Oxygen vacancy-engineered titanium-based perovskite for boosting H2O activation and lower-temperature hydrolysis of organic sulfur.

Modulation of water activation is crucial to water-involved chemical reactions in heterogeneous catalysis. Organic sulfur (COS and CS2) hydrolysis is such a typical reaction involving water (H2O) molecule as a reactant. However, limited by the strong O-H bond in H2O, satisfactory CS2 hydrolysis performance is attained at high temperature above 310 °C, which is at the sacrifice of the Claus conversion, strongly hindering sulfur recovery efficiency improvement and pollution emissions control of the Claus process. Herein, we report a facile oxygen vacancy (VO) engineering on titanium-based perovskite to motivate H2O activation for enhanced COS and CS2 hydrolysis at lower temperature. Increased amount of VO contributed to improved degree of H2O dissociation to generate more active -OH, due to lower energy barrier for H2O dissociation over surface rich in VO, particularly VO clusters. Besides, low-coordinated Ti ions adjacent to VO were active sites for H2O activation. Consequently, complete conversion of COS and CS2 was achieved over SrTiO3 after H2 reduction treatment at 225 °C, a favorable temperature for the Claus conversion, at which both satisfying COS and CS2 hydrolysis performance and improved sulfur recovery efficiency can be obtained simultaneously. Additionally, the origin of enhanced hydrolysis activity from boosted H2O activation by VO was revealed via in-depth mechanism study. This provides more explicit direction for further design of efficacious catalysts for H2O-involved reactions.

An ultrafast and facile nondestructive strategy to convert various inefficient commercial nanocarbons to highly active Fenton-like catalysts.

The Fenton-like process catalyzed by metal-free materials presents one of the most promising strategies to deal with the ever-growing environmental pollution. However, to develop improved catalysts with adequate activity, complicated preparation/modification processes and harsh conditions are always needed. Herein, we proposed an ultrafast and facile strategy to convert various inefficient commercial nanocarbons into highly active catalysts by noncovalent functionalization with polyethylenimine (PEI). The modified catalysts could be in situ fabricated by direct addition of PEI aqueous solution into the nanocarbon suspensions within 30 s and without any tedious treatment. The unexpectedly high catalytic activity is even superior to that of the single-atom catalyst and could reach as high as 400 times higher than the pristine carbon material. Theoretical and experimental results reveal that PEI creates net negative charge via intermolecular charge transfer, rendering the catalyst higher persulfate activation efficiency.

Boosting N2O Catalytic Decomposition by the Synergistic Effect of Multiple Elements in Cobalt-Based High-Entropy Oxides.

Nitrous oxide (N2O) has a detrimental impact on the greenhouse effect, and its efficient catalytic decomposition at low temperatures remains challenging. Herein, the cobalt-based high-entropy oxide with a spinel-type structure (Co-HEO) is successfully fabricated via a facile coprecipitation method for N2O catalytic decomposition. The obtained Co-HEO catalyst displays more remarkable catalytic performance and higher thermal stability compared with single and binary Co-based oxides, as the temperature of 90% N2O decomposition (T90) is 356 °C. A series of characterization results reveal that the synergistic effect of multiple elements enhances the reducibility and augments oxygen vacancy in the high-entropy system, thus boosting the activity of the Co-HEO catalyst. Moreover, density functional theory (DFT) calculations and the temperature-programmed surface reaction (TPSR) with isotope labeling demonstrate that N2O decomposition on the Co-HEO catalyst follows the Langmuir-Hinshelwood (L-H) mechanism with the promotion of abundant oxygen vacancies. This work provides a fundamental understanding of the synergistic catalytic effect in N2O decomposition and paves the way for the novel environmental catalytic applications of HEO.

Modulating the Electronic States of Pt Nanoparticles on Reducible Metal-Organic Frameworks for Boosting the Oxidation of Volatile Organic Compounds.

The adsorption and activation of pollutant molecules and oxygen play a critical role in the oxidation reaction of volatile organic compounds (VOCs). In this study, superior adsorption and activation ability was achieved by modulating the interaction between Pt nanoparticles (NPs) and UiO-66 (U6) through the spatial position effect. Pt@U6 exhibits excellent activity in toluene, acetone, propane, and aldehyde oxidation reactions. Spectroscopic studies, 16O2/18O2 kinetic isotopic experiments, and density functional theory (DFT) results jointly reveal that the encapsulated Pt NPs of Pt@U6 possess higher electron density and d-band center, which is conducive for the adsorption and dissociation of oxygen. The toluene oxidation reaction and DFT results indicate that Pt@U6 is more favorable to activate the C-H of toluene and the C═C of maleic anhydride, while Pt/U6 with lower electron density and d-band center exhibits a higher oxygen dissociation temperature and higher reactant activation energy barriers. This study provides a deep insight into the architecture-performance relation of Pt-based catalysts for the catalytic oxidation of VOCs.

Tailoring the Electronic Metal-Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation.

Metal-modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO2 support through strong electronic metal-support interactions (EMSIs), overcoming the activity-selectivity trade-off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C2H4) and oxygen (O2) and facilitating EO desorption, resulting in high C2H4 conversion. Meanwhile, the increased number of positively charge Ag+ lowers the energy barrier for C2H4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.

A review of whole-process control of industrial volatile organic compounds in China.

Volatile organic compounds (VOCs) play an important role in the formation of ground-level ozone and secondary organic aerosol (SOA), and they have been key issues in current air pollution prevention and control in China. Considerable attention has been paid to industrial activities due to their large and relatively complex VOCs emissions. The present research aims to provide a comprehensive review on whole-process control of industrial VOCs, which mainly includes source reduction, collection enhancement and end-pipe treatments. Lower VOCs materials including water-borne ones are the keys to source substitution in industries related to coating and solvent usage, leak detection and repair (LDAR) should be regarded as an efficient means of source reduction in refining, petrochemical and other chemical industries. Several types of VOCs collection methods such as gas-collecting hoods, airtight partitions and others are discussed, and airtight collection at negative pressure yields the best collection efficiency. Current end-pipe treatments like UV oxidation, low-temperature plasma, activated carbon adsorption, combustion, biodegradation, and adsorption-combustion are discussed in detail. Finally, several recommendations are made for future advanced treatment and policy development in industrial VOCs emission control.

Adsorption and membrane separation for removal and recovery of volatile organic compounds.

Volatile organic compounds (VOCs) are a crucial kind of pollutants in the environment due to their obvious features of severe toxicity, high volatility, and poor degradability. It is particularly urgent to control the emission of VOCs due to the persistent increase of concentration and the stringent regulations. In China, clear directions and requirements for reduction of VOCs have been given in the "national plan on environmental improvement for the 13th Five-Year Plan period". Therefore, the development of efficient technologies for removal and recovery of VOCs is of great significance. Recovery technologies are favored by researchers due to their advantages in both recycling VOCs and reducing carbon emissions. Among them, adsorption and membrane separation processes have been extensively studied due to their remarkable industrial prospects. This overview was to provide an up-to-date progress of adsorption and membrane separation for removal and recovery of VOCs. Firstly, adsorption and membrane separation were found to be the research hotspots through bibliometric analysis. Then, a comprehensive understanding of their mechanisms, factors, and current application statuses was discussed. Finally, the challenges and perspectives in this emerging field were briefly highlighted.

Engineering Ultrafine NiFe-LDH into Self-Supporting Nanosheets: Separation-and-Reunion Strategy to Expose Additional Edge Sites for Oxygen Evolution.

Here, a strategy is reported to prepare Ni-Fe layered double hydroxide (NiFe-LDH) with abundant exposed edge planes for enhanced oxygen evolution reaction (OER). The edge-to-edge assembly of ultrafine NiFe-LDH directed by graphite-like carbon is performed through a one-step hydrothermal process to form self-supporting nanosheet arrays (named NiFe-LDH/C), in which ascorbic acid is employed as the carbon precursor to control both the platelet size and the assembly mode of NiFe-LDH. Benefiting from the unique structural engineering, NiFe-LDH/C can not only achieve a fast surface reconstruction into the highly active γ-phase structure, but also exposes abundant active edge sites, thus leading to a superior OER performance with the overpotential as low as 234 mV at a current density of 50 mA cm-2 . Furthermore, density functional theory (DFT) calculations reveal that the unsaturated Fe-sites and the bridge-sites connecting Ni and Fe atoms, which only exist on the edge planes of NiFe-LDH, are the main active centers responsible for promoting the intrinsic OER activity. This work provides a specific and valuable reference for the rational design of high-quality electrocatalysts through structural engineering for renewable energy applications.

Recent Advances in the Catalytic Oxidation of Volatile Organic Compounds: A Review Based on Pollutant Sorts and Sources.

It is well known that urbanization and industrialization have resulted in the rapidly increasing emissions of volatile organic compounds (VOCs), which are a major contributor to the formation of secondary pollutants (e.g., tropospheric ozone, PAN (peroxyacetyl nitrate), and secondary organic aerosols) and photochemical smog. The emission of these pollutants has led to a large decline in air quality in numerous regions around the world, which has ultimately led to concerns regarding their impact on human health and general well-being. Catalytic oxidation is regarded as one of the most promising strategies for VOC removal from industrial waste streams. This Review systematically documents the progresses and developments made in the understanding and design of heterogeneous catalysts for VOC oxidation over the past two decades. It addresses in detail how catalytic performance is often drastically affected by the pollutant sources and reaction conditions. It also highlights the primary routes for catalyst deactivation and discusses protocols for their subsequent reactivation. Kinetic models and proposed oxidation mechanisms for representative VOCs are also provided. Typical catalytic reactors and oxidizers for industrial VOC destruction are further discussed. We believe that this Review will provide a great foundation and reference point for future design and development in this field.

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine.

In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N2, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N2 selectivity was impacted by the Brønsted acidity and the isolated Cu2+ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.

Sphere-Shaped Mn3O4 Catalyst with Remarkable Low-Temperature Activity for Methyl-Ethyl-Ketone Combustion.

Mn3O4, FeMnOx, and FeOx catalysts synthesized via a solvothermal method were employed for catalytic oxidation of methyl-ethyl-ketone (MEK) at low temperature. Mn3O4 with sphere-like morphology exhibited the highest activity for MEK oxidation, over which MEK was completely oxidized to CO2 at 200 °C, and this result can be comparable to typical noble metal loaded catalysts. The activation energy of MEK over Mn3O4 (30.8 kJ/mol) was much lower than that of FeMnOx (41.5 kJ/mol) and FeOx (47.8 kJ/mol). The dominant planes, surface manganese species ratio, surface-absorbed oxygen, and redox capability played important roles in the catalytic activities of catalysts, while no significant correlation was found between specific surface area and MEK removal efficiency. Mn3O4 showed the highest activity, accounting for abundant oxygen vacancies, low content of surface Mn4+ and strong reducibility. The oxidation of MEK to CO2 via an intermediate of diacetyl is a reaction pathway on Mn3O4 catalyst. Due to high efficiency and low cost, sphere-shaped Mn3O4 is a promising catalyst for VOCs abatement.

Layered sphere-shaped TiO2 capped with gold nanoparticles on structural defects and their catalysis of formaldehyde oxidation.

We describe here a one-step method for the synthesis of Au/TiO2 nanosphere materials, which were formed by layered deposition of multiple anatase TiO2 nanosheets. The Au nanoparticles were stabilized by structural defects in each TiO2 nanosheet, including crystal steps and edges, thereby fixing the Au-TiO2 perimeter interface. Reactant transfer occurred along the gaps between these TiO2 nanosheet layers and in contact with catalytically active sites at the Au-TiO2 interface. The doped Au induced the formation of oxygen vacancies in the Au-TiO2 interface. Such vacancies are essential for generating active oxygen species (*O(-)) on the TiO2 surface and Ti(3+) ions in bulk TiO2. These ions can then form Ti(3+)-O(-)-Ti(4+) species, which are known to enhance the catalytic activity of formaldehyde (HCHO) oxidation. These studies on structural and oxygen vacancy defects in Au/TiO2 samples provide a theoretical foundation for the catalytic mechanism of HCHO oxidation on oxide-supported Au materials.

Physico-chemical characterization and source tracking of black carbon at a suburban site in Beijing.

Particles from ambient air and combustion sources including vehicle emission, coal combustion and biomass burning were collected and chemically pretreated with the purpose of obtaining isolated BC (black carbon) samples. TEM (transmission electron microscopy) results indicate that BC from combustion sources shows various patterns, and airborne BC appears spherical and about 50 nm in diameter with a homogeneous surface and turbostratic structure. The BET (Barrett-Emmett-Teller) results suggest that the surface areas of these BC particles fall in the range of 3-23 m2/g, with a total pore volume of 0.03-0.05 cm3/g and a mean pore diameter of 7-53 nm. The nitrogen adsorption-desorption isotherms are indicative of the accumulation mode and uniform pore size. O2-TPO (temperature programmed oxidation) profiles suggest that the airborne BC oxidation could be classified as the oxidation of amorphous carbon, which falls in the range of 406-490°C with peaks at 418, 423 and 475°C, respectively. Generally, the BC characteristics and source analysis suggest that airborne BC most likely comes from diesel vehicle emission at this site.

Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon.

Ordered mesoporous carbon (OMC) with high specific surface area and large pore volume was synthesized and tested for use as an adsorbent for volatile organic compound (VOC) disposal. Benzene, cyclohexane and hexane were selected as typical adsorbates due to their different molecular sizes and extensive utilization in industrial processes. In spite of their structural differences, high adsorption amounts were achieved for all three adsorbates, as the pore size of OMC is large enough for the access of these VOCs. In addition, the unusual bimodal-like pore size distribution gives the adsorbates a higher diffusion rate compared with conventional adsorbents such as activated carbon and carbon molecular sieve. Kinetic analysis suggests that the adsorption barriers mainly originated from the difficulty of VOC vapor molecules entering the pore channels of adsorbents. Therefore, its superior adsorption ability toward VOCs, together with a high diffusion rate, makes the ordered mesoporous carbon a promising potential adsorbent for VOC disposal.

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts.

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption-desorption, X-ray fluorescence (XRF), H2 temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2-methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from isomerization and protolysis reactions.

Removal of cobalt(II) ion from aqueous solution by chitosan-montmorillonite.

Montmorillonite (MMT) modified with chitosan (CTS, molecular weight=5×10(4)) was applied to remove heavy metal cations by using Co(2+) as a model ion. An increase in MMT interlayer distance observed from X-ray diffraction indicates the intercalation of CTS into MMT. Together with the results of scanning electron microscopy and Fourier transform infrared spectroscopy, it was concluded that the composite material of CTS and MMT (CTS-MMT) was prepared successfully. The mass ratio of CTS to MMT had a strong influence on the adsorption performance of CTS-MMT. The highest adsorption value of 150mg/g was obtained over the composite material with CTS to MMT mass ratio of 0.25, which is much higher than those reported in other studies. The adsorption isotherms and kinetic results indicated that Co(2+) was adsorbed over CTS-MMT in a multilayer model, and the chemical sorption of Co(2+) was determined to be the rate-limiting step.

A novel iron sulfide phase with remarkable hydroxyl radical generation capability for contaminants degradation.

The hydroxyl radical (·OH) stands as one of the most potent oxidizing agents, capable of engaging in non-selective and instantaneous reactions with contaminants in water. Herein, we present a novel iron sulfide phase (S-FeS) characterized by an unprecedented structure, accompanied by its remarkable hydroxyl radical generation capability and contaminant degradation efficiency surpassing that of the conventional metastable iron sulfide phase, namely, the Mackinawite (FeS). In comparison to FeS, S-FeS exhibits enhanced degradation kinetics and higher efficacy in the removal of methylene blue, ciprofloxacin, and trivalent arsenic. Utilizing density functional theory (DFT) calculations, we postulate the mechanism for the exceptional contaminant degradation performance of S-FeS to be attributed to the increased exposure of the highly reactive (110) crystal facets. This research uncovers a new metastable phase that expands the polymorphisms within the iron sulfide family and showcases its capability for driving the oxygen reduction reaction.

Volatile organic compounds (VOCs) emissions from internal floating-roof tank in oil depots in Beijing: Influencing factors and emission reduction strategies analysis.

The internal floating-roof tank is the main type of storage tank for refined oil products. The volatile organic compounds (VOCs) emission from the internal floating-roof tank plays a dominant role in the unorganized emission source of the oil depot. In this study, we selected six typical oil depots in Beijing to investigate VOC emission characteristics from the tank top vent hole using infrared imaging technology and flame ionization detector (FID). The results reveal that infrared thermal imager is efficient in quickly identifying the emission level of the tank discharge point. The ambient temperature and wind speed have a direct effect on sealing loss, the turnover can greatly influence the wall hanging loss, and the concentration of VOCs emitted from the tank top vent hole is negatively correlated with liquid height. Furthermore, the influence of accessories type of the internal floating-roof tank on the concentration of VOCs emission from the top vent hole is also studied when other parameters remain unchanged, and find the floating deck type and sealing mode have a significant influence on their VOCs emissions, of which the combination of pontoon type floating deck and secondary seal are effective in controlling the concentration of VOCs emitted from the tank top vent hole. Finally, based on our experimental results, several feasible emission reduction strategies are proposed in terms of source prevention and process control in order to achieve the fine management of the whole process. This paper provides important technical support and policy thoughts for VOCs emission control during oil storage.

Oxophilic Ce single atoms-triggered active sites reverse for superior alkaline hydrogen evolution.

The state-of-the-art alkaline hydrogen evolution catalyst of united ruthenium single atoms and small ruthenium nanoparticles has sparked considerable research interest. However, it remains a serious problem that hydrogen evolution primarily proceeds on the less active ruthenium single atoms instead of the more efficient small ruthenium nanoparticles in the catalyst, hence largely falling short of its full activity potential. Here, we report that by combining highly oxophilic cerium single atoms and fully-exposed ruthenium nanoclusters on a nitrogen functionalized carbon support, the alkaline hydrogen evolution centers are facilely reversed to the more active ruthenium nanoclusters driven by the strong oxophilicity of cerium, which significantly improves the hydrogen evolution activity of the catalyst with its mass activity up to -10.1 A mg-1 at -0.05 V. This finding is expected to shed new light on developing more efficient alkaline hydrogen evolution catalyst by rational regulation of the active centers for hydrogen evolution.

Effective Nitric Oxide Reduction Over Core-Shell Cu-SSZ-13@meso-MOx Catalysts with Significant Catalytic Activity and Hydrothermal Stability.

In this study, Cu-SSZ-13 zeolites are successfully coated with mesoporous metal oxides (CeO2 , Fe2 O3 , TiO2 and SiO2 ) and prepared as core-shell Cu-SSZ-13@meso-MOx samples with hierarchical pore structure. Compared with Cu-SSZ-13, the catalytic activity and hydrothermal stability of the Cu-SSZ-13@meso-MOx have been greatly improved. The promoting effect of meso-MOx shell on the catalytic activity of Cu-SSZ-13 is mainly attribute to the presence of both microporous and mesoporous structures, the formation of more active isolated Cu2+ ions and more L-acid sites, and the synergistic effect between Cu-SSZ-13 and meso-MOx interaction. Moreover, all the Cu-SSZ-13@meso-MOx catalysts maintain their activities to a greater extent after hydrothermal aging. The core-shell structure may play a protective role and greatly improve the hydrothermal stability of Cu-SSZ-13. More L-acidic sites and more isolated Cu2+ ions are preserved under the protection of mesoporous structure.