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1.
Environ Sci Technol ; 58(27): 12272-12280, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38934332

RESUMO

Environmentally benign cerium-based catalysts are promising alternatives to toxic vanadium-based catalysts for controlling NOx emissions via selective catalytic reduction (SCR), but conventional cerium-based catalysts unavoidably suffer from SO2 poisoning in low-temperature SCR. We develop a strongly sulfur-resistant Ce1+1/TiO2 catalyst by spatially confining Ce atom pairs to different anchoring sites of anatase TiO2(001) surfaces. Experimental results combined with theoretical calculations demonstrate that strong electronic interactions between the paired Ce atoms upshift the lowest unoccupied states to an energy level higher than the highest occupied molecular orbital (HOMO) of SO2 so as to be catalytically inert in SO2 oxidation but slightly lower than HOMO of NH3 so that Ce1+1/TiO2 has desired ability toward NH3 activation required for SCR. Hence, Ce1+1/TiO2 shows higher SCR activity and excellent stability in the presence of SO2 at low temperatures with respect to supported single Ce atoms. This work provides a general strategy to develop sulfur-resistant catalysts by tuning the electronic states of active sites for low-temperature SCR, which has implications for practical applications with energy-saving requirements.


Assuntos
Cério , Enxofre , Cério/química , Enxofre/química , Catálise , Oxirredução , Temperatura
2.
Environ Sci Technol ; 57(20): 7858-7866, 2023 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-37161886

RESUMO

Selective catalytic reduction (SCR) of NOx with NH3 is the most efficient technology for NOx emissions control, but the activity of catalysts decreases exponentially with the decrease in reaction temperature, hindering the application of the technology in low-temperature SCR to treat industrial stack gases. Here, we present an industrially practicable technology to significantly enhance the SCR activity at low temperatures (<250 °C). By introducing an appropriate amount of O3 into the simulated stack gas, we find that O3 can stoichiometrically oxidize NO to generate NO2, which enables NO reduction to follow the fast SCR mechanism so as to accelerate SCR at low temperatures, and, in particular, an increase in SCR rate by more than four times is observed over atom-pair V1-W1 active sites supported on TiO2(001) at 200 °C. Using operando SCR tests and in situ diffuse reflectance infrared Fourier transform spectra, we reveal that the introduction of O3 allows SCR to proceed along a NH4NO3-mediated Langmuir-Hinshelwood model, in which the adsorbed nitrate species speed up the re-oxidation of the catalytic sites that is the rate-limiting step of SCR, thus leading to the enhancement of activity at low temperatures. This technology could be applicable in the real stack gas conditions because O3 exclusively oxidizes NO even in the co-presence of SO2 and H2O, which provides a general strategy to improve low-temperature SCR efficacy from another perspective beyond designing catalysts.


Assuntos
Amônia , Gases , Domínio Catalítico , Amônia/química , Oxirredução , Temperatura , Catálise
3.
Environ Sci Technol ; 56(10): 6631-6638, 2022 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-35500091

RESUMO

Environmentally benign CeO2-WO3/TiO2 catalysts are promising alternatives to commercial toxic V2O5-WO3/TiO2 for controlling NOx emission via selective catalytic reduction (SCR), but the insufficient catalytic activity of CeO2-WO3/TiO2 catalysts is one of the obstacles in their applications because of a lack of an in-depth understanding of the CeO2-WO3 interactions. Herein, we design a Ce1-W1/TiO2 model catalyst by anchoring Ce1-W1 atom pairs on anatase TiO2(001) to investigate the synergy between Ce and W in SCR. A series of characterizations combined with density functional theory calculations and in situ diffuse-reflectance infrared Fourier-transform experiments reveal that there exists a strong electronic interaction within Ce1-W1 atom pairs, leading to a much better SCR performance of Ce1-W1/TiO2 compared with that of Ce1/TiO2 and W1/TiO2. The Ce1-W1 synergy not only shifts down the lowest unoccupied states of Ce1 near the Fermi level, thus enhancing the abilities in adsorbing and oxidizing NH3 but also makes the frontier orbital electrons of W1 delocalized, thus accelerating the activation of O2. The deep insight of the Ce-W synergy may assist in the design and development of efficient catalysts with an SCR activity as high as or even higher than V2O5-WO3/TiO2.


Assuntos
Amônia , Óxidos de Nitrogênio , Catálise , Óxidos , Titânio
4.
Plant Dis ; 2022 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-35852907

RESUMO

Roselle (Hibiscus sabdariffa L.) is an annual herbaceous plant in the Malvaceae family with high anthocyanin and is widely cultivated in Nanning, Guangxi of China due to its economic and nutritional importance. In August 2021, a severe root rot disease with incidence of 42.4% (860 plants in the field) was observed in roselle plants in an open-field crop in Nanning (108°33"E, 22°84"N), Guangxi, China. The roots of the diseased plants were discolored and rotten, and the xylem became black, extending along the main root to the junction of the rhizomes. The above-ground symptoms were leaf yellowing, vascular tissue browning, wilting and death. Three diseased samples were rinsed thoroughly with sterile distilled water, cut with a sterile scalpel into approximately 0.5-cm pieces, surface disinfested with 75% ethanol for one minute, rinsed 3-4 times with sterile water, and finally incubated on potato dextrose agar (PDA) at 28 °C in the dark for 3 days. Emerging colonies were transferred to new PDA two-three times until a single colony was obtained. The aerial mycelium was initially white, turning pale yellow after 5 days of growth on PDA. Microscopic observations revealed that microconidia were hyaline and ovoid with sizes of 5.13 to 15.12 and 2.50 to 4.20 µm (average 9.02, 3.32 µm, n=30). Macroconidia were falciform with 3- to 4-septate, with sizes of 19.08 to 24.35 and 4.5 to 8.00 µm (average 24.35 and 5.23 µm, n=30). The morphological characteristics of the microscopic images were identical to those described for Fusarium solani (Leslie and Summerell 2006). A representative isolate (GXRST29) was selected for DNA extraction for further characterization. The internal transcribed spacer rRNA regions (ITSs), beta tubulin gene sequence and a fragment of the translation elongation factor 1-alpha (EF 1-α) gene sequence were amplified using the primer pairs ITS1/ITS4 (Chehri 2014), Bt-1/Bt-2 (Wang et al. 2014) and EF1-F/EF2-R (O'Donnell et al. 2010), respectively. PCR products were sequenced and deposited in GenBank (accession Nos. OL314654, ON157430 and ON157431, respectively). BLASTn analysis showed that the ITS sequence had 96.99% homology with sequence of F. solani (NR 163531), and 99.26% for Fusarium cf. solani (MG775565) obtained from Homo sapiens. The beta tubulin sequence had 97.96% similarity with BLAST sequence of F. solani (MN295052.1) and EF 1-α gene had 100% identity to published F. solani (MN977912.1). The fungus was identified as F. solani. Five roselle plants at the 5-leaf stage were artificially inoculated by root dipping into a 106-107-mL-1 spore suspension of the isolated GXRST29 for pathogenicity testing. The experiment was conducted three times, and the negative controls were replaced with sterile water. Compared to the control, the growth of plants was significantly inhibited, leaves turned yellow, plants dwarfed and wilted, and roots decayed three days post-inoculation. One week post-inoculation, all plants exhibited symptoms similar to those observed in the field, and F. solani was steadily reisolated from those diseased plants, while no positive isolations were obtained in the controls. F. solani has been reported to cause root rot on roselle in Upper Egypt (Hassan et al. 2014) and lisianthus in China (Xiao et al. 2018). To our knowledge, however, this is the first report of Fusarium wilt caused by F. solani in roselle plants in Nanning, Guangxi, China, and could result in severe crop losses.

5.
Angew Chem Int Ed Engl ; 61(52): e202212703, 2022 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-36321806

RESUMO

Effective adsorption and speedy surface reactions are vital requirements for efficient active sites in catalysis, but it remains challenging to maximize these two functions simultaneously. We present a solution to this issue by designing a series of atom-pair catalytic sites with tunable electronic interactions. As a case study, NO selective reduction occurring on V1 -W1 /TiO2 is chosen. Experimental and theoretical results reveal that the synergistic electron effect present between the paired atoms enriches high-energy spin charge around the Fermi level, simultaneously rendering reactant (NH3 or O2 ) adsorption more effective and subsequent surface reactions speedier as compared with single V or W atom alone, and hence higher reaction rates. This strategy enables us to rationally design a high-performance V1 -Mo1 /TiO2 catalyst with optimized vanadium(IV)-molybdenum(V) electronic interactions, which has exceptional activity significantly higher than the commercial or reported catalysts.

6.
Dev Genes Evol ; 231(5-6): 119-130, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34854979

RESUMO

Gene expression and translation in plant mitochondria remain poorly understood due to the complicated transcription of its mRNA. In this study, we report the 5' and 3' RNA extremities and promoters of five mitochondrial genes, atp1, atp4, atp6, atp9, and cox3. The results reveal that four genes (atp1, atp4, atp6, and cox3) are transcribed from multiple initiation sites but with a uniform transcript at the 3' end, indicating that heterogeneity of the 5' end is a common feature in the transcription of kenaf mitochondrial genes. Furthermore, we found that the transcription initiation sites of these four genes are significantly different in UG93A, UG93B, and the F1 hybrid. These data indicate that nuclear loci and unknown transcription factors within the mitochondria of different cytoplasmic types may be involved in mitochondrial transcription. Promoter architecture analysis showed that the promoter core sequences are conserved in the kenaf mitochondrial genome but are highly divergent, suggesting that these elements are essential for the promoter activity of mitochondrial genes in kenaf. Our results reveal that the heterogeneity of the 5' end and uniformity at the 3' end are common transcriptional features of mitochondrial genes. These data provide essential information for understanding the transcription of mitochondrial genes in kenaf and can be used as a reference for other plants.


Assuntos
Hibiscus , Genes Mitocondriais , Hibiscus/genética , Infertilidade das Plantas , Fatores de Transcrição
7.
Environ Sci Technol ; 55(8): 5435-5441, 2021 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-33724009

RESUMO

Although ceria-based catalysts serve as an appealing alternative to traditional V2O5-based catalysts for selective catalytic reduction (SCR) of NOx with NH3, the inevitable deactivation caused by SO2 at low temperatures severely hampers the ceria-based catalysts to efficiently control NOx emissions from SO2-containing stack gases. Here, we rationally design a strong sulfur-resistant ceria-based catalyst by tuning the electronic structures of ceria highly dispersed on acidic MoO3 surfaces. By using Ce L3-edge X-ray absorption near edge structure spectra in conjunction with various surface and bulk structural characterizations, we report that the sulfur resistance of the catalysts is closely associated with the electronic states of ceria, particularly expressed by the Ce3+/Ce4+ ratio related to the size of the ceria particles. As the Ce3+/Ce4+ ratio increases up to or over 50%, corresponding to CeO2/MoO3(x %, x ≤ 2.1) with the particle size of approximately 4 nm or less, the non-bulk electronic states of ceria appear, where the catalysts start to show strong sulfur resistance. This work could provide a new strategy for designing sulfur-resistant ceria-based SCR catalysts for controlling NOx emissions at low temperatures.


Assuntos
Amônia , Enxofre , Catálise , Eletrônica , Temperatura
8.
Chemistry ; 24(3): 681-689, 2018 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-29030889

RESUMO

Alkali-metal ions often act as promoters rather than active components due to their stable outermost electronic configurations and their inert properties in heterogeneous catalysis. Herein, inert alkali-metal ions, such as K+ and Rb+ , are activated by electron transfer from a Hollandite-type manganese oxide (HMO) support for HCHO oxidation. Results from synchrotron X-ray diffraction, absorption, and photoelectron spectroscopies demonstrate that the electronic density of states of single alkali-metal adatoms is much higher than that of K+ or Rb+ , because electrons transfer from manganese to the alkali-metal adatoms through bridging lattice oxygen atoms. Electron transfer originates from the interactions of alkali metal d-sp frontier orbitals with lattice oxygen sp3 orbitals occupied by lone-pair electrons. Reaction kinetics data of HCHO oxidation reveal that the high electronic density of states of single alkali-metal adatoms is favorable for the activation of molecular oxygen. Mn L3 -edge and O K-edge soft-X-ray absorption spectra demonstrate that lattice oxygen partially gains electrons from the Mn eg orbitals, which leads to the upshift in energy of lattice oxygen orbitals. Therefore, the facile activation of molecular oxygen by the electron-abundant alkali-metal adatoms and active lattice oxygen are responsible for the high catalytic activity in complete oxidation of HCHO. This work could assist the design of efficient and cheap catalysts by tuning the electronic states of active components.

9.
Environ Sci Technol ; 52(20): 11796-11802, 2018 10 16.
Artigo em Inglês | MEDLINE | ID: mdl-30235416

RESUMO

Low-temperature selective catalytic reduction of NO by NH3 (NH3-SCR) is a promising technology for controlling NO emission from various industrial boilers, but it remains challenging because unavoidable deposition of ammonium bisulfates (ABS) in the stack gases containing both SO2 and H2O inevitably results in deactivation of catalysts. Here we developed a stable low-temperature NH3-SCR catalyst by supporting Fe2O3 cubes on surfaces of MoO3 nanobelts with NH4+-intercalatable interlayers, which enables Fe2O3/MoO3 to spontaneously prevent ABS from depositing on the surfaces. Using in situ synchrotron X-ray diffraction, 1H magic angle spinning nuclear magnetic resonance, and temperature-programmed decomposition procedure, the results demonstrate that NH4+ of ABS was initially intercalated in the interlayers of MoO3, leading to a NH4+-HSO4- cation-anion separation by conquering their strong electrostatic interactions, and subsequently the separated NH4+ was consumed by taking part in low-temperature NH3-SCR. Meanwhile, the surface HSO4- separated from ABS oxidized the reduced catalyst during the NH3-SCR redox cycle, concomitant with release of SO2 gas, thereby resulting in decomposition of ABS. This work assists the design of stable low-temperature NH3-SCR catalysts with strong resistance against deposition of ABS.


Assuntos
Amônia , Óxido Nítrico , Sulfato de Amônio , Temperatura Baixa , Temperatura
10.
Environ Sci Technol ; 51(4): 2304-2311, 2017 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-28112911

RESUMO

The involvement of a great amount of active oxygen species is a crucial requirement for catalytic oxidation of benzene, because complete mineralization of one benzene molecule needs 15 oxygen atoms. Here, we disperse single silver adatoms on nanostructured hollandite manganese oxide (HMO) surfaces by using a thermal diffusion method. The single-atom silver catalyst (Ag1/HMO) shows high catalytic activity in benzene oxidation, and 100% conversion is achieved at 220 °C at a high space velocity of 23 000 h-1. The Mars-van Krevelen mechanism is valid in our case as the reaction orders for both benzene and O2 approach one, according to reaction kinetics data. Data from H2 temperature-programmed reduction and O core-level X-ray photoelectron spectra (XPS) reveal that Ag1/HMO possesses a great amount of active surface lattice oxygen available for benzene oxidation. Valence-band XPS and density functional theoretical calculations demonstrate that the single Ag adatoms have the upshifted 4d orbitals, thus facilitating the activation of gaseous oxygen. Therefore, the excellent activation abilities of Ag1/HMO toward both surface lattice oxygen and gaseous oxygen account for its high catalytic activity in benzene oxidation. This work may assist with the rational design of efficient metal-oxide catalysts for the abatement of volatile organic compounds such as benzene.


Assuntos
Benzeno , Prata , Catálise , Oxirredução , Oxigênio
11.
Environ Sci Technol ; 51(1): 473-478, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27977158

RESUMO

CeO2-based catalysts have attracted widespread attention in environmental-protection applications, including selective catalytic reduction (SCR) of NO by NH3, and their catalytic performance is often intimately associated with the supports used. However, the issue of how to choose the supports of such catalysts still remains unresolved. Herein, we systematically study the support effect in SCR over CeO2-based catalysts by using three representative supports, Al2O3, TiO2, and hexagonal WO3 (HWO), with different acidic and redox properties. HWO, with both acidic and reducible properties, achieves an optimal support effect; that is, CeO2/HWO exhibits higher catalytic activity than CeO2 supported on acidic Al2O3 or reducible TiO2. Transmission electron microscopy and X-ray diffraction techniques demonstrate that acidic supports (HWO and Al2O3) are favorable for the dispersion of CeO2 on their surfaces. X-ray photoelectron spectroscopy coupled with theoretical calculations reveals that reducible supports (HWO and TiO2) facilitate strong electronic CeO2-support interactions. Hence, the excellent catalytic performance of CeO2/HWO is mainly ascribed to the high dispersion of CeO2 and the optimal electronic CeO2-support interactions. This work shows that abundant Brønsted acid sites and excellent redox ability of supports are two critical requirements for the design of efficient CeO2-based catalysts.


Assuntos
Amônia/química , Cério/química , Catálise , Espectroscopia Fotoeletrônica , Difração de Raios X
12.
Environ Sci Technol ; 51(12): 7084-7090, 2017 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-28537706

RESUMO

The development of efficient alkali-based catalysts for the abatement of formaldehyde (HCHO), a ubiquitous air pollutant, is economically desirable. Here we comparatively study the catalytic performance of two single-atom catalysts, Na1/HMO and Ag1/HMO (HMO = Hollandite manganese oxide), in the complete oxidation of HCHO at low temperatures, in which the products are only CO2 and H2O. These catalysts are synthesized by anchoring single sodium ions or silver atoms on HMO(001) surfaces. Synchrotron X-ray diffraction patterns with structural refinement together with transmission electron microscopy images demonstrate that single sodium ions on the HMO(001) surfaces of Na1/HMO have the same local structures as silver atoms of Ag1/HMO. Catalytic tests reveal that Na1/HMO has higher catalytic activity in low-temperature oxidation of HCHO than Ag1/HMO. X-ray photoelectron spectra and soft X-ray absorption spectra show that the surface lattice oxygen of Na1/HMO has a higher electronic density than that of Ag1/HMO, which is responsible for its higher catalytic efficiency in the oxidation of HCHO. This work could assist the rational design of cheap alkali metal catalysts for controlling the emissions of volatile organic compounds such as HCHO.


Assuntos
Formaldeído , Prata , Sódio , Catálise , Oxirredução , Purificação da Água
13.
Environ Sci Technol ; 50(11): 5825-31, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27128185

RESUMO

Emissions of particulate matters (PMs) and volatile organic compounds (VOCs) from open burning of biomass often cause severe air pollution; a viable approach is to allow biomass to burn in a furnace to collectively control these emissions, but practical control technologies for this purpose are lacking. Here, we report a hollandite manganese oxide (HMO) catalyst that can efficiently control both typical PMs and VOCs emissions from biomass burning. The results reveal that typical alkali-rich PMs such as KCl particles are disintegrated and the K(+) ions are trapped in the HMO "single-walled" tunnels with a great trapping capacity. The K(+)-trapping HMO increases the electron density of the lattice oxygen and the redox ability, thus promoting the combustion of soot PMs and the oxidation of typical VOCs such as aldehydes and acetylates. This could pave a way to control emissions from biomass burning concomitant with its utilization for energy or heat generation.


Assuntos
Material Particulado , Compostos Orgânicos Voláteis , Poluentes Atmosféricos , Poluição do Ar , Biomassa
14.
Environ Sci Technol ; 50(21): 11951-11956, 2016 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-27689392

RESUMO

A good catalyst for efficiently controlling NOx emissions often demands strong resistance against alkali poisoning. Although the traditional ion-exchange model, based on acid-base reactions of alkalis with Brønsted acid sites, has been established over the past two decades, it is difficult to be used as a guideline to develop such an alkali-resistant catalyst. Here we establish a self-protection mechanism of deNOx catalysts against alkali poisoning by systematically studying the intrinsic nature of alkali resistance of V2O5/HWO (HWO = hexagonal WO3) that shows excellent resistance to alkali poisoning in selective catalytic reduction of NOx with NH3 (SCR). Synchrotron X-ray diffraction and absorption spectroscopies demonstrate that V2O5/HWO has spatially separated catalytically active sites (CASs) and alkali-trapping sites (ATSs). During the SCR process, ATSs spontaneously trap alkali ions such as K+, even if alkali ions initially block CASs, thus releasing CASs to realize the self-protection against alkali poisoning. X-ray photoelectron spectra coupled with theoretical calculations indicate that the electronic interaction between the alkali ions and ATSs with an energy saving is the driving force of the self-protection. This work provides a strategy to design alkali-resistant deNOx catalysts.


Assuntos
Álcalis , Álcalis/química , Catálise , Íons , Difração de Raios X
15.
Phys Chem Chem Phys ; 18(10): 7442-8, 2016 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-26898117

RESUMO

A crystalline material formed by parallel chains of silver atoms inside one-dimensional tunnels of hollandite manganese dioxide, Ag-αMnO2, is investigated through first-principles total energy calculations. Two different magnetic phases have been identified; one structure containing linear Ag chains with an antiferromagnetic ordering in the direction perpendicular to the MnO2 tunnels for T = 0 K (I4/m) and another configuration with zigzag Ag chains in a non-magnetic regime for higher temperatures (P21/c). According to phonon dispersions, both structures are stable. On the other hand, the structure with linear Ag chains in the non-magnetic state is unstable. A critical temperature of Tc≃ 125 K for the magnetostructural phase transition between the two stable structures I4/m and P21/c is predicted.

16.
Chemistry ; 21(48): 17397-402, 2015 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-26448583

RESUMO

Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation at low temperature. This work provides a general strategy for designing atomically dispersed noble-metal catalysts with highly dense active sites.

17.
Chemistry ; 21(27): 9619-23, 2015 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-25974631

RESUMO

The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low-temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod-shaped morphology and one-dimensional tunnels. Electron microscopy and synchrotron X-ray diffraction determine the surface and crystal structures of the one-dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X-ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi-tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions.

18.
Environ Sci Technol ; 49(4): 2384-90, 2015 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-25634796

RESUMO

Formaldehyde (HCHO) is a prior pollutant in both indoor and outdoor air, and catalytic oxidation proves the most promising technology for HCHO abatement. For this purpose, supported metal catalysts with single silver atoms confined at 4-fold O4-terminated surface hollow sites of a hollandite manganese oxide (HMO) as catalytic centers were synthesized and investigated in the complete oxidation of HCHO. Synchrotron X-ray diffraction patterns, X-ray absorption spectra, and electron diffraction tomography revealed that geometric structures and electronic states of the catalytic centers were tuned by the changes of HMO structures via controllable metal-support interactions. The catalytic tests demonstrated that the catalytically active centers with high electronic density of states and strong redox ability are favorable for enhancement of the catalytic efficiency in the HCHO oxidation. This work provides a strategy for designing efficient oxidation catalysts for controlling air pollution.


Assuntos
Poluentes Atmosféricos/química , Formaldeído/química , Prata/química , Poluição do Ar/prevenção & controle , Poluição do Ar em Ambientes Fechados/prevenção & controle , Catálise , Compostos de Manganês/química , Oxirredução , Óxidos/química , Propriedades de Superfície , Espectroscopia por Absorção de Raios X , Difração de Raios X
19.
Environ Sci Technol ; 49(11): 7042-7, 2015 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-25941972

RESUMO

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.


Assuntos
Álcalis/química , Minerais/química , Catálise , Elétrons , Íons/química , Espectroscopia por Absorção de Raios X , Difração de Raios X
20.
Environ Sci Technol ; 49(24): 14460-5, 2015 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-26587749

RESUMO

The development of catalysts with simultaneous resistance to alkalis and sulfur poisoning is of great importance for efficiently controlling NOx emissions using the selective catalytic reduction of NOx with NH3 (SCR), because the conventional V2O5/WO3-TiO2 catalysts often suffer severe deactivation by alkalis. Here, we support V2O5 on a hexagonal WO3 (HWO) to develop a V2O5/HWO catalyst, which has exceptional resistance to alkali and sulfur poisoning in the SCR reactions. A 350 µmol g(-1) K(+) loading and the presence of 1,300 mg m(-3) SO2 do not almost influence the SCR activity of the V2O5/HWO catalyst, and under the same conditions, the conventional V2O5/WO3-TiO2 catalysts completely lost the SCR activity within 4 h. The strong resistance to alkali and sulfur poisoning of the V2O5/HWO catalysts mainly originates from the hexagonal structure of the HWO. The HWO allows the V2O5 to be highly dispersed on the external surfaces for catalyzing the SCR reactions and has the relatively smooth surfaces and the size-suitable tunnels specifically for alkalis' diffusion and trapping. This work provides a useful strategy to develop SCR catalysts with exceptional resistance to alkali and sulfur poisoning for controlling NOx emissions from the stationary source and the mobile source.


Assuntos
Óxidos de Nitrogênio/química , Enxofre/química , Tungstênio/química , Compostos de Vanádio/química , Álcalis/química , Catálise , Titânio/química , Emissões de Veículos/prevenção & controle
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