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Journal ArticleDOI

Uncoupling the size and support effects of Ni catalysts for dry reforming of methane

01 Apr 2017-Applied Catalysis B-environmental (Elsevier)-Vol. 203, pp 625-632
TL;DR: In this paper, a unique Ni-based catalyst in which the Ni nanoparticle size and support can be varied independently was devised for dry reforming of methane (DRM) at 800°C without a significant change in the Ni size, and overlayers of various metal oxides, including SiO 2, Al 2 O 3, MgO, ZrO 2, TiO 2.
Abstract: The dry reforming of methane (DRM; CH 4 + CO 2 ↔ 2H 2 + 2CO) can be a good way to utilize greenhouse gases for the production of valuable syn-gas. Ni-based catalysts have been used for this reaction; however, the Ni size effect and support effect were highly coupled and therefore could not be observed separately. Here, a unique catalyst in which the Ni nanoparticle size and support can be varied independently was devised. Highly uniform Ni nanoparticles with sizes of 2.6, 5.2, 9.0, and 17.3 nm were tested for DRM at 800 °C without a significant change in the Ni size, and overlayers of various metal oxides, including SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , were tested with the 5.2 nm of Ni nanoparticles. The dependence of the CH 4 or CO 2 turnover frequency on the Ni size and support was evaluated separately. The 2.6 nm Ni nanoparticles showed 4.1 times higher methane turnover frequency than those with a size of 17.3 nm. When various metal oxide overlayers were tested with the same 5.2 nm Ni, Al 2 O 3 exhibited 4.3 times higher methane turnover frequency than SiO 2 . The independent observation of the effects of the Ni nanoparticle size and support will provide valuable guidelines for designing effective methane dry reforming catalysts.
Citations
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Journal ArticleDOI
TL;DR: This review provides an in-depth assessment of core-shell structured catalysts for the thermocatalysis, photocatalytic, and electrocatalytic conversion of CO2 into synthesis gas and valuable hydrocarbons.
Abstract: Catalytic conversion of CO2 to produce fuels and chemicals is attractive in prospect because it provides an alternative to fossil feedstocks and the benefit of converting and cycling the greenhouse gas CO2 on a large scale. In today's technology, CO2 is converted into hydrocarbon fuels in Fischer-Tropsch synthesis via the water gas shift reaction, but processes for direct conversion of CO2 to fuels and chemicals such as methane, methanol, and C2+ hydrocarbons or syngas are still far from large-scale applications because of processing challenges that may be best addressed by the discovery of improved catalysts-those with enhanced activity, selectivity, and stability. Core-shell structured catalysts are a relatively new class of nanomaterials that allow a controlled integration of the functions of complementary materials with optimised compositions and morphologies. For CO2 conversion, core-shell catalysts can provide distinctive advantages by addressing challenges such as catalyst sintering and activity loss in CO2 reforming processes, insufficient product selectivity in thermocatalytic CO2 hydrogenation, and low efficiency and selectivity in photocatalytic and electrocatalytic CO2 hydrogenation. In the preceding decade, substantial progress has been made in the synthesis, characterization, and evaluation of core-shell catalysts for such potential applications. Nonetheless, challenges remain in the discovery of inexpensive, robust, regenerable catalysts in this class. This review provides an in-depth assessment of these materials for the thermocatalytic, photocatalytic, and electrocatalytic conversion of CO2 into synthesis gas and valuable hydrocarbons.

368 citations

Journal ArticleDOI
TL;DR: In this paper, a review provides a contemporary assessment of progresses recorded on synergistic interplay among catalyst components (active metals, support, promoters and binders) during dry reforming using state-of-the-art experimental and theoretical techniques.
Abstract: The abrupt and massive deactivation of methane dry reforming catalysts especially Ni-based is still a monumental impediment towards its industrialization and commercialization for production of value-added syngas via Fischer-Tropsch process. The need for further and more critical understanding of inherent and tailored interactions of catalyst components for performance and stability enhancement during reforming reaction cannot be over-emphasized. This review provides a contemporary assessment of progresses recorded on synergistic interplay among catalyst components (active metals, support, promoters and binders) during dry reforming using state-of-the-art experimental and theoretical techniques. Advancements achieved during interplay leading to improvements in properties of existing catalysts and discovery of novel ones were stated and expatiated. Reaction pathways, catalytic activities, selection of appropriate synthesis route and metal/support deactivation via sintering or carbon deposition have over time been successfully studied and explained using information from these crucial component interactions. This perspective describes the roles of these interactions and their applications towards development of robust catalysts configurations for successful industrial applications.

367 citations

Journal ArticleDOI
TL;DR: In this paper, a sandwiched core-shell structured Ni-SiO2@CeO2 catalyst, with nickel nanoparticles encapsulated between silica and ceria, was developed and applied for dry reforming of biogas under low temperature conditions to test its coke inhibition properties.
Abstract: In this paper, a novel sandwiched core–shell structured Ni-SiO2@CeO2 catalyst, with nickel nanoparticles encapsulated between silica and ceria, was developed and applied for dry reforming of biogas (CH4 / CO2 = 3/2) under low temperature conditions to test its coke inhibition properties. Ni-phyllosilicate was used as the Ni precursor in order to produce highly dispersed Ni nanoparticles on SiO2. Cerium oxide was chosen as the shell due to its high redox potential and oxygen storage capacity, that can reduce coke formation under severe dry reforming conditions. The core shell Ni-SiO2@CeO2 catalyst showed excellent coke inhibition property under low temperature (600 °C) reforming of biogas, with no coke detected after a 72 h catalytic run. Under the same conditions, Ni-SiO2 catalyst deactivated within 22 h due to heavy coke formation and reactor blockage, while Ni-CeO2 catalyst showed very low activity. The higher activity of the core–shell catalyst is attributed to its higher Ni dispersion and reducibility. TEM and XRD results show that the core–shell catalyst shows higher resistance to Ni particle sintering and agglomeration during the reaction than the Ni-SiO2 and Ni-CeO2 catalysts. In-situ DRIFTS on the Ni-SiO2@CeO2 catalyst indicate a change in the reaction mechanism from a mono-functional pathway on the Ni-SiO2 catalysts to a bi-functional route on the Ni-SiO2@CeO2 catalyst with active participation of oxygen species from CeO2 in carbon gasification. The confinement effect of the sandwich structure and the bifunctional mechanism of dry reforming are the primary reasons for the excellent coke resistance of the Ni-SiO2@CeO2 catalyst.

326 citations


Cites methods from "Uncoupling the size and support eff..."

  • ...Table 3 shows a comparison of the coke inhibition property of the Ni-SiO2@CeO2 catalyst with some of the recent Ni-based catalysts developed for carbon free dry reforming reaction [5, 20, 23, 55-67]....

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Journal ArticleDOI
TL;DR: Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH4, thus avoiding methane deep decomposition into carbon and offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.
Abstract: Dry reforming of methane (DRM) is an attractive route to utilize CO2 as a chemical feedstock with which to convert CH4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH4, thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

320 citations

Journal ArticleDOI
TL;DR: In this article, a review deals with the currently existing alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase process stability, and then delves with the fundamental phenomena occurring during this catalysts deactivation.
Abstract: Undoubtedly, hydrogen (H2) is a clean feedstock and energy carrier whose sustainable production should be anticipated. The pyrolysis of biomass or waste plastics and the subsequent reforming over base (transition) or noble metals supported catalysts allows reaching elevated H2 yields. However, the catalyst used in the reforming step undergoes a rapid and severe deactivation by means of a series of physicochemical phenomena, including metal sintering, metallic phase oxidation, thermal degradation of the support and, more notoriously, coke deposition. This review deals with the currently existing alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase process stability, and then delves with the fundamental phenomena occurring during this catalyst deactivation. An emphasis is placed on coke deposition and its influence on deactivation, which depends on its location, chemical nature, morphology, precursors or formation mechanism, among others. We also discuss the challenges for increasing the value of the carbon materials formed and therefore, enhance process viability.

248 citations

References
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Journal ArticleDOI
TL;DR: In this article, a system of chemical reactions has been developed which permits the controlled growth of spherical silica particles of uniform size by means of hydrolysis of alkyl silicates and subsequent condensation of silicic acid in alcoholic solutions.

12,884 citations

Journal ArticleDOI
TL;DR: Hydrogen Production by Water−Gas Shift Reaction 4056 4.1.
Abstract: 1.0. Introduction 4044 2.0. Biomass Chemistry and Growth Rates 4047 2.1. Lignocellulose and Starch-Based Plants 4047 2.2. Triglyceride-Producing Plants 4049 2.3. Algae 4050 2.4. Terpenes and Rubber-Producing Plants 4052 3.0. Biomass Gasification 4052 3.1. Gasification Chemistry 4052 3.2. Gasification Reactors 4054 3.3. Supercritical Gasification 4054 3.4. Solar Gasification 4055 3.5. Gas Conditioning 4055 4.0. Syn-Gas Utilization 4056 4.1. Hydrogen Production by Water−Gas Shift Reaction 4056

7,067 citations

Journal ArticleDOI
TL;DR: In this article, the Fischer-Tropsch (FT) reaction is used to produce purified syngas and its composition should match the overall usage ratio of the FT reactions, which depends on the product selectivity.

1,779 citations

Journal ArticleDOI
TL;DR: Dry (CO2) reforming of methane literature for catalysts based on Rh, Ru, Pt, and Pd metals is reviewed, including the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.
Abstract: Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.

1,472 citations