Sacrificial Adsorbate Strategy Achieved Strong Metal–Support Interaction of Stable Cu Nanocatalysts

Wang, Xiuyun; Liu, Yi; Peng, Xuanbei; Lin, Bingyu; Cao, Yanning; Jiang, Lilong

doi:10.1021/acsaem.8b00049

Cited by 29 publications

(30 citation statements)

References 27 publications

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Section: Water-gas Shift Reaction (Wgsr)mentioning

confidence: 99%

“…Finally, the WGSR activity and the sintering resistance of the CuO x /CeO 2 catalysts can be further enhanced by improving the metal-support interactions through appropriate pretreatment protocols [290,296]. As for example, the treatment of CuO x /CeO 2 catalyst in a gas mixture of 20CO 2 /2H 2 led to highly active catalysts, due to the electron enrichment of copper atoms via electronic metal-support interactions [290]. Moreover, ceria pretreatment in different atmosphere (air, vacuum or H 2 ) affected the WGSR performance of CuO x /CeO 2 catalysts, with the H 2 -pretreated samples exhibiting the highest conversion performance, due to the strong synergism between the two oxide phases, the small CuO x particle size, and the high concentration in oxygen vacancies [296].…”

Section: Water-gas Shift Reaction (Wgsr)mentioning

confidence: 99%

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Recent Advances on the Rational Design of Non-Precious Metal Oxide Catalysts Exemplified by CuOx/CeO2 Binary System: Implications of Size, Shape and Electronic Effects on Intrinsic Reactivity and Metal-Support Interactions

Konsolakis

Lykaki

2020

Catalysts

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Catalysis is an indispensable part of our society, massively involved in numerous energy and environmental applications. Although, noble metals (NMs)-based catalysts are routinely employed in catalysis, their limited resources and high cost hinder the widespread practical application. In this regard, the development of NMs-free metal oxides (MOs) with improved catalytic activity, selectivity and durability is currently one of the main research pillars in the area of heterogeneous catalysis. The present review, involving our recent efforts in the field, aims to provide the latest advances—mainly in the last 10 years—on the rational design of MOs, i.e., the general optimization framework followed to fine-tune non-precious metal oxide sites and their surrounding environment by means of appropriate synthetic and promotional/modification routes, exemplified by CuOx/CeO2 binary system. The fine-tuning of size, shape and electronic/chemical state (e.g., through advanced synthetic routes, special pretreatment protocols, alkali promotion, chemical/structural modification by reduced graphene oxide (rGO)) can exert a profound influence not only to the reactivity of metal sites in its own right, but also to metal-support interfacial activity, offering highly active and stable materials for real-life energy and environmental applications. The main implications of size-, shape- and electronic/chemical-adjustment on the catalytic performance of CuOx/CeO2 binary system during some of the most relevant applications in heterogeneous catalysis, such as CO oxidation, N2O decomposition, preferential oxidation of CO (CO-PROX), water gas shift reaction (WGSR), and CO2 hydrogenation to value-added products, are thoroughly discussed. It is clearly revealed that the rational design and tailoring of NMs-free metal oxides can lead to extremely active composites, with comparable or even superior reactivity than that of NMs-based catalysts. The obtained conclusions could provide rationales and design principles towards the development of cost-effective, highly active NMs-free MOs, paving also the way for the decrease of noble metals content in NMs-based catalysts.

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Section: Water-gas Shift Reaction (Wgsr)mentioning

confidence: 99%

Section: Water-gas Shift Reaction (Wgsr)mentioning

confidence: 99%

Recent Advances on the Rational Design of Non-Precious Metal Oxide Catalysts Exemplified by CuOx/CeO2 Binary System: Implications of Size, Shape and Electronic Effects on Intrinsic Reactivity and Metal-Support Interactions

Konsolakis

Lykaki

2020

Catalysts

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“…The catalytic performances were largely determined by the structure of the catalysts. CeO 2 has been well known as suitable support for Cu catalysts, since the strong interaction between CuO and CeO 2 could achieve homogeneous Cu dispersion 39–41 . For the fresh CeO 2 /Cu catalyst, such interaction could be confirmed by temperature-programmed reduction by H 2 (H 2 -TPR), with the fact that reducibility for CuO was enhanced after CeO 2 addition (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

Construction of stabilized bulk-nano interfaces for highly promoted inverse CeO2/Cu catalyst

et al. 2019

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As the water-gas shift (WGS) reaction serves as a crucial industrial process, strategies for developing robust WGS catalysts are highly desiderated. Here we report the construction of stabilized bulk-nano interfaces to fabricate highly efficient copper-ceria catalyst for the WGS reaction. With an in-situ structural transformation, small CeO 2 nanoparticles (2–3 nm) are stabilized on bulk Cu to form abundant CeO 2 -Cu interfaces, which maintain well-dispersed under reaction conditions. This inverse CeO 2 /Cu catalyst shows excellent WGS performances, of which the activity is 5 times higher than other reported Cu catalysts. Long-term stability is also very solid under harsh conditions. Mechanistic study illustrates that for the inverse CeO 2 /Cu catalyst, superb capability of H 2 O dissociation and CO oxidation facilitates WGS process via the combination of associative and redox mechanisms. This work paves a way to fabricate robust catalysts by combining the advantages of bulk and nano-sized catalysts. Catalysts with such inverse configurations show great potential in practical WGS applications.

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“…Interestingly, a similar 20 % CO 2 /2 % H 2 pre-treatment was used by Wang et al 146 for Cu/CeO 2 catalysts for WGS. However, they mainly used the adsorbate-mediated SMSI strategy to prevent sintering of the Cu NPs and the effect on intrinsic activity was modest, although also some charge transfer from the support to the Cu NPs was inferred from XPS.…”

Section: Treatmentsmentioning

confidence: 98%

Niobia-Supported Metal Catalysts for Synthesis Gas Conversion

Carlos¹

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ZnO 53 (Figure 2.2a). Charge transfer occurred to a different extent from various supports to Au NPs of 2-4 nm size and correlated inversely with the electron donation capacity of the support. Hydride transfer from the alcohol to Au was argued to be the rate determining in this case and would account for lower activity of more negatively charged Au NP.In photocatalysis, a semiconductor support's bandgap of appropriate size and position facilitates light absorption and transfer of the generated charge to or from metal NPs performing catalysis. The activity of Rh/TiO 2 in steam reforming of methane was already 13 times higher than that of Rh/SiO 2 and Rh/ZrO 2 in dark conditions and the activity of Rh/TiO 2 was enhanced further nearly 3 times when exposed to light (Figure 2.2b) 54 . However, the opposite has been observed as well; Pt/Ta 2 O 5 was more active than Pt/TiO 2 for 2-propanol oxidation to acetone, because hot electrons generated on the Pt NPs were not transferred to the support and hence drove the catalysis on the Pt NPs 55 . XPS analysis indicated that the Pt phase was more negatively charged on Ta 2 O 5 than on other supports. Similar considerations also apply to electrocatalysis. The activity of Pt NPs for electrocatalytic reduction of oxygen was significantly enhanced when a mixture of boron carbide and graphite was used as support instead of pure graphite and it was argued that this was solely an electronic effect 56 .Perovskites are a class of metal oxides with the general formula ABO 3 in which a large variety of metal ions can be incorporated in the A-and B-sites of their crystal structures. Some of these ions can be extracted from the perovskite lattice upon reduction to form nanoparticles. This approach has received great attention for electrochemical systems 57 mainly due to the beneficial conductive properties of perovskites for electrodes. However, this approach has been employed to a lesser extent for catalysis due to the resulting low metal loading and limitation to easy-to-reduce metal ions, such as noble metals. Recently, non-stoichiometric perovskites with A-site deficiency extended the range of metal ions capable of forming nanoparticles to more difficult to reduce metal ions (e.g., Ti 4+ , Fe 2+/3+ , Mn 2+/3+ , Ni 2+ ) 58,59 . The resulting nanoparticles resisted the harsh conditions of methane reforming due to partial embedding in the support, avoiding the formation of carbon fibres at the periphery of the nanoparticles. Formation of alloyed nanoparticles is also possible by use of this strategy. Alloyed Pt 3 Ni nanoparticles obtained from La 0.9 Mn 0.9 Pt 0.075 Ni 0.025 O x perovskite have shown high activity for the electrocatalytic oxygen reduction reaction 60 . The strong connection with the conductive perovskite, uniform NP distribution and small NP size for the obtained particles were beneficial to the measured activity.The disadvantage, however, of using perovskites to form nanoparticles in catalysis is the low specific surface area of these compounds, due to the high tempe...

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Sacrificial Adsorbate Strategy Achieved Strong Metal–Support Interaction of Stable Cu Nanocatalysts

Cited by 29 publications

References 27 publications

Recent Advances on the Rational Design of Non-Precious Metal Oxide Catalysts Exemplified by CuOx/CeO2 Binary System: Implications of Size, Shape and Electronic Effects on Intrinsic Reactivity and Metal-Support Interactions

Recent Advances on the Rational Design of Non-Precious Metal Oxide Catalysts Exemplified by CuOx/CeO2 Binary System: Implications of Size, Shape and Electronic Effects on Intrinsic Reactivity and Metal-Support Interactions

Construction of stabilized bulk-nano interfaces for highly promoted inverse CeO2/Cu catalyst

Niobia-Supported Metal Catalysts for Synthesis Gas Conversion

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