RÉSUMÉ
In this research, a range of Pt/CeO2 catalysts featuring varying Pt-O-Ce bond contents were developed by modulating the oxygen vacancies of the CeO2 support for toluene abatement. The Pt/CeO2-HA catalyst generated a maximum quantity of Pt-O-Ce bonds (possessed the strongest metal-support interaction), as evidenced by the visible Raman results, which demonstrated outstanding toluene catalytic performance. Additionally, the UV Raman results revealed that the strong metal-support interaction stimulated a substantial increase in oxygen vacancies, which could facilitate the activation of gaseous oxygen to generate abundant reactive oxygen species accumulated on the Pt/CeO2-HA catalyst surface, a conclusion supported by the H2-TPR, XPS, and toluene-TPSR results. Furthermore, the results from quasi-in situ XPS, in situ DRIFTS, and DFT indicated that the Pt/CeO2-HA catalyst with a strong metal-support interaction led to improved mobility of reactive oxygen species and lower oxygen activation energies, which could transfer a large number of activated reactive oxygen species to the reaction interface to participate in the toluene oxidation, resulting in the relatively superior catalytic performance. The approach of tuning the metal-support interaction of catalysts offers a promising avenue to develop highly active catalysts for toluene degradation.
RÉSUMÉ
Strong metal-support interaction (SMSI), which has drawn widespread attention in heterogeneous catalysis, is thought to significantly affect the catalytic performance for volatile organic chemical (VOC) abatement. In the present study, strong interactions between platinum and ceria are constructed by modulating the oxygen vacancy concentration of CeO2 through a NaBH4 reduction method. For a catalyst with higher content of oxygen vacancy, more electrons would transfer from ceria to Pt, which is attributed to the stronger effect of SMSI. The obtained electron-richer Pt sites exhibit higher ability for toluene activation, contributing to better performance for toluene oxidation. On the other hand, the stronger metal-support interaction would facilitate CeOx species migrating to the Pt nanoparticle surface and forming an encapsulated structure. Smaller Pt dispersion leads to fewer sites for toluene adsorption and activation, which is to the disadvantage of the reaction. Therefore, taking the negative and positive effects together, the Pt/CeO2-0.5 catalyst has the highest catalytic performance for toluene abatement. Our study provides new insights into strong metal-support interaction on toluene oxidation and contributes to designing noble metal catalysts for VOC abatement.
RÉSUMÉ
It is a great challenge to remove VOCs and NOx simultaneously from flue gas in nonelectric industries. This study focuses on the construction of Fe-MnO2 catalysts that perform well in the simultaneous removal of toluene and NOx at low temperatures. Utilizing the Fe-induced phase transition of MnO2, Fe-MnO2-F&R catalysts with a composite morphology of nanoflowers and nanorods were successfully prepared that provided an abundant microporous structure to facilitate the diffusion of molecules of different sizes. Through in-depth investigation of the active sites and reaction mechanism, we discovered that Fe-induced phase transition could modulate the surface acidity of Fe-MnO2-F&R. The higher concentration of surface Mn4+ provided numerous Brønsted acid sites, which effectively promoted the activation of toluene to reactive intermediates, such as benzyl alcohol/benzoate/maleic acid. Simultaneously, Fe provided a large number of Lewis acid sites that anchor and activate NH3 species, thereby inhibiting NH3 nonselective oxidation. Furthermore, additional Brønsted acid sites were generated during the simultaneous reaction process, enhancing toluene activation. Consequently, the simultaneous removal of toluene and NOx was achieved through regulation of the physical structure and the concentration of acidic sites. The present work provides new insights into the rational design of bifunctional catalysts for the synergistic control of VOCs and NOx emissions.
Sujet(s)
Toluène , Toluène/composition chimique , Composés du manganèse/composition chimique , Catalyse , Oxydes/composition chimique , Transition de phase , Oxydes d'azote/composition chimique , Basse températureRÉSUMÉ
Different Br-doped metal-organic frameworks (MOFs) derived (Brx@UiO-66) have been prepared by heat treatment using UiO-66 as the precursor. The experimental results showed that Br0.2@UiO-66 exhibited the best photocatalytic oxidation and adsorption performances toward acetaldehyde. In the dynamic system, the acetaldehyde removal rate and adsorption capacity of Br0.2@UiO-66 were 93.2 % and 230.59 mg/g, respectively. The improvement of the photocatalytic performance can be attributed to the presence of Br ions and CBr bonds, which facilitated the rapid separation of electrons and holes and the production of â¢O2-. In addition, Br0.2@UiO-66 had a better adsorption performance than 300UiO-66, mainly because of the increased Lewis acidity of the metal active sites due to Br doping. Radical capture experiments indicated that â¢O2- and e- were the primary active substances in acetaldehyde oxidation, and allowed establishing the possible mechanism of acetaldehyde oxidation. This work shows that MOFs can have high catalytic oxidation performances toward volatile organic compounds (VOCs) while retaining their adsorption capacity, and can be used for practical applications in the adsorption-catalytic integrated degradation of VOCs.
RÉSUMÉ
Atom-doped Co3O4 catalysts loaded with Ag were examined as cost-effective catalysts for methane oxidation. The synthesized Ag/Co2NiOx catalysts exhibited distinctive surface characteristics in contrast with Ag/Co3O4 and Ag/Co2CuOx catalysts prepared using a similar method. Characterization results unveiled that Ag/Co2NiOx featured a higher presence of active surface oxygen species, lattice defects, a larger surface area, and enhanced reducibility. A methane oxidation catalytic performance followed the sequence: Ag/Co2NiOx > Ag/Co3O4 > Ag/Co2CuOx. The investigation delved into methane degradation pathways on the surfaces of three catalysts, examining their behavior under both aerobic and anaerobic atmospheres through in-situ DRIFTS analysis. Furthermore, introducing Ag showed a marked positive effect on Co-Ni mixed oxide, inducing electron transfer and a more active electron system, whereas it exhibited an inverse impact within the surface of Co-Cu mixed oxide. This work provides innovative perspectives on the development of forthcoming environmental catalysts.
RÉSUMÉ
With the development of industries, air pollution in north-central Henan is becoming increasingly severe. The TROPOspheric Monitoring Instrument (TROPOMI) provides nitrogen dioxide (NO2) column densities with high spatial resolution. Based on TROPOMI, in this study, the nitrogen oxides (NOx) emissions in north-central Henan are derived and the emission hotspots are identified with the flux divergence method (FDM) from May to September 2021. The results indicate that Zhengzhou has the highest NOx emissions in north-central Henan. The most prominent hotspots are in Guancheng Huizu District (Zhengzhou) and Yindu District (Anyang), with emissions of 448.4 g/s and 300.3 g/s, respectively. The Gaussian Mixture Model (GMM) is applied to quantify the characteristics of emission hotspots, including the diameter, eccentricity, and tilt angle, among which the tilt angle provides a novel metric for identifying the spatial distribution of pollution sources. Furthermore, the results are compared with the CAMS global anthropogenic emissions (CAMS-GLOB-ANT) and Multi-resolution Emission Inventory model for Climate and air pollution research (MEIC), and they are generally in good agreement. However, some point sources, such as power plants, may be missed by both inventories. It is also found that for emission hotspots near transportation hubs, CAMS-GLOB-ANT may not have fully considered the actual traffic flow, leading to an underestimation of transportation emissions. These findings provide key information for the accurate implementation of pollution prevention and control measures, as well as references for future optimization of emission inventories. Consequently, deriving NOx emissions from space, quantifying the characteristics of emission hotspots, and combining them with bottom-up inventories can provide valuable insights for targeted emission control.
RÉSUMÉ
It is a promising research direction to develop catalysts with high stability and ozone utilization for low-temperature ozone catalytic oxidation of VOCs. While bimetallic catalysts exhibit excellent catalytic activity compared with conventional single noble metal catalysts, limited success has been achieved in the influence of the bimetallic effect on the stability and ozone utilization of metal catalysts. Herein, it is necessary to systematically study the enhancement effect in the ozone catalytic reaction induced by the second metal. With a simple continuous impregnation method, a platinum-cerium bimetallic catalyst is prepared. Also highlighted are studies from several aspects of the contribution of the second metal (Ce) to the stability and ozone utilization of the catalysts, including the "electronic effect" and "geometric effect". The synergistic removal rate of toluene and ozone is nearly 100% at 30 °C, and it still shows positive stability after high humidity and a long reaction time. More importantly, the instructive significance, which is the in-depth knowledge of enhanced catalytic mechanism of bimetallic catalysts resulting from a second metal, is provided by this work.
Sujet(s)
Cérium , Ozone , Oxydoréduction , Métaux , CatalyseRÉSUMÉ
Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.
Sujet(s)
Ammoniac , Cuivre , Oxydoréduction , Cuivre/composition chimique , Ammoniac/composition chimique , Catalyse , Nanotubes de carbone/composition chimique , Polluants atmosphériques/composition chimique , Température , Modèles chimiquesRÉSUMÉ
Photothermal catalysis exhibits promising prospects to overcome the shortcomings of high-energy consumption of traditional thermal catalysis and the low efficiency of photocatalysis. However, there is still a challenge to develop catalysts with outstanding light absorption capability and photothermal conversion efficiency for the degradation of atmospheric pollutants. Herein, we introduced the Co3O4 layer and Pt nanoclusters into the three-dimensional (3D) porous membrane through the atomic layer deposition (ALD) technique, leading to a Pt/Co3O4/AAO monolithic catalyst. The 3D ordered nanochannel structure can significantly enhance the solar absorption capacity through the light-trapping effect. Therefore, the embedded Pt/Co3O4 catalyst can be rapidly heated and the O2 adsorbed on the Pt clusters can be activated to generate sufficient O2- species, exhibiting outstanding activity for the diverse VOCs (toluene, acetone, and formaldehyde) degradation. Optical characterization and simulation calculation confirmed that Pt/Co3O4/AAO exhibited state-of-the-art light absorption and a notable localized surface plasmon resonance (LSPR) effect. In situ diffuse reflectance infrared Fourier transform spectrometry (in situ DRIFTS) studies demonstrated that light irradiation can accelerate the conversion of intermediates during toluene and acetone oxidation, thereby inhibiting byproduct accumulation. Our finding extends the application of AAO's optical properties in photothermal catalytic degradation of air pollutants.
Sujet(s)
Acétone , Cobalt , Oxydes , Toluène , Oxydoréduction , Catalyse , Toluène/analyse , Toluène/composition chimiqueRÉSUMÉ
Daily use of passenger vehicles leads to considerable emission of volatile organic compounds (VOCs), which are key precursors to the ground-level ozone pollution. While evaporative and tailpipe emission of VOCs from the passenger vehicles can be eliminated largely, or even completely, by electrification, VOCs emission from the use of coatings in auto-repair is unavoidable and has long been ignored. Here, we present for the first time, to the best of our knowledge, a comprehensive investigation on the emission factors and process-specified characteristics of VOCs from auto-repair painting, based on field measurements over 15 representative auto-repair workshops in the Pearl-River-Delta area, China. Replacement of solvent-borne coatings with water-borne counterparts, which was only achieved partially in the Basecoat step but not in the Putty, Primer and Clearcoat steps, could reduce the per automobile VOCs emission from 756.5 to 489.6 g and the per automobile ozone formation potential (OFP) from 2776.5 to 1666.4 g. Implementation of exhaust after-treatment led to a further reduction of the per automobile VOCs emission to 340.9 g, which is still ca. 42% higher than that from the state-of-art painting processes for the manufacture of passenger vehicles. According to the analysis of VOCs compositions, the Putty process was dominated by the emission of styrene, while Primer, Basecoat (solvent-borne) and Clearcoat steps were all characterized by the emission of n-butyl acetate and xylenes. By contrast, water-borne Basecoat step showed a prominent emission of n-amyl alcohol. Notably, for the full painting process to repair an automobile, n-butyl acetate emerged as the most abundant species in the VOCs emission, whereas xylenes contributed most significantly to the OFP. Scenario analysis suggested that reducing VOCs contents in the coatings, as well as improving the after-treatment efficiency, were highly potential solutions for effective reduction of VOCs emission from auto-repair. Our study contributes to an update of industrial inventories of VOCs emission, and may provide valuable insights for reducing VOCs emission and OFPs from the auto-repair industry.
RÉSUMÉ
TiO2, ZrO2 and a series of TiO2-ZrO2 (TxZ1, x means the atomic ratio of Ti/Zr = 10, 5, 1, 0.2 and 0.1) composite oxide supports were prepared through co-precipitation, and then 3 wt% Co was loaded through wetness impregnation methods. The obtained 3 wt% Co/TiO2 (3CT), 3 wt% Co/ZrO2 (3CZ) and 3 wt% Co/TxZ1 (3CTxZ1) catalysts were evaluated for the oxidative ethane dehydrogenation reaction with CO2 (CO2-ODHE) as a soft oxidant. 3CT1Z1 catalyst exhibits excellent catalytic properties, with C2H4 yield, C2H6 conversion and CO2 conversion about 24.5 %, 33.8 % and 18.0 % at 650 °C, respectively. X-Ray Diffraction (XRD), in-situ Raman, UV-vis diffuse reflectance spectra (UV-vis DRS), H2 temperature-programmed reduction (H2-TPR), Electron paramagnetic resonance (EPR) and quasi in-situ X-ray Photoelectron Spectroscopy (XPS) have been utilized to thoroughly characterize the investigated catalysts. The results revealed that 3CT1Z1 produced TiZrO4 solid solution with more metal defect sites and oxygen vacancies (Ov), promoting the formation of Co2+-TiZrO4 structure. Furthermore, the presence of Ov and Ti3+can facilitate the high dispersion and stabilization of Co2+, as well as suppressing the severe reduction of Co2+, leading to superior ethane oxidative dehydrogenation activity. Besides, less Co0 is beneficial to ODHE reaction, because of its promotion effects for reverse water gas shift reaction; however, more Co0 results in dry reforming reaction (DRE). This work will shed new lights for the design and preparation of highly efficient catalysts for ethylene production.
RÉSUMÉ
Waste resource utilization of petroleum coke is crucial for achieving global carbon emission reduction. Herein, a series of N-doped microporous carbons were fabricated from petroleum coke using a one-pot synthesis method. The as-prepared samples had a large specific surface area (up to 2512 m2/g), a moderate-high N content (up to 4.82 at.%), and high population (55%) of ultra-micropores (<0.7 nm). Regulating the N content and ultra-microporosity led to efficient CO2 adsorption and separation. At ambient pressure, the optimal N-doped petroleum coke-based microporous carbon exhibited the highest CO2 uptake of 4.25 mmol/g at 25°C and 6.57 mmol/g at 0°C. These values are comparable or even better than those of numerous previously reported adsorbents prepared by multistep synthesis, primarily due to the existence of ultra-micropores. The sample exhibited excellent CO2/N2 selectivity at 25°C owing to the abundant basic pyridinic and pyrrolic N species; and showed superior CO2 adsorption-desorption cycling performance, which was maintained at 97% after 10 cycles at 25°C. Moreover, petroleum coke-based microporous carbon, with a considerably high specific surface area and hierarchical pore structure, exhibited excellent electrochemical performance over the N-doped sample, maintaining a favorable specific capacitance of 233.25 F/g at 0.5 A/g in 6 mol/L KOH aqueous electrolyte. This study provides insight into the influence of N-doping on the porous properties of petroleum coke-based carbon. Furthermore, the as-prepared carbons were found to be promising adsorbents for CO2 adsorption, CO2/N2 separation and electrochemical application.
Sujet(s)
Carbone , Coke , Carbone/composition chimique , Dioxyde de carbone/composition chimique , Adsorption , PorositéRÉSUMÉ
The printing industry has always been the key source of volatile organic compound(VOC) emissions in China. However, owing to the complexity of raw materials and processes, the fine emission inventory and its future emission reduction potential of VOCs from the printing industry have not been well characterized. In this study, the existing VOCs emission factors of the printing industry were improved, considering the neglected semi/intermediate VOCs(S/IVOCs). An emissions inventory of VOCs from the printing industry in the period of 2011-2020 in China was compiled. Through scenario analysis, the emission of VOCs under different scenarios in 2030 was predicted, and the emission reduction potential was analyzed. VOCs emissions from the printing industry in China increased first and then decreased in the period of 2011-2020. Compared with that in 2011, VOCs emissions increased by 29.6% in 2020, with an average annual growth rate of 3.0%. This was mainly due to the increasing consumption demand in the printing industry market and the lack of effective measures for integrated management of VOCs. The VOCs emission of the printing industry in China in 2020 was 861 Gg. Gravure printing and packaging processing were the two most important processes, accounting for 52.0% and 28.7%, respectively. Guangdong, Jiangsu, and Zhejiang were the largest contributors to VOC emissions, accounting for 44.12% of the total emissions. VOCs emissions of the printing industry in 2030 were 1187 Gg, 684 Gg, and 362 Gg for the baseline scenario, the general control scenario, and the strict control scenario, respectively. Compared to that in 2020, emissions under different control scenarios in 2030 increased by 37.9% and decreased by 20.6% and 57.9%, respectively. Gravure printing and packaging processing are still the focus of emission reduction.
RÉSUMÉ
Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni-N4 and Fe-N4 pair sites is designed for boosting gas-solid CO2 reduction with H2 O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)-N-C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16â µmol g-1 h-1 ), CH4 (135.35â µmol g-1 h-1 ) and CH3 OH (59.81â µmol g-1 h-1 ), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe-N-C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)-N-C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni-N-N-Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar-driven photothermal CO2 reduction to initial CO production.
RÉSUMÉ
Volatile organic compounds (VOCs) are one of the main classes of air pollutants, and it is important to develop efficient adsorbents to remove them from the atmosphere. To do this most efficiently, we need to understand the mechanism of VOC adsorption. In this work, we described how the metal organic framework (MOF), ZIF-8, was used as a precursor to generate MOF derivatives (Zn-GC) through temperature-controlled calcination, which had adjustable metal sites and hierarchical pore structure. It was used as a model adsorbent to study the adsorption and desorption characteristics of different VOCs. Zn-GC-850 with developed pores exhibited higher adsorption performance for the benzene series, whereas Zn-GC-650 with more metal sites had a better adsorption capacity for oxygen-containing VOCs. By tuning the molecular structure of the VOCs, we revealed the adsorption mechanism of different VOCs at the molecular level. The more developed hierarchical pore structure obtained at the higher temperature facilitates the diffusion of the benzene series, and the noncovalent interaction between their methyl group(s) and the carbonized MOF derivatives improves the adsorption affinity; while the higher exposure of Zn sites obtained at lower temperature favors the adsorption of oxygen-containing VOCs by Zn-O bonds. The mass transfers of VOCs and the role of the adsorbent were simulated by multiple theoretical models. This study strengthens the basis for the design and optimization of the adsorbent and catalyst for VOCs treatment.
Sujet(s)
Réseaux organométalliques , Composés organiques volatils , Composés organiques volatils/composition chimique , Benzène , Adsorption , Métaux , OxygèneRÉSUMÉ
Ammonia-mediated selective catalytic reduction (NH3-SCR) is currently the key approach to abate nitrogen oxides (NOx) emitted from heavy-duty lean-burn vehicles. The state-of-art NH3-SCR catalysts, namely, copper ion-exchanged chabazite (Cu-CHA) zeolites, perform rather poorly at low temperatures (below 200 °C) and are thus incapable of eliminating effectively NOx emissions under cold-start conditions. Here, we demonstrate a significant promotion of low-temperature NOx reduction by reinforcing the dynamic motion of zeolite-confined Cu sites during NH3-SCR. Combining complex impedance-based in situ spectroscopy (IS) and extended density-functional tight-binding molecular dynamics simulation, we revealed an environment- and temperature-dependent nature of the dynamic Cu motion within the zeolite lattice. Further coupling in situ IS with infrared spectroscopy allows us to unravel the critical role of monovalent Cu in the overall Cu mobility at a molecular level. Based on these mechanistic understandings, we elicit a boost of NOx reduction below 200 °C by reinforcing the dynamic Cu motion in various Cu-zeolites (Cu-CHA, Cu-ZSM-5, Cu-Beta, etc.) via facile postsynthesis treatments, either in a reductive mixture at low temperatures (below 250 °C) or in a nonoxidative atmosphere at high temperatures (above 450 °C).
Sujet(s)
Zéolites , Zéolites/composition chimique , Cuivre , Ammoniac/composition chimique , Oxydes d'azote/composition chimique , Température , CatalyseRÉSUMÉ
China became the world leader in crude oil processing capacity in 2021. However, petroleum refining generates significant volatile organic compound (VOC) emissions, and the composite source profile, source-specific emission factors, and emission inventories of VOCs in the petroleum refining industry remain poorly understood. In this study, we focused on Guangdong, China's major province for crude oil processing, and systematically evaluated the historical emissions and reduction of VOCs in the petroleum refining industry from 2001 to 2020. We accomplished this by establishing local source-specific emission factors and composite source profiles. Finally, we quantitatively assessed the potential impact of these emissions on ozone and secondary organic aerosol formation. Our results revealed that VOC emissions from the petroleum refining industry in Guangdong followed an increasing-then-decreasing trend from 2001 to 2020, peaking at 37.3 Gg in 2016 and declining to 18.7 Gg in 2020. Storage tanks and wastewater collection and treatment remained the two largest sources, accounting for 41.9 %-53.4 % and 20.6 %-27.5 % of total emissions, respectively. Initially, Guangzhou and Maoming made the most significant contributions, with Huizhou becoming a notable contributor after 2008. Emission reduction efforts for VOCs in Guangdong's petroleum refining industry began showing results in 2017, with an average annual VOC emission reduction of 21.5 Gg from 2017 to 2020 compared to the unabated scenario. Storage tanks, wastewater collection and treatment, and loading operations were the primary sources of emission reduction, with significant contributions from Maoming, Huizhou, and Guangzhou. Alkanes made the largest contribution to VOC emissions, while alkenes/alkynes and aromatics comprised the most significant portions of ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAP). We also estimated VOC emissions and reduction from petroleum refining for China from 2001 to 2020, and measures such as "one enterprise, one policy" and deep control strategies could reduce emissions by at least 103.9 Gg.
RÉSUMÉ
The low-temperature mechanism of chabazite-type small-pore Cu-SSZ-13 zeolite, a state-of-the-art catalyst for ammonia-assisted selective reduction (NH3-SCR) of toxic NOx pollutants from heavy-duty vehicles, remains a debate and needs to be clarified for further improvement of NH3-SCR performance. In this study, we established experimental protocols to follow the dynamic redox cycling (i.e., CuII â CuI) of Cu sites in Cu-SSZ-13 during low-temperature NH3-SCR catalysis by in situ ultraviolet-visible spectroscopy and in situ infrared spectroscopy. Further integrating the in situ spectroscopic observations with time-dependent density functional theory calculations allows us to identify two cage-confined transient states, namely, the O2-bridged Cu dimers (i.e., µ-η2:η2-peroxodiamino dicopper) and the proximately paired, chemically nonbonded CuI(NH3)2 sites, and to confirm the CuI(NH3)2 pair as a precursor to the O2-bridged Cu dimer. Comparative transient experiments reveal a particularly high reactivity of the CuI(NH3)2 pairs for NO-to-N2 reduction at low temperatures. Our study demonstrates direct experimental evidence for the transient formation and high reactivity of proximately paired CuI sites under zeolite confinement and provides new insights into the monomeric-to-dimeric Cu transformation for completing the Cu redox cycle in low-temperature NH3-SCR catalysis over Cu-SSZ-13.
Sujet(s)
Zéolites , Théorie de la fonctionnelle de la densité , Zéolites/composition chimique , Oxydoréduction , Spectrophotométrie IR , Catalyse , Ammoniac/composition chimiqueRÉSUMÉ
Catalytic complete oxidation is an efficient approach to reducing methane emissions, a significant contributor to global warming. This approach requires active catalysts that are highly resistant to sintering and water vapor. In this work, we demonstrate that Pd nanoparticles confined within silicalite-1 zeolites (Pd@S-1), fabricated using a facile in situ encapsulation strategy, are highly active and stable in catalyzing methane oxidation and are superior to those supported on the S-1 surface due to a confinement effect. The activity of the confined Pd catalysts was further improved by co-confining a suitable amount of Ce within the S-1 zeolite (PdCe0.4@S-1), which is attributed to confinement-reinforced Pd-Ce interactions that promote the formation of oxygen vacancies and highly reactive oxygen species. Furthermore, the introduction of Ce improves the hydrophobicity of the S-1 zeolite and, by forming Pd-Ce mixed oxides, inhibits the transformation of the active PdO phase to inactive Pd(OH)2 species. Overall, the bimetallic PdCe0.4@S-1 catalyst delivers exceptional outstanding activity and durability in complete methane oxidation, even in the presence of water vapor. This study may provide new prospects for the rational design of high-performance and durable Pd catalysts for complete methane oxidation.
RÉSUMÉ
Near-surface ozone pollution is becoming an increasingly serious air quality issue in China, especially in "2 + 26" cities (Beijing-Tianjin-Hebei and nearby cities). HN2 + 26 cities ("2 + 26" cities of Henan Province) are located in the south of "2 + 26" cities, with frequent and severe ozone pollution events in recent years. This study investigated the diurnal evolution characteristics of ozone formation sensitivity (OFS) of HN2 + 26 cities from May to September in 2021 by the innovative combination of Global Ozone Monitoring Experiment (GOME-2B) and Ozone Monitoring Instrument (OMI) satellite data, and assessed the impact of ozone pollution control measures (OPCMs) implemented from June 26 to July 1, 2021. The localized FNR (ratio of formaldehyde to nitrogen dioxide of satellite measurement) threshold (1.4-2.55) was established, and it was found that OFS in May-September 2021 was mainly in VOCs-limited regime in the morning (â¼10:00), while transitional/NOx-limited regime in the afternoon (â¼14:00). Three periods (before, during and after the OPCMs) were divided to evaluate the impact of OPCMs on OFS. It was indicated that OPCMs had no impact on the morning OFS, but had a significant impact on the afternoon OFS. Specifically, the OFS in two industrial cities Xinxiang (XX) and Zhengzhou (ZZ) shifted from transitional regime to NOx-limited regime after the OPCMs. We further investigated OFS differences between urban and suburban areas and found that OFS shift of XX only existed in urban areas, while that of ZZ existed in both urban and suburban areas. We compared their measures and found that it is effective to take hierarchical control measures on different levels of ozone pollution days to alleviate ozone pollution. This study provides an improved understanding of diurnal evolution characteristics of OFS and the impacts of OPCMs on it, which will provide a theoretical basis for formulating more scientific ozone pollution control policies.