Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 20
Filtrar
Mais filtros

Base de dados
Tipo de documento
Intervalo de ano de publicação
1.
Environ Sci Technol ; 58(28): 12742-12753, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38959431

RESUMO

Short carbon chain alkanes, as typical volatile organic compounds (VOCs), have molecular structural stability and low molecular polarity, leading to an enormous challenge in the catalytic oxidation of propane. Although Ru-based catalysts exhibit a surprisingly high activity for the catalytic oxidation of propane to CO2 and H2O, active RuOx species are partially oxidized and sintered during the oxidation reaction, leading to a decrease in catalytic activity and significantly inhibiting their application in industrial processes. Herein, the Ru/Ce@Co catalyst is synthesized with a specific structure, in which cerium dioxide is dispersed in a thin layer on the surface of Co3O4, and Ru nanoparticles fall preferentially on cerium oxide with high dispersity. Compared with the Ru/CeO2 and Ru/Co3O4 catalysts, the Ru/Ce@Co catalyst demonstrates excellent catalytic activity and stability for the oxidation of propane, even under severe operating conditions, such as recycling reaction, high space velocity, a certain degree of moisture, and high temperature. Benefiting from this particular structure, the Ru/Ce@Co (5:95) catalyst with more Ce3+ species leads to the Ru species being anchored more firmly on the CeO2 surface with a low-valent state and has a strong potential for adsorption and activation of propane and oxygen, which is beneficial for RuOx species with high activity and stability. This work provides a novel strategy for designing high-efficiency Ru-based catalysts for the catalytic combustion of short carbon alkanes.


Assuntos
Oxirredução , Catálise , Cério/química , Propano/química , Propano/análogos & derivados , Rutênio/química
2.
Environ Sci Technol ; 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38319875

RESUMO

Light alkanes (LAs), typical VOCs existing in both stationary and mobile sources, pose significant environmental concerns. Although noble metal catalysts demonstrate strong C-H bond activation, their effectiveness in degrading LAs is hindered by inherent challenges, including poor chemical stability and water resistance. Here, from a new perspective, we propose a feasible strategy that adjusting the metal bond lengths within Pd clusters through partial substitution of smaller radius 3d transition metals (3dTMs) to prioritize the activation of low-energy C-C bonds within LAs. Benefiting from this, PdCo/CeO2 exhibits exceptional catalytic performance in propane degradation due to their high capacity for C-C cleavage stemming from the shorter Pd-Co length (2.51 Å) and lower coordination number (1.73), boosting the activation of α-H and ß-H of propane simultaneously and accelerating the mobility of postactivated oxygen species to prevent Pd center deep oxidation. The presence of 3dTMs on Pd clusters improves the redox and charge transfer ability of catalysts, resulting in an amplified generation of oxygen vacancies and facilitating the adsorption and activation of reactants. Mechanistic studies and DFT calculations suggest that the substitution of 3dTMs significantly accelerate C-C bond cleavage within C3 intermediates to generate the subsequent C2 and C1 intermediates, suppressing the generation of harmful byproducts.

3.
Environ Sci Technol ; 56(23): 17278-17287, 2022 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-36335508

RESUMO

Pt-based catalysts have attracted widespread attention in environmental protection applications, especially in the catalytic destruction of light alkane pollutants. However, developing a satisfying platinum catalyst with high activity, excellent water-resistance, and practical suitability for hydrocarbon combustion at low temperature is challenging. In this study, the Pt catalyst supported on the selected Nb2O5 oxide exhibited an efficient catalytic activity in propane oxidation and exceeded that of most catalysts reported in the literature. More importantly, the Pt/Nb2O5 catalyst maintained excellent activity and durability even after high-temperature aging at 700 °C and under harsh working conditions, such as a certain degree of moisture, high space velocity, and composite pollutants. The excellent performance of the Pt/Nb2O5 catalyst was attributed to the abundant metallic Pt species stabilized on the surface of Nb2O5, which prompted the C-H bond dissociation ability as the rate-determining step. Furthermore, propane was initially activated via oxidehydrogenation and followed the acrylate species path as a more efficient propane oxidation path on the Pt/Nb2O5 surface. Overall, Pt/Nb2O5 can be considered a promising catalyst for the catalytic oxidation of alkanes from industrial sources and could provide inspiration for designing superb catalysts for the oxidation of light alkanes.

4.
Environ Sci Technol ; 56(13): 9661-9671, 2022 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-35695747

RESUMO

Developing efficient catalysts for the total oxidation of light alkane at low temperatures is challenging. In this study, superior catalytic performance in the total oxidation of light alkane was achieved by modulating the acidity and redox property of a Pt/CeO2 catalyst through phosphorus modification. Surface modification with phosphorus resulted in electron withdrawal from Pt, leading to platinum species with high valency and the generation of Brönsted acid sites, leading to increased acidity of the Pt/CeO2 catalyst. Consequently, the ability of the Pt/CeO2 catalyst to activate the C-H bond increased with increasing P content in the catalyst owing to the synergistic effect of Ptδ+-(CeO2-POx)δ- dipolar catalytic sites. In contrast, the redox property of the Pt/CeO2 catalyst weakened at first; subsequently, it was partially restored owing to the recovery of a part of the bare ceria surface with increasing P content. The turnover frequency in propane oxidation over the phosphate-modified Pt/CeO2 catalyst with a P/Ce atomic ratio of 0.06 was 10-fold higher than that over the unmodified Pt/CeO2 catalyst at 220 °C. This comprehensive study not only sheds light on the mechanism underlying the surface modification process but also offers a strategy for realizing higher catalytic activity in the total oxidation of light alkanes.

5.
J Environ Sci (China) ; 116: 79-89, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35219427

RESUMO

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH3 treatment strategy. The effects of NH3 treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co3+ (serving as active sites) while a largest increased amount of surface Co2+ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH3 treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T90 (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co3+ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C3H8 total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO2 over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH3 treatment.


Assuntos
Óxidos , Propano , Hidróxido de Alumínio , Carvão Mineral , Hidróxido de Magnésio , Óxidos/química , Oxigênio/análise , Temperatura
6.
Appl Environ Microbiol ; 87(14): e0022721, 2021 06 25.
Artigo em Inglês | MEDLINE | ID: mdl-33962978

RESUMO

The families of copper-containing membrane-bound monooxygenases (CuMMOs) and soluble di-iron monooxygenases (SDIMOs) are involved not only in methane oxidation but also in short-chain alkane oxidation. Here, we describe Rhodococcus sp. strain ZPP, a bacterium able to grow with ethane or propane as the sole carbon and energy source, and report on the horizontal gene transfer (HGT) of actinobacterial hydrocarbon monooxygenases (HMOs) of the CuMMO family and the sMMO (soluble methane monooxygenase)-like SDIMO in the genus Rhodococcus. The key function of HMO in strain ZPP for propane oxidation was verified by allylthiourea inhibition. The HMO genes (designated hmoCAB) and those encoding sMMO-like SDIMO (designated smoXYB1C1Z) are located on a linear megaplasmid (pRZP1) of strain ZPP. Comparative genomic analysis of similar plasmids indicated the mobility of these plasmids within the genus Rhodococcus. The plasmid pRZP1 in strain ZPP could be conjugatively transferred to a recipient Rhodococcus erythropolis strain in a mating experiment and showed similar ethane- and propane-consuming activities. Finally, our findings demonstrate that the horizontal transfer of plasmid-based CuMMO and SDIMO genes confers the ability to use ethane and propane on the recipient. IMPORTANCE CuMMOs and SDIMOs initiate the aerobic oxidation of alkanes in bacteria. Here, the supposition that horizontally transferred plasmid-based CuMMO and SDIMO genes confer on the recipient similar abilities to use ethane and propane was proposed and confirmed in Rhodococcus. This study is a living example of HGT of CuMMOs and SDIMOs and outlines the plasmid-borne properties responsible for gaseous alkane degradation. Our results indicate that plasmids can support the rapid evolution of enzyme-mediated biogeochemical processes.


Assuntos
Proteínas de Bactérias/genética , Oxigenases de Função Mista/genética , Rhodococcus/genética , Etano/metabolismo , Transferência Genética Horizontal , Genes Bacterianos , Oxirredução , Plasmídeos , Propano/metabolismo , Rhodococcus/metabolismo
7.
Chemistry ; 27(14): 4738-4745, 2021 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-33405257

RESUMO

Unsatisfactory oxygen mobility is a considerable barrier to the development of perovskites for low-temperature volatile organic compounds (VOCs) oxidation. This work introduced small amounts of dispersed non-metal boron into the LaCoO3 crystal through an easy sol-gel method to create more oxygen defects, which are conducive to the catalytic performance of propane (C3 H8 ) oxidation. It reveals that moderate addition of boron successfully induces a high distortion of the LaCoO3 crystal, decreases the perovskite particle size, and produces a large proportion of bulk Co2+ species corresponding to abundant oxygen vacancies. Additionally, surface Co3+ species, as the acid sites, which are active for cleaving the C-H bonds of C3 H8 molecules, are enriched. As a result, the LCB-7 (molar ratio of Co/B=0.93:0.07) displays the best C3 H8 oxidation activity. Simultaneously, the above catalyst exhibits superior thermal stability against CO2 and H2 O, lasting 200 h. This work provides a new strategy for modifying the catalytic VOCs oxidation performance of perovskites by the regulation of amorphous boron dispersion.

8.
Nanomaterials (Basel) ; 14(11)2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38869532

RESUMO

Defect manipulation in metal oxide is of great importance in boosting catalytic performance for propane oxidation. Herein, a selective atom removal strategy was developed to construct a defective manganese oxide catalyst, which involved the partial etching of a Mg dopant in MnOx. The resulting MgMnOx-H catalysts exhibited superior low-temperature catalytic activity (T50 = 185 °C, T90 = 226 °C) with a propane conversion rate of 0.29 µmol·gcat.-1·h-1 for the propane oxidation reaction, which is 4.8 times that of pristine MnOx. Meanwhile, a robust hydrothermal stability was guaranteed at 250 °C for 30 h of reaction time. The comprehensive experimental characterizations revealed that the catalytic performance improvement was closely related to the defective structures including the abundant (metal and oxygen) vacancies, distorted crystals, valence imbalance, etc., which prominently weakened the Mn-O bond and stimulated the mobility of surface lattice oxygen, leading to the elevation in the intrinsic oxidation activity. This work exemplifies the significance of defect engineering for the promotion of the oxidation ability of metal oxide, which will be valuable for the further development of efficient non-noble metal catalysts for propane oxidation.

9.
J Hazard Mater ; 475: 134917, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38889472

RESUMO

Crystal facet and defect engineering are crucial for designing heterogeneous catalysts. In this study, different solvents were utilized to generate NiO with distinct shapes (hexagonal layers, rods, and spheres) using nickel-based metal-organic frameworks (MOFs) as precursors. It was shown that the exposed crystal facets of NiO with different morphologies differed from each other. Various characterization techniques and density functional theory (DFT) calculations revealed that hexagonal-layered NiO (NiO-L) possessed excellent low-temperature reducibility and oxygen migration ability. The (111) crystal plane of NiO-L contained more lattice defects and oxygen vacancies, resulting in enhanced propane oxidation due to its highest O2 adsorption energy. Furthermore, the higher the surface active oxygen species and surface oxygen vacancy concentrations, the lower the C-H activation energy of the NiO catalyst and hence the better the catalytic activity for the oxidation of propane. Consequently, NiO-L exhibited remarkable catalytic activity and good stability for propane oxidation. This study provided a simple strategy for controlling NiO crystal facets, and demonstrated that the oxygen defects could be more easily formed on NiO(111) facets, thus would be beneficial for the activation of C-H bonds in propane. In addition, the results of this work can be extended to the other fields, such as propane oxidation to propene, fuel cells, and photocatalysis.

10.
Materials (Basel) ; 17(5)2024 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-38473476

RESUMO

The properties of a catalyst support are closely related to the catalyst activity, yet the focus is often placed on the active species, with little attention given to the support properties. In this work, we specifically investigated the changes in support properties after the addition of P, as well as their impact on catalyst activity when used for catalyst preparation. We prepared the CeO2-ZrO2-P2O5-Al2O3 (CeZrPAl) composite oxides using the sol-gel, impregnation, and mechanical mixing methods, and characterized the support properties using techniques such as XRD, XPS, SEM-EDS, N2 adsorption-desorption, and Raman spectra. The results showed that the support prepared using the sol-gel method can exhibit a more stable phase structure, larger surface area, higher adsorption capacity for oxygen species, and greater oxygen storage capacity. The addition of an appropriate amount of P is necessary. On the one hand, the crystallization and growth of CePO4 can lead to a decrease in the Ce content in the cubic phase ceria-zirconia solid solution, resulting in a phase separation of the ceria-zirconia solid solution. On the other hand, CePO4 can lock some of the Ce3+/Ce4+ redox pairs, leading to a reduction in the adsorption of oxygen species and a decrease in the oxygen storage capacity of the CeZrPAl composite oxides. The research results indicated that the optimal P addition is 6 wt.% in the support. Therefore, we prepared a Pd/CeZrPAl catalyst using CeZrAl with 6 wt.% P2O5 as the support and conducted the catalytic oxidation of C3H8. Compared with the support without P added, the catalyst activity of the support loaded with P was significantly improved. The fresh and aged (1000 °C/5 h) catalysts decreased by 20 °C and 5 °C in T50 (C3H8 conversion temperature of 50%), and by 81 °C and 15 °C in T90 (C3H8 conversion temperature of 90%), respectively.

11.
J Colloid Interface Sci ; 641: 48-58, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36924545

RESUMO

Photothermal catalysis has an advantage in effective and economical elimination technology of volatile organic compounds (VOCs) in the ascendant. Herein, various surface defect engineering routes were adopted to enhance the low-temperature propane oxidation of δ-MnO2. Compared to reducing etchants urea and vitamin C, δ-MnO2 treated with urea - H2O2 exhibited an excellent thermal (T90 = 240 ℃) and photothermal (T90 = 196 ℃) activities of propane oxidation. Urea - H2O2 treatment provided high concentration of Mn4+ and surface-active oxygen (Mn4+-Osur) species as surface-active sites, and produced numerous oxygen vacancies to improve charge separation and superoxide species generation capacity. Thus, the photothermal conversion efficiency and low-temperature reducibility were remarkably enhanced. Furthermore, the photothermal synergistic catalytic mechanism was proposed based on in-situ diffuse reflectance infrared Fourier transform spectroscopy and control experiments. The strategy here offered insight into the rational design of efficient transition catalysts, and in-depth understanding of the photothermal catalytic VOCs removal mechanism.

12.
J Hazard Mater ; 452: 131319, 2023 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-37004446

RESUMO

Defects engineering in metal oxide is an important avenue for the promotion of VOCs catalytic oxidation. Herein, the influence of crystal facet of Co3O4 is first investigated for the propane oxidation. An intelligent Cu doping is subsequently performed in the most active (110) facet exposed Co3O4 catalyst. The optimized Cu-Co3O4-110-3 catalyst exhibits a prominently enhanced activity with propane conversion rate of 1.9 µmol g-1 s-1 at reaction temperature of 192 °C and the propane mass space velocity of 60,000 mL g-1 h-1, about 2.4 times that of the pristine Co3O4. Systematic experimental characterizations (XAS, EPR, Raman, TPR, XPS, etc.) combined with density functional theory calculations point out that the incorporated Cu could increase the electrophilicity of nearby O atom and implant beneficial defect structures (lattice distortion, coordination unsaturation, abundant oxygen vacancies, etc.), which could significantly activate Co-O bond in Co3O4, leading to the facilitated generation of active oxygen species as well as promoted oxidation ability. This study could set an illuminating paradigm for the boost of the intrinsic oxidation activity by the precise defect construction in Co3O4 catalyst, which will help drive ahead the pursuit of non-precious metal catalyst for VOCs abatement.

13.
J Colloid Interface Sci ; 642: 380-392, 2023 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-37018963

RESUMO

Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. The modulation of the interfacial coupling effect of manganese oxides by chemical means is considered a critical and effective way to improve the catalytic performance. Herein, a novel one-step synthetic strategy of highly-efficient ultrathin manganese-based catalysts is proposed through optimal regulation of metal/manganese oxide multi-interfacial coupling. Carbon monoxide (CO) and propane (C3H8) oxidation are employed as probe reactions to investigate the structure-catalytic mechanism - catalytic performance relationship. The ultrathin manganese (Mn)-based catalyst exhibits superior low-temperature catalytic activity with a 90% conversion of CO/C3H8 realized at 106℃ and 350℃. Subsequently, the effect of "interfacial effect" on the intrinsic properties of manganese oxides is revealed. The ultrathin appearance of two-dimensional (2D) manganese dioxide (MnO2) nanosheets changes the binding force in the vertical direction, thus resulting in an increase in the average manganese-oxygen (Mn-O) bond length and exposing more surface defects. Besides, the introduction of Copper (Cu) species into the catalyst further weakens the Mn-O bond and promotes the generation of oxygen vacancies, which subsequently enhances the oxygen migration rate. This study provides new insights into the optimal design of transition metal oxide interfacial assemblies for efficient catalytic reactions.

14.
J Colloid Interface Sci ; 650(Pt B): 1415-1423, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37460387

RESUMO

Adjusting the interaction between dual active components for enhancing volatile organic compounds (VOCs) degradation is an effective but still challenging means of air pollution control. Herein, a limited pyrolysis oxidation strategy was adopted to prepare Pd-Mn3O4 spinel catalysts with uniform morphology and active component dispersion. Among these, 1.08Pd-Mn3O4 presented the highest catalytic efficiency with a T90 value of 240 °C, which was 94 °C lower than that of Mn3O4. Characterization and density functional theory (DFT) calculation results revealed that the strong metal-support interaction (SMSI) effect between Pd and Mn3O4 promoted the redistribution of surface charges, thus strengthening the oxidation-reduction ability of the active sites. Moreover, the SMSI effect led to a better migration of surface oxygen species, and boosted the generation of active surface oxygen species. Simultaneously, the Pd catalyst further reduced the energy barrier in the initial stage of the dehydrogenation of propane. Overall, this study provided a novel design strategy for dual active components catalysts with SMSI effect and extended the application of these catalysts in the important field of VOCs elimination.

15.
ChemSusChem ; 16(23): e202300699, 2023 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-37561115

RESUMO

Electrochemical conversion of alkanes to high value-added oxygenated products under a mild condition is of significance. Herein, we effectively couple the electrocatalysis of H2 O2 with the thermo-catalysis of propane oxidation in the cathode of proton exchange membrane fuel cell. Specifically, H2 O2 is in-situ generated on the nitric acid-treated carbon black (C-acid) via 2e- process of oxygen reduction reaction, and then transports to the Fe active sites of MIL-53 (Al, Fe) metal-organic frameworks for propane oxidation. Based on this strategy, the space-time yield of C3 oxygenated products of propane oxidation reaches 2.65 µmol h-1 cm-2 , which represents a new benchmark for electrochemical alkane oxidation in the fuel-cell-type electrolyzer. This study highlights the importance of multifunctional composite catalysts in the field of electrosynthesis.

16.
Chempluschem ; 87(2): e202100455, 2022 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35103416

RESUMO

A high-surface-area Ce doped mullite YMn2 O5 was developed via a facile hydrothermal approach, which exhibited higher catalytic activity with a long thermal stability towards propane oxidation in regards to pristine mullite YMn2 O5 . T90 (the temperature at 90 % conversion of reactant) of propane over the mixed oxides is ∼40 °C lower than that over pristine YMn2 O5 mullite (147 m2 /g). The complete oxidation temperature occurs at as low as 225 °C (1000 ppm C3 H8 and 10 % O2 balanced with N2 , WHSV=30,000 mL/g h). Notably, the mixed oxides maintain superior catalytic stability at 250 °C for 120 h without noticeable loss in the activity. Fundamentally, the remarkable performance stems from the abundant oxygen defects caused by the lattice mismatch between CeO2 and YMn2 O5 , which is conducive to the gas phase oxygen adsorption and activation, thereby enhancing the low temperature catalytic activity of the material. In addition, the CeO2 on the catalyst's surface acts as an oxygen reservoir and provides additional adsorption sites for propane to promote the oxidation reaction. In situ DRIFTS results indicates that the dissociation of acrylate could be the key step for propane oxidation since acrylate is more difficult to decompose and desorb than formate and acetate. These findings revealed the roles of ceria on mullite oxides for propane oxidation activity.

17.
ACS Appl Mater Interfaces ; 14(9): 11435-11447, 2022 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-35195398

RESUMO

The ability to harness the catalytic oxidation of hydrocarbons is critical for both clean energy production and air pollutant elimination, which requires a detailed understanding of the dynamic role of the nanophase structure and surface reactivity under the reaction conditions. We report here findings of an in situ/operando study of such details of a ternary nanoalloy under the propane oxidation condition using high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalysts are derived by alloying Pt with different combinations of second (Pd) and third (Ni) transition metals, showing a strong dependence of the catalytic activity on the Ni content. The evolution of the phase structure of the nanoalloy is characterized by HE-XRD/PDF probing of the lattice strain, whereas the surface activity is monitored by DRIFTS detection of the surface intermediate formation during the oxidation of propane by oxygen. The results reveal the dominance of the surface intermediate species featuring a lower degree of oxygenation upon the first C-C bond cleavage on the lower-Ni-content nanoalloy and a higher degree of oxygenation upon the second C-C bond cleavage on the higher-Ni-content nanoalloy. The face-centered-cubic-type phase structures of the nanoalloys under the oxidation condition are shown to exhibit Ni-content-dependent changes of lattice strains, featuring the strongest strain with little variation for the higher-Ni-content nanoalloy, in contrast to the weaker strains with oscillatory variation for the lower-Ni-content nanoalloys. This process is also accompanied by oxygenation of the metal components in the nanoalloy, showing a higher degree of oxygenation for the higher-Ni-content nanoalloy. These subtle differences in phase structure and surface activity changes correlate with the Ni-composition-dependent catalytic activity of the nanoalloys, which sheds a fresh light on the correlation between the dynamic change of atomic strains and the surface reactivity and has significant implications for the design of oxidation catalysts with enhanced activities.

18.
ACS Appl Mater Interfaces ; 13(23): 27106-27118, 2021 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-34097390

RESUMO

Modulating the catalyst electronic structure is a promising direction to enhance the catalytic oxidation performance. Herein, we report an innovative synthesis of the nanohybrid spinel@CuO catalyst with a broad biphasic interface for propane oxidation. The reaction rate of spinel@CuO catalyst was significantly increased compared to the physically mixed spinel+CuO catalyst. Lattice distortions and severe blurring of lattice fringes adjacent to the interface (between the spinel and CuO) comes with the spinel@CuO system, which enhanced interfacial interaction to form defect structures. The cobalt cations were selectively doped into the spinel lattice and occupied both the A and the B sites, while the CuO was not affected. At lower temperatures (∼200 °C), the enrichment of Brønsted acid sites increased the adsorption energy of propane. At higher temperatures (∼350 °C), the A and B sites cobalt weakened the Cu-O bond to make the oxygen vacancies form more readily, thereby enriching the Lewis acid sites. The substitution doping also resulted in lattice distortion in the spinel species, promoting the formation of a defect structure. The broad interface and temperature-dependent acid sites were conducive to propane oxidation.

19.
J Hazard Mater ; 406: 124695, 2021 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-33310339

RESUMO

A one-dimensional (1D) core-shell of Co-Ce oxide has been prepared by multifluidic coaxial electrospinning method and evaluated for the total oxidation of propane (C3H8). Activity and morphological characterizations show that the CeO2@Co3O4 nanofiber catalyst, of which the core is CeO2 and the shell is Co3O4, exhibits excellent oxidation activity. The exposed Co3O4 grown on the outside of the fibers can rapidly react with C3H8 while CeO2 with high oxygen storage capacity in the inside is conductive to the enhanced oxidation rate. Besides, the continuous grain boundary provides a fast mass transfer channel for lattice oxygen, and rich oxygen vacancies favor the mobility of active oxygen species. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) confirms that the CeO2@Co3O4 catalyst have a faster rate of C3H8 adsorption and better oxidation activity with respect to the counterpart using a single-needle electrospinning method. Moreover, the CeO2@Co3O4 catalyst displays excellent thermal stability, and strong resistance against 5 vol% H2O and 5 vol% CO2 at both 300 and 400 °C. Our strategy can give some new insights into morphological engineering to promote active oxygen mobility via the construction of one-dimensional core-shell of metal oxides for catalytic oxidation of VOCs.

20.
ACS Appl Mater Interfaces ; 10(11): 9220-9224, 2018 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-29498506

RESUMO

Most of the industrial and environmental catalytic reactions are operated at high temperature for a long time, and the sintering of the active centers is the main factor leading to catalysts deactivation, especially for noble metal catalysts. Herein we develop a dual confinement (enhanced metal-oxide interaction and the porous shell confinement) strategy to prepare Pd-Sn pseudo solid solution and in situ embedded in microporous silica for the first time and showed superior catalytic performance for CO and propane total oxidation (two main vehicle emission gases), even stored more than 640 days.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA