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1.
Small ; 20(3): e2305517, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37670220

RESUMO

A novel and sustainable carbon-based material, referred to as hollow porous carbon particles encapsulating multi-wall carbon nanotubes (MWCNTs) (CNTs@HPC), is synthesized for use in supercapacitors. The synthesis process involves utilizing LTA zeolite as a rigid template and dopamine hydrochloride (DA) as the carbon source, along with catalytic decomposition of methane (CDM) to simultaneously produce MWCNTs and COx -free H2 . The findings reveal a distinctive hierarchical porous structure, comprising macropores, mesopores, and micropores, resulting in a total specific surface area (SSA) of 913 m2  g-1 . The optimal CNTs@HPC demonstrates a specific capacitance of 306 F g-1 at a current density of 1 A g-1 . Moreover, this material demonstrates an electric double-layer capacitor (EDLC) that surpasses conventional capabilities by exhibiting additional pseudocapacitance characteristics. These properties are attributed to redox reactions facilitated by the increased charge density resulting from the attraction of ions to nickel oxides, which is made possible by the material's enhanced hydrophilicity. The heightened hydrophilicity can be attributed to the presence of residual silicon-aluminum elements in CNTs@HPC, a direct outcome of the unique synthesis approach involving nickel phyllosilicate in CDM. As a result of this synthesis strategy, the material possesses excellent conductivity, enabling rapid transportation of electrolyte ions and delivering outstanding capacitive performance.

2.
Int J Mol Sci ; 25(12)2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38928465

RESUMO

In environmental chemistry, photocatalysts for eliminating organic contaminants in water have gained significant interest. Our study introduces a unique heterostructure combining MIL-101(Cr) and bismuth oxyiodide (Bi5O7I). We evaluated this nanostructure's efficiency in adsorbing and degrading tetracycline (TC) under visible light. The Bi5O7I@MIL-101(Cr) composite, with a surface area of 637 m2/g, prevents self-aggregation seen in its components, enhancing visible light absorption. Its photocatalytic efficiency surpassed Bi5O7I and MIL-101(Cr) by 33.4 and 9.2 times, respectively. Comprehensive analyses, including scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirmed the successful formation of the heterostructure with defined morphological characteristics. BET analysis demonstrated its high surface area, while X-ray diffraction (XRD) confirmed its crystallinity. Electron spin resonance (ESR) tests showed significant generation of reactive oxygen species (ROS) like h+ and·â€¢O2- under light, crucial for TC degradation. The material maintained exceptional durability over five cycles. Density functional theory (DFT) simulations and empirical investigations revealed a type I heterojunction between Bi5O7I and MIL-101(Cr), facilitating efficient electron-hole pair separation. This study underscores the superior photocatalytic activity and stability of Bi5O7I@MIL-101(Cr), offering insights into designing innovative photocatalysts for water purification.


Assuntos
Bismuto , Estruturas Metalorgânicas , Tetraciclina , Estruturas Metalorgânicas/química , Bismuto/química , Catálise , Tetraciclina/química , Luz , Poluentes Químicos da Água/química , Purificação da Água/métodos , Espécies Reativas de Oxigênio/química , Adsorção , Processos Fotoquímicos
3.
Small ; 19(26): e2207272, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36942900

RESUMO

Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide-supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. The results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.

4.
Small ; 19(39): e2301121, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37271929

RESUMO

Optimizing catalysts for competitive photocatalytic reactions demand individually tailored band structure as well as intertwined interactions of light absorption, reaction activity, mass, and charge transport.  Here, a nanoparticulate host-guest structure is rationally designed that can exclusively fulfil and ideally control the aforestated uncompromising requisites for catalytic reactions. The all-inclusive model catalyst consists of porous Co3 O4 host and Znx Cd1- x S guest with controllable physicochemical properties enabled by self-assembled hybrid structure and continuously amenable band gap. The effective porous topology nanoassembly, both at the exterior and the interior pores of a porous metal-organic framework (MOF), maximizes spatially immobilized semiconductor nanoparticles toward high utilization of particulate heterojunctions for vital charge and reactant transfer. In conjunction, the zinc constituent band engineering is found to regulate the light/molecules absorption, band structure, and specific reaction intermediates energy to attain high photocatalytic CO2 reduction selectivity. The optimal catalyst exhibits a H2 -generation rate up to 6720 µmol g-1 h-1 and a CO production rate of 19.3 µmol g-1 h-1 . These findings provide insight into the design of discrete host-guest MOF-semiconductor hybrid system with readily modulated band structures and well-constructed heterojunctions for selective solar-to-chemical conversion.

5.
Molecules ; 28(5)2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36903274

RESUMO

Novel polymers applied in economic membrane technologies are a perennial hot topic in the fields of natural gas purification and O2 enrichment. Herein, novel hypercrosslinked polymers (HCPs) incorporating 6FDA-based polyimide (PI) MMMs were prepared via a casting method for enhancing transport of different gases (CO2, CH4, O2, and N2). Intact HCPs/PI MMMs could be obtained due to good compatibility between the HCPs and PI. Pure gas permeation experiments showed that compared with pure PI film, the addition of HCPs effectively promotes gas transport, increases gas permeability, and maintains ideal selectivity. The permeabilities of HCPs/PI MMMs toward CO2 and O2 were as high as 105.85 Barrer and 24.03 Barrer, respectively, and the ideal selectivities of CO2/CH4 and O2/N2 were 15.67 and 3.00, respectively. Molecular simulations further verified that adding HCPs was beneficial to gas transport. Thus, HCPs have potential utility in fabrication of MMMs for facilitating gas transport in the fields of natural gas purification and O2 enrichment.

6.
Angew Chem Int Ed Engl ; 62(10): e202211174, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36562773

RESUMO

Electrochemically reducing CO2 to valuable fuels or feedstocks is recognized as a promising strategy to simultaneously tackle the crises of fossil fuel shortage and carbon emission. Sn-based catalysts have been widely studied for electrochemical CO2 reduction reaction (CO2 RR) to make formic acid/formate, which unfortunately still suffer from low activity, selectivity and stability. In this work, halogen (F, Cl, Br or I) was introduced into the Sn catalyst by a facile hydrolysis method. The presence of halogen was confirmed by a collection of ex situ and in situ characterizations, which rendered a more positive valence state of Sn in halogen-incorporated Sn catalyst as compared to unmodified Sn under cathodic potentials in CO2 RR and therefore tuned the adsorption strength of the key intermediate (*OCHO) toward formate formation. As a result, the halogen-incorporated Sn catalyst exhibited greatly enhanced catalytic performance in electrochemical CO2 RR to produce formate.

7.
Chem Soc Rev ; 49(10): 2937-3004, 2020 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-32407432

RESUMO

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.

8.
Environ Sci Technol ; 53(16): 9937-9946, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31355635

RESUMO

A novel dual-functional catalytic perovskite hollow fiber membrane reactor was fabricated by integrating BaBi0.05Co0.8Nb0.15O3-δ (BBCN) perovskite hollow fiber membrane with Ni-phyllosilicate hollow sphere catalysts for simultaneous NO decomposition and partial oxidation of methane (POM) reaction. With this novel catalytic membrane reactor, NO could be completely converted to N2 at a medium-low temperature (675 °C) owing to instantaneous oxygen removal from the NO decomposition reaction system. Coupled POM reaction on the other side of BBCN hollow fiber membrane not only increased the driving force for oxygen permeation but also produced valuable products (syngas). This novel membrane reactor showed high NO removal capacity at comparatively low temperatures (675-700 °C), which is 100-200 °C lower than those of other membrane reactors reported in literature. In addition, even with the presence of a 2-5% oxygen concentration in NO stream, NO could still be completely decomposed to N2 via this catalytic BBCN membrane reactor. Evidently, the application of this novel catalytic membrane reactor could overcome the inhibition of oxygen present atmosphere for NO decomposition and achieve a remarkably high efficiency for NO removal.


Assuntos
Metano , Titânio , Compostos de Cálcio , Óxidos , Temperatura
9.
Chemphyschem ; 18(22): 3117-3134, 2017 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-28710875

RESUMO

In recent years, CO2 reforming of methane (dry reforming of methane, DRM) has become an attractive research area because it converts two major greenhouse gasses into syngas (CO and H2 ), which can be directly used as fuel or feedstock for the chemical industry. Ni-based catalysts have been extensively used for DRM because of its low cost and good activity. A major concern with Ni-based catalysts in DRM is severe carbon deposition leading to catalyst deactivation, and a lot of effort has been put into the design and synthesis of stable Ni catalysts with high carbon resistance. One effective and practical strategy is to introduce a second metal to obtain bimetallic Ni-based catalysts. The synergistic effect between Ni and the second metal has been shown to increase the carbon resistance of the catalyst significantly. In this review, a detailed discussion on the development of bimetallic Ni-based catalysts for DRM including nickel alloyed with noble metals (Pt, Ru, Ir etc.) and transition metals (Co, Fe, Cu) is presented. Special emphasis has been provided on the underlying principles that lead to synergistic effects and enhance catalyst performance. Finally, an outlook is presented for the future development of Ni-based bimetallic catalysts.

10.
Langmuir ; 30(48): 14694-705, 2014 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-25397692

RESUMO

Ni@Ni-Mgphy (Ni-Mgphy = Ni-Mg phyllosilicate) core-shell catalysts were designed by hydrothermally treating Ni@SiO2 nanoparticles with magnesium nitrate salt. The porosity and basicity of the catalysts were easily tuned by forming Ni-Mgphy shell using Ni originating from Ni@SiO2 during the hydrothermal treatment process and Mg(NO3)2 as the Ni and Mg sources, respectively. Among Ni@Ni-Mgphy core-shell catalysts synthesized under different hydrothermal durations, the catalyst treated for 10 h achieved the best catalytic performance for CO2 reforming of CH4 reaction with stable CO2 and CH4 conversions of around 81% and 78%, respectively, within 95 h reaction duration at 700 °C. The high Ni accessibility, strong basicity, and high structural stability for Ni@Ni-Mgphy core-shell catalyst with 10 h treatment time accounted for its superb catalytic performance. This method to simultaneously tune the porosity and basicity of Ni@SiO2 core-shell nanoparticles demonstrates a general way to modify the properties of other silica based core-shell nanoparticles through treating them with different metal salts.

11.
Int J Biol Macromol ; 269(Pt 1): 131988, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38701999

RESUMO

The disposal of waste lithium batteries, especially waste separators, has always been a problem, incineration and burial will cause environmental pollution, therefore, the development of degradable and high-performance separators has become an important challenge. Herein, UiO-66-NH2 particles were successfully anchored onto bacterial cellulose (BC) separators by epichlorohydrin (ECH) as a crosslinker, then a BC/UiO-66-NH2 composite separator was prepared by vacuum filtration. The ammonia groups (-NH2) from UiO-66-NH2 can form hydrogen bonds with PF6- in the electrolyte, promoting lithium-ion transference. Additionally, UiO-66-NH2 can store the electrolyte and tune the porosity of the separator. The lithium ion migration number (0.62) of the battery assembled with BC/UiO-66-NH2 composite separator increased by 50 % compared to the battery assembled with commercial PP separator (0.45). The discharge specific capacity of the battery assembled with BC/UIO-66-NH2 composite separator after 50 charge and discharge cycles is 145.4 mAh/g, which is higher than the average discharge specific capacity of 114.3 mAh/g of the battery assembled with PP separator. When the current density is 2C, the minimum discharge capacity of the battery assembled with BC/UiO-66-NH2 composite separator is 85.3 mAh/g. The electrochemical performance of the BC/UiO-66-NH2 composite separator is significantly better than that of the commercial PP separator. In addition, -NH2 can offer a nitrogen source to facilitate degradation of the BC separators, whereby the BC/UiO-66-NH2 composite separator could be completely degraded in 15 days.


Assuntos
Celulose , Fontes de Energia Elétrica , Lítio , Lítio/química , Celulose/química , Íons/química , Biodegradação Ambiental
12.
J Colloid Interface Sci ; 656: 58-67, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-37984171

RESUMO

Selective oxidations are important reactions in organic synthesis for fine chemical industry and conventional methods are expensive and produce a lot of toxic wastes. Herein, we demonstrate a facile and environmentally benign technique for liquid phase selective oxidation based on graphene-supported Mn single-atom-catalyst (SAMn-G) for efficient peroxymonosulfate (PMS) activation. The active Mn component in the developed SAMn-G catalyst reached single-atomic dispersion on graphene substrate via the coordination of individual Mn atoms with the doped N from the graphene framework. SAMn-G activated PMS via a nonradical-dominated pathway, which could convert aromatic alcohols into aldehydes or ketones at a mild temperature. The SAMn-G catalyst exhibited superior conversion and aldehyde selectivity in alcohol oxidation in comparison with their counterpart catalysts possessing either homogeneous Mn ions or oxide particles. The high activation efficiency of SAMn-G is due to the synergistic effect between Mn atoms and graphene substrate, as well as the dominated reaction pathway from nonradical oxidation, which is more selective than these free radicals to oxidize the alcohols. Concerted experimental evidence indicates that the non-radical oxidation process was highly possible to follow the electron transfer mechanism by PMS/organic adsorption on the surface of the catalyst. This study provides a fundamental understanding of PMS activation mediated by single atom catalyst for organic synthesis and the achieved insights can also help the catalyst design for other liquid phase selective oxidation processes.

13.
Adv Mater ; 36(21): e2313378, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38340031

RESUMO

Green hydrogen, derived from water splitting powered by renewable energy such as solar and wind energy, provides a zero-emission solution crucial for revolutionizing hydrogen production and decarbonizing industries. Catalysts, particularly those utilizing defect engineering involving the strategical introduction of atomic-level imperfections, play a vital role in reducing energy requirements and enabling a more sustainable transition toward a hydrogen-based economy. Stacking fault (SF) defects play an important role in enhancing the electrocatalytic processes by reshaping surface reactivity, increasing active sites, improving reactants/product diffusion, and regulating electronic structure due to their dense generation ability and profound impact on catalyst properties. This review explores SF in metal-based materials, covering synthetic methods for the intentional introduction of SF and their applications in hydrogen production, including oxygen evolution reaction, photo- and electrocatalytic hydrogen evolution reaction, overall water splitting, and various other electrocatalytic processes such as oxygen reduction reaction, nitrate reduction reaction, and carbon dioxide reduction reaction. Finally, this review addresses the challenges associated with SF-based catalysts, emphasizing the importance of a detailed understanding of the properties of SF-based catalysts to optimize their electrocatalytic performance. It provides a comprehensive overview of their various applications in electrocatalytic processes, providing valuable insights for advancing sustainable energy technologies.

14.
J Colloid Interface Sci ; 674: 778-790, 2024 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-38955009

RESUMO

The CO preferential oxidation reaction (CO-PROX) is an effective strategy to remove residual poisonous CO in proton exchange membrane fuel cells, in which oxygen vacancies play a critical role in CO adsorption and activation. Herein, a series of CuO/CeO2 catalysts derived from Ce-MOFs precursors were synthesized using different organic ligands via the hydrothermal method and the CO-PROX performance was investigated. The CuO/CeO2-135 catalyst derived from homophthalic tricarboxylic acid (1,3,5-H3BTC) exhibited superior catalytic performance with 100 % CO conversion at a relatively low temperature (T100% = 100 °C), with a wide reaction temperature range and excellent stability. The superior catalytic properties were attributed to the structural improvements provided by the 1,3,5-H3BTC precursors and the promotional effects of oxygen vacancies. Additionally, in-situ Raman spectroscopy was performed to verify the dynamic roles of oxygen vacancies for CO adsorption and activation, while in-situ DRIFTS analysis revealed key intermediates in the CO-PROX reaction, shedding light on the mechanistic aspects of the catalytic process. This work not only demonstrates insights into the effective CuO/CeO2 catalysts for CO preferential oxidation, but also provides a feasible way to synthesize MOF-derived catalysts.

15.
Environ Sci Technol ; 47(24): 14510-7, 2013 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-24274713

RESUMO

CO2 utilization in catalytic membrane reactors for syngas production is an environmentally benign solution to counter the escalating global CO2 concerns. In this study, integration of a La0.6Sr0.4Co0.8Ga0.2O3-δ (LSCG) hollow fiber membrane reactor with Ni/LaAlO3-Al2O3 catalyst for the oxidative CO2 reforming of methane (OCRM) reaction was successfully tested for 160 h of reaction. High CH4 and CO2 conversions of ca. 94% and 73% were obtained with O2 flux ca. 1 mL·min(-1)·cm(-2) at 725 °C for the 160-h stability test. Surface temperature programmed desorption studies of the membrane were conducted with H2, CO, and CO2 as probe gases to facilitate understanding on the effect of H2 and CO product gases as well as CO2 reactant gases on the membrane surface. Scanning electron microscopy-energy dispersive X-ray (SEM-EDX), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) analysis of the postreacted membrane after 160-h stability tests suggests Sr-enriched phases with the presence of adsorbed carbonate and hydrogenated carbon. This shows the subsequent reactant spillover on the membrane surface from the catalyst bed took place due to the reaction occurring on the catalyst. However, XRD analysis of the bulk structure does not show any phase impurities, thus confirming the structural integrity of the LSCG hollow fiber membrane.


Assuntos
Dióxido de Carbono/química , Recuperação e Remediação Ambiental/instrumentação , Membranas Artificiais , Metano/química , Adsorção , Monóxido de Carbono/análise , Catálise , Hidrogênio/análise , Microscopia Eletrônica de Varredura , Oxirredução , Oxigênio/química , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície , Temperatura , Difração de Raios X
16.
J Colloid Interface Sci ; 648: 951-962, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37329606

RESUMO

Lack of safety and unenough electrochemical performance have been known as a fundamental obstacle limiting the extensive application of lithium-ion batteries (LIBs). It is really preferable but challenging to fabricate thermal-response separator with shutdown function for high-performance LIBs. Herein, a thermal-response sodium-alginate modified PMIA (Na-Alg/PMIA) composite separator with shutdown function was designed and prepared by non-solvent phase induced separation (NIPs). PMIA and Na-Alg are combined by hydrogen bonding. While Na-Alg increases polar groups and makes Li+ easy to be transported, a small amount of Na+ can provide Li+ active sites, accelerate Li+ deposition coating and effectively inhibit the formation of Li dendrites. The as-prepared Na-Alg/PMIA composite separators can close pores at 200 °C and maintain dimensional integrity without obvious thermal shrinkage. In addition, the Na-Alg/PMIA composite separators has excellent wettability and ionic conductivity, resulting in high specific capacity and retention during the charge-discharge cycles. After 50 cycles, the capacity retention of cells with the Na-Alg/PMIA-20 composite separator is 84.3 %. At 2 C, cells with the Na-Alg/PMIA-20 composite separators still held 101.1 mAh g-1. This facile yet effective method improves the electrochemical performance while ensuring the safety of the LIBs, which provides ideas for the commercial application of PMIA separators.

17.
J Colloid Interface Sci ; 643: 151-161, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37058890

RESUMO

Catalytic methane decomposition (CMD) has emerged as an appealing technology for large-scale production of H2 and carbon nanostructures from natural gas. As the CMD process is mildly endothermic, the application of concentrated renewable energy sources such as solar energy under a low-temperature regime could potentially represent a promising approach towards CMD process operation. Herein, Ni/Al2O3-La2O3 yolk-shell catalysts are fabricated using a straightforward single-step hydrothermal approach and tested for their performance in photothermal CMD. We show that the morphology of the resulting materials, dispersion and reducibility of Ni nanoparticles, and nature of metal-support interactions can be tuned by addition of varying amounts of La. Notably, the addition of an optimal amount of La (Ni/Al-20La) improved the H2 yield and catalyst stability relative to the base Ni/Al2O3 material, while also favoring base growth of carbon nanofibers. Additionally, we show for the first time a photothermal effect in CMD, whereby the introduction of 3 suns light irradiation at a constant bulk temperature of 500 °C reversibly increased the H2 yield of catalyst by about 1.2 times relative to the rate in the dark, accompanied by a decrease in apparent activation energy from 41.6 kJ mol-1 to 32.5 kJ mol-1. The light irradiation further suppressed undesirable CO co-production at low temperatures. Our work reveals photothermal catalysis as a promising route for CMD while providing an insightful understanding of the roles of modifier in enriching methane activation sites on Al2O3-based catalysts.

18.
Commun Chem ; 6(1): 273, 2023 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-38087001

RESUMO

Feedstock properties play a crucial role in thermal conversion processes, where understanding the influence of these properties on treatment performance is essential for optimizing both feedstock selection and the overall process. In this study, a series of van Krevelen diagrams were generated to illustrate the impact of H/C and O/C ratios of feedstock on the products obtained from six commonly used thermal conversion techniques: torrefaction, hydrothermal carbonization, hydrothermal liquefaction, hydrothermal gasification, pyrolysis, and gasification. Machine learning methods were employed, utilizing data, methods, and results from corresponding studies in this field. Furthermore, the reliability of the constructed van Krevelen diagrams was analyzed to assess their dependability. The van Krevelen diagrams developed in this work systematically provide visual representations of the relationships between feedstock and products in thermal conversion processes, thereby aiding in optimizing the selection of feedstock and the choice of thermal conversion technique.

19.
iScience ; 25(12): 105343, 2022 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-36483017

RESUMO

Zeolite-based catalytic membrane reactors have been successfully applied in overcoming the thermodynamic limitations of CO2 hydrogenations and dry reforming of methane (DRM) reactions. This review summarizes the zeolites as membrane reactor components regarding the permeance, permselectivity, durability, conversion, selectivity, and stability by referring to the synergy of catalyst and membrane. Also, five operation parameters (temperature, pressure, feed ratio, sweeping gas flow rate, and gas hourly space velocity) are introduced regarding their impacts on the performance of membrane reactor. Besides, synthesis methods and conditions for zeolite membranes are critically illustrated in the category. Moreover, representative surface and structure properties of zeolite membranes are discussed by relating to the synthesis-structure-performance relationships. Finally, conclusive remarks are demonstrated and possible solutions to existing challenges are proposed. So far, this is the first time to discuss the applications of zeolite membrane reactors in the CO2 adsorption, separation, activation, and conversion in reforming and hydrogenation processes.

20.
ACS Appl Mater Interfaces ; 14(4): 5363-5375, 2022 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-35072474

RESUMO

Plasma-catalytic direct nonoxidative coupling of methane (NCM) into C2 hydrocarbons was investigated over ceria-supported atomically dispersed Pt (Pt/CeO2-SAC) and nanoparticle Pt (Pt/CeO2-NP) catalysts in dielectric barrier discharge (DBD) plasma. Nonthermal plasma facilitated C-H bond dissociation in CH4 at low temperatures (<150 °C) and atmospheric pressure. The presence of Pt/CeO2 catalysts in plasma further enhanced CH4 conversion and C2 hydrocarbon selectivity by enabling the conversion of vibrationally excited methane species with high internal energy on active Pt sites. Noticeably, the Pt/CeO2-SAC catalyst displayed a more remarkable performance, with a CH4 conversion of 39% and a C2 selectivity of 54% at 54 W. The enhanced CH4 conversion was attributed to abundant coordinatively unsaturated Pt sites in Pt/CeO2-SAC, which were more active for C-H bond scission. Meanwhile, isolated Pt atoms in Pt/CeO2-SAC promoted C2 hydrocarbon formation by hindering the unselective formation of coke from deep dehydrogenation of CHx• intermediates and higher hydrocarbons from oligomerization reactions.

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