Recent Advances in Direct Synthesis of Value‐Added Aromatic Chemicals from Syngas by Cascade Reactions over Bifunctional Catalysts

Kasipandi, Saravanan; Bae, Jong Wook

doi:10.1002/adma.201803390

Cited by 112 publications

(78 citation statements)

References 98 publications

(219 reference statements)

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“…To the best of our knowledge, comprehensive review paper on promoted catalytic conversion of CO x in confined spaces is still lacking, although many review articles have been published on the preparation and applications of confinement catalysts for variety of transformations, [8,[13][14][15][16][17][18][19][20][21] and also on the designing of various catalysts for selective conversion of CO x into fuels and high-value chemicals. [2,7,[9][10][11]22,23] The present review contributes to present the advances and prospect of the catalytic conversion of CO x into fuels and value-added chemicals in confined spaces. Especially, the specific promoting mechanism for selective conversion of CO x in confined spaces by confinement effect has been highlighted.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7] The selectively catalytic transformation of carbon oxide (CO x , including CO 2 and CO) into fuels and highvalue chemicals has attracted much attention in recent years. [3][4][5][6][7][8][9][10][11][12] Recently, although extensive studies have been devoted to catalytic transformation of CO x , the state-of-the-art development of catalysts for thus transformations of CO x to fuels and value-added chemicals for industrial applications is far from satisfactory. The further improvement in catalytic activity, selectivity, and stability, especially selectivity, is highly desirable.…”

Section: Introductionmentioning

confidence: 99%

“…[8,[14][15][16][17][18][19][20][21][22][23] Currently, confinement catalysis has been extensively applied to the catalytic conversion of CO x regarding of improvement in catalytic activity, selectivity, and stability (Scheme 1). [9][10][11][12][24][25][26] Especially, the confined spaces of catalysts efficiently improve the catalytic selectivity for CO x conversion into fuels and high-value chemicals through the modulation of active sites and also the products self-regulation by the confined shell, which represents a promising direction for the selective conversion and utilization of carbon oxides.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Conversion of Carbon Oxides in Confined Spaces: Status and Prospects

Zhao

2020

ChemCatChem

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Owing to the depletion of fossil reserves and the global warming by released greenhouse gas from the consumption of fossil resources, the catalytic conversion of carbon oxide (COx, including CO2 and CO) into fuels and high‐value chemicals has attracted tremendous interest in the field of catalysis. Developing high‐performance and practical catalysts with high activity, selectivity, and stability is of great importance but remains a huge challenge. A variety of new strategies were developed to take advantage of confinement effect to address the challenges that are relevant to the highly‐efficient transformation and utilization of COx by performing catalytic reactions in a confined space. The status on this issue can be divided into three aspects: improvement in catalytic activity, increase in catalytic selectivity and enhancement in catalytic stability. In this review, the progress in the field of promoted catalytic conversion of COx in confined spaces will be presented and discussed. Especially, the specific promoting mechanism in terms of the confinement effect for COx‐related transformations in confined spaces and the relationship between the impact of the confined space on the catalytic activity, selectivity, and stability regarding of COx conversions are highlighted. Finally, the future prospects on the opportunities and challenges of catalytic conversion of COx in confined spaces are outlined.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalytic Conversion of Carbon Oxides in Confined Spaces: Status and Prospects

Zhao

2020

ChemCatChem

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“…The conversion of syngas is a promising route to obtain high value chemicals from non-petroleum resources due to the wide variety of sources of syngas [2]. Considerable efforts have been made in the conversion of syngas to a range of hydrocarbons such as lower olefins, gasoline, diesel, and aromatics [3][4][5][6]. Syngas to hydrocarbons reaction was firstly achieved in 1923, known as the Fischer-Tropsch synthesis (FTS).…”

Section: Introductionmentioning

confidence: 99%

The Effects of the Crystalline Phase of Zirconia on C–O Activation and C–C Coupling in Converting Syngas into Aromatics

et al. 2020

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Zirconia has recently been used as an efficient catalyst in the conversion of syngas. The crystalline phases of ZrO2 in ZrO2/HZSM-5 bi-functional catalysts have important effects on C–O activation and C–C coupling in converting syngas into aromatics and been investigated in this work. Monoclinic ZrO2 (m-ZrO2) and tetragonal ZrO2 (t-ZrO2) were synthesized by hydrothermal and chemical precipitation methods, respectively. The results of in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTs) revealed that there were more active hydroxyl groups existing on the surface of m-ZrO2, and CO temperature programmed desorption (CO-TPD) results indicated that the CO adsorption capacity of m-ZrO2 was higher than that of t-ZrO2, which can facilitate the C–O activation of m-ZrO2 for syngas conversion compared to that of t-ZrO2. And the CO conversion on the m-ZrO2 catalyst was about 50% more than that on the t-ZrO2 catalyst. 31P and 13C magic angle spinning nuclear magnetic resonance (MAS NMR) analysis revealed a higher acid and base density of m-ZrO2 than that of t-ZrO2, which enhanced the C–C coupling. The selectivity to CH4 on the m-ZrO2 catalyst was about 1/5 of that on the t-ZrO2 catalyst in syngas conversion. The selectivity to C2+ hydrocarbons over m-ZrO2 or t-ZrO2 as well as the proximity of the ZrO2 sample and HZSM-5 greatly affected the further aromatization in converting syngas into aromatics.

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Manganese Oxide Modified Nickel Catalysts for Photothermal CO Hydrogenation to Light Olefins

Wang

Zhao

Liu

et al. 2019

Advanced Energy Materials

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from FTS reactions include light olefins, [2] higher hydrocarbons, methanol, [3] ethylene glycol, [4] dimethyl ether, [5] and aromatics. [6] Among all the products of FTS, light olefins (ethene, propene, and butene) are perhaps the most valuable and widely used in the production of fine chemicals, plastics, coatings, and cosmetics. [7] In FTS, the most commonly used catalysts are group VIIIB transition metals, especially iron, cobalt, nickel, and ruthenium. These catalysts differ in their CO hydrogenation activity and product selectivity, with several of these metals often being used together (in alloy form) to achieve a high CO conversion or to enhance the selectivity toward a specific product or group of products. Iron-based catalysts show good initial selectivity toward light olefins during FTS. [8] During FTS, metallic iron is gradually transformed to iron carbide during reaction (which is considered the true active phase of iron-based FTS catalysts). Iron carbide has a relatively mild hydrogenation ability and the ability to promote CC coupling reactions. However, FTS over iron-based catalysts typically requires temperatures above 300 °C, which can lead to coke formation and sintering of active sites, leading to catalyst deactivation. Co-based catalysts are suitable for CO hydrogenation to Ni-based catalysts are traditionally considered unsuitable for the Fischer-Tropsch syntheses of olefins, due to the very strong hydrogenation ability of metallic Ni. Herein, this paradigm is challenged. A series of MnO supports nickel catalysts (denoted herein as Ni-x) are fabricated by H 2 reduction of a nickel-manganese mixed metal oxide at temperatures (x) ranging from 250 to 600 °C. The Ni-500 catalyst displays unprecedented performance for photothermal CO hydrogenation to olefins, with an olefin selectivity of 33.0% under ultraviolet-visible irradiation. High-resolution transmission electron microscopy, X-ray absorption spectroscopy (XAS), and X-ray diffraction analyses reveal that the Ni-x catalysts contain metallic Ni nanoparticles supported by MnO. X-ray photoelectron spectroscopy and XAS establish that electron transfer from MnO to the Ni 0 nanoparticles is responsible for modifying the electronic structure of nickel (creating Ni δ− states), thereby shifting the CO hydrogenation selectivity toward light olefins. Further, density functional theory calculations show that this electron transfer lowers the adsorption energies of olefins on Ni surfaces, thus minimizing the undesirable deep hydrogenation reactions to higher alkanes. This study conclusively demonstrates that MnO-modified Ni-based catalyst systems can be highly selective for CO hydrogenation to light olefins.

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Recent Advances in Direct Synthesis of Value‐Added Aromatic Chemicals from Syngas by Cascade Reactions over Bifunctional Catalysts

Cited by 112 publications

References 98 publications

Catalytic Conversion of Carbon Oxides in Confined Spaces: Status and Prospects

Catalytic Conversion of Carbon Oxides in Confined Spaces: Status and Prospects

The Effects of the Crystalline Phase of Zirconia on C–O Activation and C–C Coupling in Converting Syngas into Aromatics

Manganese Oxide Modified Nickel Catalysts for Photothermal CO Hydrogenation to Light Olefins

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