Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity

Deelen, Tom W. van; Mejía, Carlos Hernández; Jong, Krijn P. de

doi:10.1038/s41929-019-0364-x

Cited by 1,560 publications

(1,127 citation statements)

References 151 publications

(168 reference statements)

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“…In view of the above, very recently, the modulation of metal-support interactions as a tool to enhance the catalytic performance was thoroughly reviewed, disclosing that up to fifteen-fold productivity enhancement can be achieved in reactions related to C1 chemistry by controlling metal-support interactions [61]. However, it is well established today-thanks to the rapid development of sophisticated characterization techniques-that various interrelated factors, such as the composition, the size, the shape, and the electronic state of MOs different counterparts can exert a profound influence on the local surface chemistry and metal-support interactions, and in turn, on the catalytic activity of these multifunctional materials [6,48,51,52,[62][63][64][65][66][67][68][69][70][71][72][73][74].…”

Section: Introductionmentioning

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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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: Introductionmentioning

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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“…By contrast, precious metals are always much easier to reduce. In the case of single-atom, precious-metal catalysts, the support almost always plays a key role [39,40].…”

Section: Discussionmentioning

confidence: 99%

Atomic Layer Deposition for Preparing Isolated Co Sites on SiO2 for Ethane Dehydrogenation Catalysis

Huang

Cheng

et al. 2020

Nanomaterials

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Unlike Co clusters, isolated Co atoms have been shown to be selective for catalytic dehydrogenation of ethane to ethylene; however, preparation of isolated Co sites requires special preparation procedures. Here, we demonstrate that Atomic Layer Deposition (ALD) of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(III) (Co(TMHD)3) on silica and other supports is effective in producing these isolated species. Silica-supported catalysts prepared with one ALD cycle showed ethylene selectivities greater than 96% at 923 K and were stable when CO2 was co-fed with the ethane. Co catalysts prepared by impregnation formed clusters that were significantly less active, selective, and stable. Rates and selectivities also decreased for catalysts with multiple ALD cycles. Isolated Co catalysts prepared on Al2O3 and MgAl2O4 showed reasonable selectivity for ethane dehydrogenation but were not as effective as their silica counterpart.

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“…During the loading of NCs/BNCs, the reaction was carriedi nm ethanol under an argon blanket at 0 8Ct oa ssist the reduction step of metal ions with as toichiometrica mount of NaBH 4 for controlled nucleation under the provided conditions, thereby generating the M-MO-G-SH ('M' stands for metal) nanointerfaces across the whole hybrid material. [35] Structural and compositional characterization After the functionalization, the change in the structural network was probed from the Db and (sp 2 C-C E 2g symmetric mode) and Gb and (defects and sp 3 C-C ,A 1g symmetric mode) around 1365-1620 cm À1 in at ypical Ramans pectrum( Figure S1 ai n the Supporting Information). In fact, the Dband is highly sensitive to perturbation and structural defects, whicha re usually generated after chemical functionalizationa nd doping and thereby the relative intensity (I D /I G )c an be used to examine the extent of defective sites andt he change in GO framework.…”

Section: Functionalization and Synthesismentioning

confidence: 99%

Controlled Assembly of Cu/Co‐Oxide Beaded Nanoclusters on Thiolated Graphene Oxide Nanosheets for High‐Performance Oxygen Evolution Catalysts

Munir

Haq

Hussain

et al. 2020

Chemistry A European J

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The use of water splitting modules is highly desired for the sustainable production of H2 as a future energy carrier. However, the sluggish kinetics and demand of high anodic potential are the bottlenecks for half‐the cell oxygen evolution reaction (OER), which severely hamper the overall conversion efficiency. Although transition metal oxides based electrocatalysts have been envisioned as cost‐effective and potential contenders for this quest, nevertheless, their low conductivity, instability, and limited number of active sites are among the common impediments that need to be addressed to eventually enhance their inherent catalytic potential for enhanced OER activity. Herein, the controlled assembly of transition metal oxides, that is, Cu@CuOx nanoclusters (NCs, ≈2 nm) and Co@CoOx beaded nanoclusters (BNCs, ≈2 nm), on thiol‐functionalized graphene oxide (G‐SH) nanosheets is reported to form novel and highly efficient electrocatalysts for OER. The thiol (‐SH) functionality was incorporated by selective epoxidation on the surface of graphene oxide (GO) to achieve chemically exfoliated nanosheets to enhance its conductivity and trapping ability for metal oxides in nanoscale dimensions (≈2 nm). During the electrocatalytic reaction, overpotentials of 290 mV and 310 mV are required to achieve a current density of 10 mA cm−2 for BNCs and NCs, respectively, and the catalysts exhibit tremendous long‐term stability (≈50 h) in purified alkaline medium (1 m KOH) with no dissolution in the electrolyte. Moreover, the smaller Tafel slopes (54 mV/dec for BNCs and 66 mV/dec for NCs), and a Faradic efficiency of approximately 96 % indicate not only the selectivity but also the tailored heterogeneous electrons transfer (HET) rate, which is required for fast electrode kinetics. It is anticipated that such ultrasmall metal oxide nanoclusters and their controlled assembly on a conducting surface (G‐SH) may offer high electrochemical accessibility and a plethora of active sites owing to the drastic decrease in dimensions and thus can synergistically ameliorate the challenging OER process.

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Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity

Cited by 1,560 publications

References 151 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

Atomic Layer Deposition for Preparing Isolated Co Sites on SiO2 for Ethane Dehydrogenation Catalysis

Controlled Assembly of Cu/Co‐Oxide Beaded Nanoclusters on Thiolated Graphene Oxide Nanosheets for High‐Performance Oxygen Evolution Catalysts

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