaction procedures, utilization of metal/support interactions to immobilize single atom on supports plays a crucial role on the stability of SACs, and the development of effective synthesis strategies is indispensable to realize the distribution and chemical bonding of active sites on supports for the further applications of SACs.In particular, high density of active sites with well-defined local coordination structure to give appreciable catalytic activity/ selectivity and long-term stability are the ultimate goals in catalysis. [7] Thus, long-standing interest exists in fabricating heterogeneous catalysts that feature atomically dispersed metal atoms as active sites for catalytic processes. Even though, considerable efforts have been devoted to, and many advances have been achieved in supported NM-SACs for various heterogeneous catalytic applications, inclusive of CO oxidation, selective hydrogenation, water-gas shift, CO 2 reduction, electrocatalysis, and etc. [2b,7b,8] The achievements from recent studies have greatly contributed to the fast development of single-atom catalysis and paves the way for the rational design of efficient SACs in much broader catalytic systems.In this review, we will focus on this new kind of material, with great attention on the geometric and electronic structure of the single atom active sites, as well as its stability on supports. The recently developed strategies for synthesizing SACs with high metal loading and precise structure are also Single-atom catalysts (SACs), with atomically distributed active metal sites on supports, serve as a newly advanced material in catalysis, and open broad prospects for a wide variety of catalytic processes owing to their unique catalytic behaviors. To construct SACs with precise structures and high density of accessible single-atom sites, while preventing aggregation to large nanoparticles, various strategies for their chemical synthesis have been recently developed by improving the distribution and chemical bondi...

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Remarkable Carbon Dioxide Hydrogenation to Ethanol on a Palladium/Iron Oxide Single‐Atom Catalyst

Cited by 105 publications

References 25 publications

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

Highly Selective Synthesis of Ethanol via CO₂ Hydrogenation over CoMoC_x Catalysts

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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Remarkable Carbon Dioxide Hydrogenation to Ethanol on a Palladium/Iron Oxide Single‐Atom Catalyst

Cited by 105 publications

References 25 publications

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation

Highly Selective Synthesis of Ethanol via CO2 Hydrogenation over CoMoCx Catalysts

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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Highly Selective Synthesis of Ethanol via CO₂ Hydrogenation over CoMoC_x Catalysts