Electron transferring with oxygen defects on Ni-promoted Pd/Al2O3 catalysts for low-temperature lean methane combustion.

Methane (CH4) is the second most consequential greenhouse gas after CO2, with a substantial global warming potential. The CH4 catalytic combustion offers an efficient method for the elimination of CH4. However, improving the catalytic performance of Pd-based materials for low-temperature CH4 combustion remains a big challenge. In this study, we synthesized an enhanced Pd/5NiAlOx catalyst that demonstrated superior catalytic activity and improved water resistance compared to the Pd/Al2O3 catalyst. Specifically, the T90 was decreased by over 100 °C under both dry and wet conditions. Introducing Ni resulted in an enormously enhanced number of oxygen defects on the obtained 5NiAlOx support. This defect-rich support facilitates the anchoring of PdO through increased electron transfer, thereby inhibiting the production of high-valence Pd(2+δ)+ and stimulating the generation of unsaturated Pd sites. Pd0 can effectively activate surface oxygen and PdO plays a significant role in activating CH4, resulting in high activity for Pd/5NiAlOx. On the other hand, the increased water resistance of Pd/5NiAlOx was mainly due to the generation of *OOH species and the lower accumulation of surface -OH species during the reaction process.

Precisely Identifying the Sources of Magnetic Particles by Hierarchical Classification-Aided Isotopic Fingerprinting.

Magnetic particles (MPs), with magnetite (Fe3O4) and maghemite (γ-Fe2O3) as the most abundant species, are ubiquitously present in the natural environment. MPs are among the most applied engineered particles and can be produced incidentally by various human activities. Identification of the sources of MPs is crucial for their risk assessment and regulation, which, however, is still an unsolved problem. Here, we report a novel approach, hierarchical classification-aided stable isotopic fingerprinting, to address this problem. We found that naturally occurring, incidental, and engineered MPs have distinct Fe and O isotopic fingerprints due to significant Fe/O isotope fractionation during their generation processes, which enables the establishment of an Fe-O isotopic library covering complex sources. Furthermore, we developed a three-level machine learning model that not only can distinguish the sources of MPs with a high precision (94.3%) but also can identify the multiple species (Fe3O4 or γ-Fe2O3) and synthetic routes of engineered MPs with a precision of 81.6%. This work represents the first reliable strategy for the precise source tracing of particles with multiple species and complex sources.

Creating Atomically Iridium-Doped PdOx Nanoparticles for Efficient and Durable Methane Abatement.

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdOx nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdOx nanoparticles, creating an Ir4f-O-Pdcus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdOx and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir4f-O-Pdcus, reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr0.1/S-1 showed outstanding low-temperature activity for methane combustion (T50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr0.1/S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al2O3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NOx with NH3.

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet-visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites.

Combined Experimental and Density Functional Theory Study on the Mechanism of the Selective Catalytic Reduction of NO with NH3 over Metal-Free Carbon-Based Catalysts.

Metal-free carbon-based catalysts are attracting much attention in the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR). However, the mechanism of the NH3-SCR reaction on carbon-based catalysts is still controversial, which severely limits the development of carbon-based SCR catalysts. Herein, we successfully reconstructed carbon-based catalysts through oxidation treatment with nitric acid, thereby enhancing their low-temperature activity in NH3-SCR. Combining experimental results and density functional theory (DFT) calculations, we proposed a previously unreported NH3-SCR reaction mechanism over carbon-based catalysts. We demonstrated that C-OH and C-O-C groups not only effectively activate NH3 but also remarkedly promote the decomposition of intermediate NH2NO. This study enhances the understanding of the NH3-SCR mechanism on carbon-based catalysts and paves the way to develop low-temperature metal-free SCR catalysts.

Identification of Direct Anchoring Sites for Monoatomic Dispersion of Precious Metals (Pt, Pd, Ag) on CeO2 Support.

Monoatomic dispersion of precious metals on the surface of CeO2 nanocrystals is a highly practical approach for dramatically reducing the usage of precious metals while exploiting the unique properties of single-atom catalysts. However, the specific atomic sites for anchoring precious metal atoms on the CeO2 support and underlying chemical mechanism remain partially unknown. Herein, we show that the terminal hydroxyls on the (100) surface are the most stable sites for anchoring Ag atoms on CeO2 , indicating that CeO2 nanocubes are the most efficient substrates to achieve monoatomic dispersion of Ag. Importantly, the newly identified chemical mechanism for single-metal-atom dispersion on CeO2 nanocubes appears to be generic and can thus be extended to other precious metals (Pt and Pd). In fact, our experiments also show that atomically dispersed Pt/Pd species exhibit morphology- and temperature-dependent CO selectivity in the catalytic CO2 hydrogenation reaction.

Efficient Pt/KFI zeolite catalysts for the selective catalytic reduction of NOx by hydrogen.

Aiming at purification of NOx from hydrogen internal combustion engines (HICEs), the hydrogen selective catalytic reduction (H2-SCR) reaction was investigated over a series of Pt/KFI zeolite catalysts. H2 can readily reduce NOx to N2 and N2O while O2 inhibited the deNOx efficiency by consuming the reductant H2. The Pt/KFI zeolite catalysts with Pt loading below 0.1 wt.% are optimized H2-SCR catalysts due to its suitable operation temperature window since high Pt loading favors the H2-O2 reaction which lead to the insufficient of reactants. Compared to metal Pt0 species, Ptδ+ species showed lower activation energy of H2-SCR reaction and thought to be as reasonable active sites. Further, Eley-Rideal (E-R) reaction mechanism was proposed as evidenced by the reaction orders in kinetic studies. Last, the optimized reactor was designed with hybrid Pt/KFI catalysts with various Pt loading which achieve a high NOx conversion in a wide temperature range.

Design of Ca-type todorokite catalysts with highly active for the selective reduction of NOx by NH3 at low temperatures.

Ca-type todorokite catalysts were designed and prepared by a simple redox method and applied to the selective reduction of NOx by NH3 (NH3-SCR) for the first time. Compared with the Na-type manjiroite prepared by the same method, the todorokite catalysts with different Mn/Ca ratios showed greatly improved catalytic activity for NOx reduction. Among them, Mn8Ca4 catalyst exhibited the best NH3-SCR performance, achieving 90% NOx conversion within temperature range of 70-275°C and having a high sulphur resistance. Compared to the Na-type manjiroite sample, Ca-type todorokite catalysts possessed an increased size of tunnel, resulting in a larger specific surface area. As increased the amounts of Ca doping, the Na content in Ca-type todorokite catalysts significantly decreased, providing larger amounts of Brønsted acid sites for NH3 adsorption to produce NH4+. The NH4+ species were highly active for reaction with NO + O2, playing a determining role in NH3-SCR process at low temperatures. Meanwhile, larger amounts of surface adsorbed oxygen contained over the Ca-doping samples than that over Na-type manjiroite, promoting the oxidation of NO and fast SCR processes. Over the Ca-type todorokite catalysts, furthermore, nitrates produced during the flow of NO + O2, were more active for reaction with NH3 than that over Na-type manjiroite, benefiting the occurrence of NH3-SCR process. This study provides novel insights into the design of NH3-SCR catalysts with high performance.

Cemento-Osseous Dysplasia: A Detailed Comparison of the 2005 and 2017 WHO Classifications and Case Analysis.

The WHO substantially redefined cemento-osseous dysplasia (COD) in 2017. The descriptions of COD in the 2005 and 2017 WHO classifications are quite different. In this study, we compared the difference in COD description between the 2005 and 2017 editions of the WHO classifications in detail. There are remarkable differences in the terminology, definition, synonyms, epidemiology, classifications, clinical features, radiation/pathology, prognosis, and predictive factors of COD between the two versions. At present, the surgical treatment of COD is less defined, and there is no clear guidance for the treatment of sclerotic bone. In this study, we extracted the affected teeth without removing the sclerotic bone when the bone absorption line can be only found between the root and the lesion, and we extracted the teeth as well as the lesion and curetted the granulation tissue when a bone absorption line could be seen between the lesion and the alveolar bone. According to our observation, the position of the bone absorption line can be used as a reference for the selection of sclerotic bone treatment. Sclerotic bone preservation did not increase its volume and density after tooth extraction. Sclerotic bone was composed of highly mineralized tissue with less blood vessels and cells. The position of the bone resorption line can be used as a basis for treatment selection. The high mineralization of the lesion may weaken its anti-infection ability.

In Situ Synthesis of Encapsulated Pd@silicalite-2 for Highly Stable Methane Catalytic Combustion.

Methane emissions from vehicles have made a significant contribution to the greenhouse effect, primarily due to its high global warming potential. Supported noble metal catalysts are widely employed in catalytic combustion of methane in vehicles, but they still face challenges such as inadequate low-temperature activity and deactivation due to sintering under harsh operating conditions. In the present work, a series of encapsulated structured catalysts with palladium nanoparticles confined in hydrophobic silicalite-2 were prepared by an in situ synthesis method. Based on various characterization methods, including XRD, HR-TEM, XPS, H2-TPR, O2-TPD, H2O-TPD, CH4-TPR, Raman, and in situ DRIFTS-MS, it was confirmed that PdOx nanoparticles were mainly encapsulated inside the silicalite-2 zeolite, which further maintained the stability of the nanoparticles under harsh conditions. Specifically, the 3Pd@S-2 sample exhibited high catalytic activity for methane oxidation even after harsh hydrothermal aging at 750 °C for 16 h and maintained long-term stability at 400 °C for 130 h during wet methane combustion. In situ Raman spectroscopy has confirmed that PdOx species act as active species for methane oxidation. During this reaction, methane reacts with PdOx to produce CO2 and H2O, while simultaneously reducing PdOx to metallic Pd species, which is further reoxidized by oxygen to replenish the PdOx catalyst.

Insight into the Promotion Effect of Trace Pd Doping on the Catalytic Performance of Ag/Al2O3 for C3H6-SCR of NOx.

The mechanistic cause of the enhancement of the C3H6-SCR activity of Ag/Al2O3 by trace Pd doping and the corresponding structure-property relationship were investigated. Pd doping enhanced the water resistance of Ag/Al2O3 for C3H6-SCR by changing the reaction pathway. Under wet conditions, a series of in situ DRIFT studies indicated that the production of an active acetate intermediate on Ag/Al2O3 was suppressed during the partial oxidation of C3H6, while trace Pd doping promoted the formation of another active intermediate, an enolic species. Furthermore, a pathway for the formation of enolic species by the reaction of acrylate with hydroxyl species was proposed. DFT calculations revealed that the surface of Ag clusters was easily covered by hydroxyl in the presence of water vapor, which could inhibit the formation of acetates. Doping with Pd facilitated the activation of acrylate which might further react with hydroxyl species to form enolic species. These findings can be helpful for the future design of efficient HC-SCR catalysts.

Heat Treatment Improves the Activity and Water Tolerance of Pt/Al2O3 Catalysts in Ammonia Catalytic Oxidation.

Ammonia selective catalytic oxidation (NH3-SCO) is a commercial technology applied to diesel vehicles to eliminate ammonia leakage. In this study, a series of Pt/Al2O3 catalysts were synthesized by an impregnation method, and the state of Pt species was carefully adjusted by heat treatment. These Pt/Al2O3 catalysts were further systematically characterized by Brunauer-Emmett-Teller, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption fine structure, UV-vis, H2-tempertaure-programmed reduction, and NH3-temperature-programmed desorption. The characterization results showed that dispersed oxidized Pt species were present on conventional Pt/Al2O3 samples, while high-temperature treatment induced the aggregation of platinum species to form metallic Pt nanoparticles. The Pt/Al2O3 catalysts treated at high temperatures showed superior activity and water tolerance in the NH3-SCO reaction. Diffuse reflectance infrared Fourier-transform spectroscopy combined with mass spectrometry experiments revealed that the Lewis acid sites were more reactive than the Brønsted acid sites. Moreover, compared to oxidized Pt species, metallic Pt nanoparticles were beneficial for oxygen activation and were less affected by water vapor, thus contributing to the superior activity and water tolerance of Pt/Al-800.

Insight into the Mechanism and Kinetics of the Heterogeneous Reaction between SO2 and NO2 on Diesel Black Carbon under Light Irradiation.

The heterogeneous oxidation of SO2 by NO2 has been extensively proposed as an important pathway of sulfate production during haze events in China. However, the kinetics and mechanism of oxidation of SO2 by NO2 on the surface of complex particles remain poorly understood. Here, we systematically explore the mechanism and kinetics of the reaction between SO2 and NO2 on diesel black carbon (DBC) under light irradiation. The experimental results prove that DBC photochemistry can not only significantly promote the heterogeneous reduction of NO2 to produce HONO via transferring photoinduced electrons but also indirectly promote OH radical formation. These reduction products of NO2 as well as NO2 itself greatly promote the heterogeneous oxidation of SO2 on DBC. NO2 oxidation, HONO oxidation, and the surface photo-oxidation process are proven to be three major surface oxidation pathways of SO2. The kinetics results indicate that the surface photooxidation pathway accounts for the majority of the total SO2 uptake (∼63%), followed by the HONO oxidation pathway (∼27%) and direct oxidation by NO2 (∼10%). This work highlights the significant synergistic roles of DBC, NO2, and light irradiation in enhancing the atmospheric oxidation capacity and promoting the heterogeneous formation of sulfate.

Mechanistic Insight into the Promotion of the Low-Temperature NH3-Selective Catalytic Reduction Activity over MnxCe1-xOy Catalysts: A Combined Experimental and Density Functional Theory Study.

CeO2 has attracted much attention in the field of selective catalytic reduction of NO with NH3 (NH3-SCR). However, poor low-temperature activity and a narrow operation window restrict the industrial application of Ce-based oxide catalysts. Herein, the low-temperature NH3-SCR activity of Ce-based oxide catalysts was dramatically improved by Mn doping, and the mechanism was elucidated at the atomic level by experimental measurements and density functional theory calculations. We found that the addition of Mn significantly promoted the formation of surface oxygen vacancies. The oxygen vacancies easily captured O2 in air and formed active oxygen species (superoxide and peroxide) on the surface. The surface active oxygen species efficiently oxidized NO into NO2 and then facilitated the "fast SCR" reaction. This study provides atomic-level insights into the promotion of the NH3-SCR activity over Mn-Ce composite oxides and is beneficial for the development of low-temperature Ce-based catalysts.

Hydrothermal Aging Alleviates the Phosphorus Poisoning of Cu-SSZ-39 Catalysts for NH3-SCR Reaction.

As a new type of catalyst with the potential for commercial application in NOx removal from diesel engine exhausts, Cu-SSZ-39 catalysts must have excellent resistance to complex and harsh conditions. In this paper, the effects of phosphorus on Cu-SSZ-39 catalysts before and after hydrothermal aging treatment were investigated. Compared with fresh Cu-SSZ-39 catalysts, phosphorus poisoning significantly decreased the low-temperature NH3-SCR catalytic activity. However, such activity loss was alleviated by further hydrothermal aging treatment. To reveal the reason for this interesting result, a variety of characterization techniques including NMR, H2-TPR, X-ray photoelectron spectroscopy, NH3-TPD, and in situ DRIFTS measurements were employed. It was found that Cu-P species produced by phosphorus poisoning decreased the redox ability of active copper species, resulting in the observed low-temperature deactivation. After hydrothermal aging treatment, however, Cu-P species partly decomposed with the formation of active CuOx species and a release of active copper species. As a result, the low-temperature NH3-SCR catalytic activity of Cu-SSZ-39 catalysts was recovered.

Insights into SO2 Poisoning Mechanisms of Fresh and Hydrothermally Aged Cu-KFI Catalysts for NH3-SCR Reaction.

The complex poisoning of Cu-KFI catalysts by SO2 and hydrothermal aging (HTA) was investigated. The low-temperature activity of Cu-KFI catalysts was restrained by the formation of H2SO4 and then CuSO4 after sulfur poisoning. Hydrothermally aged Cu-KFI exhibited better SO2 resistance than fresh Cu-KFI since HTA significantly reduced the number of Brønsted acid sites, which were considered to be the H2SO4 storage sites. The high-temperature activity of SO2-poisoned Cu-KFI was basically unchanged compared to the fresh catalyst. However, SO2 poisoning promoted the high-temperature activity of hydrothermally aged Cu-KFI since it triggered CuOx into CuSO4 species, which was considered as an important role in the NH3-SCR reaction at high temperatures. In addition, hydrothermally aged Cu-KFI catalysts were more easily regenerated after SO2 poisoning than fresh Cu-KFI on account of the instability of CuSO4.

Nano-sized alumina supported palladium catalysts for methane combustion with excellent thermal stability.

Pd/Al2O3 catalysts supported on Al2O3 of different particle sizes were synthesized and applied in methane combustion. These catalysts were systematically characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), high resolution-transmission electron microscopy (HR-TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), H2-temperature-programmed reduction (H2-TPR), O2-temperature-programmed oxidation (O2-TPO), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS). The characterization results indicated that nano-sized Al2O3 enabled the uniform dispersion of palladium nanoparticles, thus contributing to the excellent catalytic performance of these nano-sized Pd/Al2O3 catalysts. Among them, Pd/Al2O3-nano-10 (Pd/Al2O3 supported by alumina with an average particle size of 10 nm) showed superior catalytic activity and stability for methane oxidation under harsh practical conditions. It maintained excellent catalytic performance for methane oxidation for 50 hr and remained stable even after harsh hydrothermal aging in 10 vol.% steam at 800°C for 16 hr. Characterization results revealed that the strong metal-support interactions and physical barriers provided by Al2O3-nano-10 suppressed the coalescence ripening of palladium species, and thus contributed to the superior sintering resistance of the Pd/Al2O3-nano-10 catalyst.

Advances in emission control of diesel vehicles in China.

Diesel vehicles have caused serious environmental problems in China. Hence, the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in the latest China VI standard. To fulfill this stringent legislation, two major technical routes, including the exhaust gas recirculation (EGR) and high-efficiency selective catalytic reduction (SCR) routes, have been developed for diesel engines. Moreover, complicated aftertreatment technologies have also been developed, including use of a diesel oxidation catalyst (DOC) for controlling carbon monoxide (CO) and hydrocarbon (HC) emissions, diesel particulate filter (DPF) for particle mass (PM) emission control, SCR for the control of NOx emission, and an ammonia slip catalyst (ASC) for the control of unreacted NH3. Due to the stringent requirements of the China VI standard, the aftertreatment system needs to be more deeply integrated with the engine system. In the future, aftertreatment technologies will need further upgrades to fulfill the requirements of the near-zero emission target for diesel vehicles.

Si/Al Ratio Determines the SCR Performance of Cu-SSZ-13 Catalysts in the Presence of NO2.

A comparative study was performed to investigate the NH3-selective catalytic reduction (SCR) reaction activity of Cu-SSZ-13 zeolites having Si/Al ratios (SARs) of 5, 18, and 30. Remarkably, the Cu-SSZ-13 zeolite catalysts exhibited completely opposite behaviors as a function of SAR under standard SCR (SSCR) and fast SCR (FSCR) reaction atmospheres. Under SSCR conditions, the NOx conversion increased as expected with the decreasing SAR. Under FSCR conditions, however, the NOx conversion decreased as the SAR decreased, contrary to expectations. In this study, based on characterization of the catalysts by X-ray diffraction, transmission electron microscopy, electron paramagnetic resonance, H2-temperature-programmed reduction, temperature-programmed desorption, and diffuse reflectance infrared Fourier transform spectroscopy, together with theoretical calculations, the authors found that the amount of Brønsted acid sites goes up while the SAR goes down, leading to an increase in the accumulation of NH4NO3 under FSCR reaction conditions. Moreover, the accumulated NH4NO3 is of greater stability for those low SAR Cu-SSZ-13 catalysts. These two reasons cause the FSCR performance of Cu-SSZ-13 to decrease with a decrease in SAR. As a result, the NO2 effect on SCR activity changes from promotion to inhibition as the SAR decreases.

Treatment effect analysis of curettage for jaw cysts based on volumetric assessment and image registration.

The study was conducted to develop a visual and intuitive quantitative evaluation method for maxillary cystic lesions after curettage. Mimics 16.0 and Geomagic Studio 2013 were used to form a precise reconstruction of the cystic lesion morphology of 60 cases; the average reduction rates and 95% confidence interval were calculated. Computed tomography (CT) registration was performed before and after surgery to observe morphology features of the bone regeneration of the cystic area. The average reduction rates (RR) of the cysts after curettage were (43.56 ± 16.79)%, (54.33 ± 17.15)% and (68.53 ± 15.99)% at 3 months, 6 months and 12 months after surgery, respectively. The average monthly reduction rates (MRR) were (12.07 ± 4.35)%, (8.16 ± 2.84)% and (5.35 ± 1.52)% at 3 months, 6 months and 12 months after surgery, respectively. Correlation analysis by comparing with each group showed that the effect of sex and age in the 3-month group and the initial size in the 12-month group on RR and MRR were statistically significant. Within the limitations of the study it seems that the chosen approach for quantitative evaluation of the therapeutic effect of curettage for jaw cystic lesions might facilitate visual and quantitative follow-up of cyst curettage and timely detection of recurrence.