Boosting Catalytic and Anti-fluorination Performance of the Ru/Vanadia-Titania Catalyst for the Oxidative Destruction of Freon by Sulfuric Acid Modification.

Chlorofluorocarbons (CFCs) exert a strong greenhouse effect and constitute the largest contributor to ozone depletion. Catalytic removal is considered an effective pathway for eliminating low-concentration CFCs under mild conditions. The key issue is the easy deactivation of the catalysts due to their surface fluorination. We herein report a comparative investigation on catalytic dichlorodifluoromethane (CFC-12) removal in the absence or presence of water over the sulfuric-acid-modified three-dimensionally ordered macroporous vanadia-titania-supported Ru (S-Ru/3DOM VTO) catalysts. The S-Ru/3DOM VTO catalyst exhibited high activity (T90% = 278 °C at space velocity = 40 000 mL g-1 h-1) and good stability within 60 h of on-stream reaction in the presence of 1800 ppm of water due to the improvements in acid site amount and redox ability that promoted the adsorption of CFC-12 and the activation of C-F bonds. Compared with the case under dry conditions, catalytic performance for CFC-12 removal was better over the S-Ru/3DOM VTO catalyst in the presence of water. Water introduction mitigated surface fluorination by the replenishment of hydroxyl groups, inhibited the formation of halogenated byproducts via the surface fluorine species cleaning effect, and promoted the reaction pathway of COX2 (X = Cl/F) → carboxylic acid → CO2.

PdPtVOx/CeO2-ZrO2: Highly efficient catalysts with good sulfur dioxide-poisoning reversibility for the oxidative removal of ethylbenzene.

The PdPtVOx/CeO2-ZrO2 (PdPtVOx/CZO) catalysts were obtained by using different approaches, and their physical and chemical properties were determined by various techniques. Catalytic activities of these materials in the presence of H2O or SO2 were evaluated for the oxidation of ethylbenzene (EB). The PdPtVOx/CZO sample exhibited high catalytic activity, good hydrothermal stability, and reversible sulfur dioxide-poisoning performance, over which the specific reaction rate at 160°C, turnover frequency at 160°C (TOFPd or Pt), and apparent activation energy were 72.6 mmol/(gPt⋅sec) or 124.2 mmol/(gPd⋅sec), 14.2 sec-1 (TOFPt) or 13.1 sec-1 (TOFPd), and 58 kJ/mol, respectively. The large EB adsorption capacity, good reducibility, and strong acidity contributed to the good catalytic performance of PdPtVOx/CZO. Catalytic activity of PdPtVOx/CZO decreased when 50 ppm SO2 or (1.0 vol.% H2O + 50 ppm SO2) was added to the feedstock, but was gradually restored to its initial level after the SO2 was cut off. The good reversible sulfur dioxide-resistant performance of PdPtVOx/CZO was associated with the facts: (i) the introduction of SO2 leads to an increase in surface acidity; (ii) V can adsorb and activate SO2, thus accelerating formation of the SOx2- (x = 3 or 4) species at the V and CZO sites, weakening the adsorption of sulfur species at the PdPt active sites, and hence protecting the PdPt active sites to be not poisoned by SO2. EB oxidation over PdPtVOx/CZO might take place via the route of EB â†’ styrene â†’ phenyl methyl ketone â†’ benzaldehyde â†’ benzoic acid â†’ maleic anhydride â†’ CO2 and H2O.

Highly Selective Activation of C-H Bond and Inhibition of C-C Bond Cleavage by Tuning Strong Oxidative Pd Sites.

Improving the product selectivity meanwhile restraining deep oxidation still remains a great challenge over the supported Pd-based catalysts. Herein, we demonstrate a universal strategy where the surface strong oxidative Pd sites are partially covered by the transition metal (e. g., Cu, Co, Ni, and Mn) oxide through thermal treatment of alloys. It could effectively inhibit the deep oxidation of isopropanol and achieve the ultrahigh selectivity (>98%) to the target product acetone in a wide temperature range of 50-200 °C, even at 150-200 °C with almost 100% isopropanol conversion over PdCu1.2/Al2O3, while an obvious decline in acetone selectivity is observed from 150 °C over Pd/Al2O3. Furthermore, it greatly improves the low-temperature catalytic activity (acetone formation rate at 110 °C over PdCu1.2/Al2O3, 34.1 times higher than that over Pd/Al2O3). The decrease of surface Pd site exposure weakens the cleavage for the C-C bond, while the introduction of proper CuO shifts the d-band center (εd) of Pd upward and strengthens the adsorption and activation of reactants, providing more reactive oxygen species, especially the key super oxygen species (O2-) for selective oxidation, and significantly reducing the barrier of O-H and ß-C-H bond scission. The molecular-level understanding of the C-H and C-C bond scission mechanism will guide the regulation of strong oxidative noble metal sites with relatively inert metal oxide for the other selective catalytic oxidation reactions.

A General Dual-Metal Nanocrystal Dissociation Strategy to Generate Robust High-Temperature-Stable Alumina-Supported Single-Atom Catalysts.

Designing new synthesis routes to fabricate highly thermally durable precious metal single-atom catalysts (SACs) is challenging in industrial applications. Herein, a general strategy is presented that starts from dual-metal nanocrystals (NCs), using bimetallic NCs as a facilitator to spontaneously convert a series of noble metals to single atoms on aluminum oxide. The metal single atoms are captured by cation defects in situ formed on the surface of the inverse spinel (AB2O4) structure, which process provides numerous anchoring sites, thus facilitating generation of the isolated metal atoms that contributes to the extraordinary thermodynamic stability. The Pd1/AlCo2O4-Al2O3 shows not only improved low-temperature activity but also unprecedented (hydro)thermal stability for CO and propane oxidation under harsh aging conditions. Furthermore, our strategy exhibits a small scaling-up effect by the simple physical mixing of commercial metal oxide aggregates with Al2O3. The good regeneration between oxidative and reductive atmospheres of these ionic palladium species makes this catalyst system of potential interest for emissions control.

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation.

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H2-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOFCo) being 245°C, 1.23 × 10-3 moltoluene/(gcat·sec), and 11.58 × 10-3 sec-1 for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO2, SO2 or NH3, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O2 and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H2O and CO2.

Graphitic carbon nitride-based photocatalysts in the applications of environmental catalysis.

Semiconductor photocatalytic technology has shown great prospects in converting solar energy into chemical energy to mitigate energy crisis and solve environmental pollution problems. The key issue is the development of high-efficiency photocatalysts. Various strategies in the state-of-the-art advancements, such as heterostructure construction, heteroatom doping, metal/single atom loading, and defect engineering, have been presented for the graphitic carbon nitride (g-C3N4)-based nanocomposite catalysts to design their surface chemical environments and internal electronic structures to make them more suitable for different photocatalytic applications. In this review, nanoarchitecture design, synthesis methods, photochemical properties, potential photocatalytic applications, and related reaction mechanisms of the modified high-efficiency carbon nitride-based photocatalysts were briefly summarized. The superior photocatalytic performance was identified to be associated with the enhanced visible-light response, fast photoinduced electron-hole separation, efficient charge migration, and increased unsaturated active sites. Moreover, the further advance of the visible-light harvesting and solar-to-energy conversions are proposed.

Enhanced Water Resistance and Catalytic Performance of Ru/TiO2 by Regulating Brønsted Acid and Oxygen Vacancy for the Oxidative Removal of 1,2-Dichloroethane and Toluene.

The compositions of volatile organic compounds (VOCs) under actual industrial conditions are often complex; especially, the interaction of intermediate products easily leads to more toxic emissions that are harmful to the atmospheric environment and human health. Herein, we report a comparative investigation on 1,2-dichloroethane (1,2-DCE) and (1,2-DCE + toluene) oxidation over the Ru/TiO2, phosphotungstic acid (HPW)-modified Ru/TiO2, and oxygen vacancy-rich Ru/TiOx catalysts. The doping of HPW successfully introduced the 1,2-DCE adsorption sites to promote its oxidation and exhibited outstanding water resistance. For the mixed VOCs, Ru/HPW-TiO2 promoted the preferential and superfluous adsorption of toluene and resulted in the inhibition of 1,2-DCE degradation. Therefore, HPW modification is a successful strategy in catalytic 1,2-DCE oxidation, but Brønsted acid sites tend to adsorb toluene in the mixed VOC oxidation. The Ru/TiOx catalyst exhibited excellent activity and stability in the oxidation of mixed VOCs and could inhibit the generation of byproducts and Cl2 compared with the Ru/HPW-TiO2 catalyst. Compared with the Brønsted acid modification, the oxygen vacancy-rich catalysts are significantly suitable for the oxidation of multicomponent VOCs.

Photothermal Synergistic Effect of Pt1/CuO-CeO2 Single-Atom Catalysts Significantly Improving Toluene Removal.

Photothermal synergistic catalytic oxidation of toluene over single-atom Pt catalysts was investigated. Compared with the conventional thermocatalytic oxidation in the dark, toluene conversion and CO2 yield over 0.39Pt1/CuO-CeO2 under simulated solar irradiation (λ = 320-2500 nm, optical power density = 200 mW cm-2) at 180 °C could be increased about 48%. An amount of CuO was added to CeO2 to disperse single-atom Pt with a maximal Pt loading of 0.83 wt %. The synergistic effect between photo- and thermocatalysis is very important for the development of new pollutant treatment technology with high efficiency and low energy consumption. Both light and heat played an important role in the present photothermal synergistic catalytic oxidation. 0.39Pt1/CuO-CeO2 showed good redox performance and excellent optical properties and utilized the full-spectrum solar energy. Light illumination induced the generation of reactive oxygen species (•OH and •O2-), which accelerated the transformation of intermediates, promoted the release of active sites on the catalyst surface, and improved the oxidation reaction.

Engineering Platinum Catalysts via a Site-Isolation Strategy with Enhanced Chlorine Resistance for the Elimination of Multicomponent VOCs.

Pt-based catalysts can be poisoned by the chlorine formed during the oxidation of multicomponent volatile organic compounds (VOCs) containing chlorinated VOCs. Improving the low-temperature chlorine resistance of catalysts is important for industrial applications, although it is yet challenging. We hereby demonstrate the essential catalytic roles of a bifunctional catalyst with an atomic-scale metal/oxide interface constructed by an intermetallic compound nanocrystal. Introducing trichloroethylene (TCE) exhibits a less negative effect on the catalytic activity of the bimetallic catalyst for o-xylene oxidation, and the partial deactivation caused by TCE addition is reversible, suggesting that the bimetallic, HCl-etched Pt3Sn(E)/CeO2 catalyst possesses much stronger chlorine resistance than the conventional Pt/CeO2 catalyst. On the site-isolated Pt-Sn catalyst, the presence of aromatic hydrocarbon significantly inhibits the adsorption strength of TCE, resulting in excellent catalytic stability in the oxidation of the VOC mixture. Furthermore, the large amount of surface-adsorbed oxygen species generated on the electronegative Pt is highly effective for low-temperature C-Cl bond dissociation. The adjacent promoter (Sn-O) possesses the functionality of acid sites to provide sufficient protons for HCl formation over the bifunctional catalyst, which is considered critical to maintaining the reactivity of Pt by removing Cl and decreasing the polychlorinated byproducts.

Synergistic Effect of Reactive Oxygen Species in Photothermocatalytic Removal of VOCs from Cooking Oil Fumes over Pt/CeO2/TiO2.

The volatile organic compounds (VOCs) from cooking oil fumes are very complex and do harm to humans and the environment. Herein, we develop the high-efficiency and energy-saving synergistic photothermocatalytic oxidation approach to eliminate the mixture of heptane and hexanal, the representative VOCs with high concentrations in cooking oil fumes. The Pt/CeO2/TiO2 catalyst with nanosized Pt particles was prepared by the simple hydrothermal and impregnation methods, and the physicochemical properties of the catalyst were measured using numerous techniques. The Pt/CeO2/TiO2 catalyst eliminated the VOC mixture at low light intensity (100 mW cm-2) and low temperature (200 °C). In addition, it showed 25 h of catalytic stability and water resistance (water concentration up to 20 vol %) at 140 or 190 °C. It is concluded that O2 picked up the electrons from Pt to generate the •O2- species, which were transformed to the O22- and O- species after the rise in temperature. In the presence of water, the •OH species induced by light irradiation on the catalyst surface and the •OOH species formed via the thermal reaction were both supplementary oxygen species for VOC oxidation. The synergistic interaction of photo- and thermocatalysis was generated by the reactive oxygen species.

An investigation on catalytic performance and reaction mechanisms of Fe/OMS-2 for the oxidation of carbon monoxide, ethyl acetate, and toluene.

The octahedral molecular sieve (OMS-2)-supported Fe (xFe/OMS-2: x = 1, 3, 5, and 10) catalysts were prepared using the pre-incorporation method. Physicochemical properties of the as-synthesized materials were characterized by means of various techniques, and their catalytic activities for CO, ethyl acetate, and toluene oxidation were evaluated. Among all of the samples, performed the best, with the reaction temperature required to achieve 90% conversion (T90%) being 160°C for CO oxidation, 210°C for ethyl acetate oxidation, and 285°C for toluene oxidation. Such a good catalytic performance of 5Fe/OMS-2 was associated with its high (Mn3+ + Mn2+) content and adsorbed oxygen species concentration, and good low-temperature reducibility and lattice oxygen mobility as well as strong interaction between Fe and OMS-2. In addition, catalytic mechanisms of the oxidation of three pollutants over the 5Fe/OMS-2 catalyst were also studied. It was found that CO, ethyl acetate or toluene was first adsorbed, then the related intermediates were formed, and finally the formed intermediates were completely converted into CO2 and H2O.

Synergy in Au-CuO Janus Structure for Catalytic Isopropanol Oxidative Dehydrogenation to Acetone.

The controlled oxidation of alcohols to the corresponding ketones or aldehydes via selective cleavage of the ß-C-H bond of alcohols under mild conditions still remains a significant challenge. Although the metal/oxide interface is highly active and selective, the interfacial sites fall far behind the demand, due to the large and thick support. Herein, we successfully develop a unique Au-CuO Janus structure (average particle size=3.8 nm) with an ultrathin CuO layer (0.5 nm thickness) via a bimetal in situ activation and separation strategy. The resulting Au-CuO interfacial sites prominently enhance isopropanol adsorption and decrease the energy barrier of ß-C-H bond scission from 1.44 to 0.01 eV due to the strong affinity between the O atom of CuO and the H atom of isopropanol, compared with Au sites alone, thereby achieving ultrahigh acetone selectivity (99.3 %) over 1.1 wt % AuCu0.75 /Al2 O3 at 100 °C and atmospheric pressure with 97.5 % isopropanol conversion. Furthermore, Au-CuO Janus structures supported on SiO2 , TiO2 or CeO2 exhibit remarkable catalytic performance, and great promotion in activity and acetone selectivity is achieved as well for other reducible oxides derived from Fe, Co, Ni and Mn. This study should help to develop strategies for maximized interfacial site construction and structure optimization for efficient ß-C-H bond activation.

Electronically Engineering Water Resistance in Methane Combustion with an Atomically Dispersed Tungsten on PdO Catalyst.

Improving the low-temperature water-resistance of methane combustion catalysts is of importance for industrial applications and it is challenging. A stepwise strategy is presented for the preparation of atomically dispersed tungsten species at the catalytically active site (Pd nanoparticles). After an activation process, a Pd-O-W1 -like nanocompound is formed on the PdO surface with an atomic scale interface. The resulting supported catalyst has much better water resistance than the conventional catalysts for methane combustion. The integrated characterization results confirm that catalytic combustion of methane involves water, proceeding via a hydroperoxyl-promoted reaction mechanism on the catalyst surface. The results of density functional theory calculations indicate an upshift of the d-band center of palladium caused by electron transfer from atomically dispersed tungsten, which greatly facilitates the adsorption and activation of oxygen on the catalyst.

High Selectivity to HCl for the Catalytic Removal of 1,2-Dichloroethane Over RuP/3DOM WOx: Insights into the Effects of P-Doping and H2O Introduction.

Ru-based catalysts for catalytic combustion of high-toxicity Cl-containing volatile organic compounds are inclined to produce Cl2 instead of ideal HCl due to the Deacon reaction. We herein reported that the three-dimensionally ordered macroporous (3DOM) WOx-supported RuP nanocatalyst greatly improved HCl selectivity (at 400 °C, increased from 66.0% over Ru/3DOM WOx to 96.4% over RuP/3DOM WOx) and reduced chlorine-containing byproducts for 1,2-dichloroethane (1,2-DCE) oxidation. P-doping enhanced the number of structural hydroxyl groups and Brønsted acid sites. The isotopic 1,2-DCE temperature-programmed desorption experiment in the presence of H218O indicated the generation of a new active oxygen species 16O18O that participated in the reaction. Generally, P-doping and H2O introduction could promote the exchange reaction between Cl and hydroxyl groups, rather than oxygen defects, and then benefit the production of HCl and reduce the generation of other chlorine species or Cl2, via the reaction processes of C2H3Cl → alcohol → aldehyde → carboxylic acids.

Low-temperature (NO + O2) adsorption performance of alkaline earth metal-doped C-FDU-15.

To improve the removal capacity of NO + O2 effectively, the alkaline earth metal-doped order mesoporous carbon (A-C-FDU-15(0.001) (A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15(x) (x = 0.001-0.003) samples were prepared, and their physicochemical and NO + O2 adsorption properties were determined by means of various techniques. The results show that the sequence in (NO + O2) adsorption performance was as follows: Mg-C-FDU-15(0.001) (93.2 mg/g) > Ca-C-FDU-15(0.001) (82.2 mg/g) > Sr-C-FDU-15(0.001) (76.1 mg/g) > Ba-C-FDU-15(0.001) (72.9 mg/g) > C-FDU-15 (67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest (NO + O2) adsorption capacity (106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O2 on the A-C-FDU-15(x) samples, and (NO + O2) adsorption on the samples was mainly chemical adsorption. Combined with the results of (NO + O2)-temperature-programmed desorption ((NO + O2)-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization, we deduced that there were two main pathways of (NO + O2) adsorption: one was first the conversion of NO and O2 to NO2 and then part of NO2 was converted to NO2- and NO3-; and the other was the direct oxidation of NO to NO2- and NO3-.

Carbon dioxide adsorption behaviors of aluminum-pillared montmorillonite-supported alkaline earth metals.

The Al-pillared montmorillonite-supported alkaline earth metal 5M/Al-PILC (PILC = pillared clay, M = Mg, Ca, Sr, and Ba) and xMg/Al-PILC (x = 1, 3, 5, and 7 wt.%) samples were prepared using an impregnation method. Physical properties of the materials were determined by means of X-ray diffraction (XRD) and N2 adsorption-desorption, and their CO2 adsorption behaviors were investigated using the thermogravimetric analyzer (TG), CO2 temperature-programmed desorption (CO2-TPD), and in situ diffuse reflectance infrared transform spectroscopy (in situ-DRIFTS) techniques. It is shown that 5Mg/Al-PILC possessed the highest CO2 adsorption capacity (2.559 mmol/g). The characterization results indicate that Al-pillaring increased the specific surface area of montmorillonite, which was beneficial for the adsorption of CO2. The CO2 adsorption process on the sample was mainly chemical adsorption, and alkalinity was the main factor influencing its adsorption capacity. The alkalinity of the sample was enhanced by loading an appropriate amount of alkaline earth metal, and the adsorbed CO2 was present in the form of bicarbonate and carbonate. In addition, the 5Mg/Al-PILC sample exhibited an excellent regeneration efficiency. We believe that the outcome of this research would provide a good option for developing highly effective CO2 adsorption materials.

Adsorption performance of CMK-3 and C-FDU-15 in NO removal at low temperature.

CMK-3 and C-FDU-15 samples were synthesized using hard-templating and evaporation-induced self-assembly (EISA) methods, respectively. The pore structures of CMK-3 and C-FDU-15 as well as commercial activated carbon were characterized by means of X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and N2 adsorption-desorption. Adsorption of NO was investigated by means of thermogravimetric analysis, temperature-programmed desorption of NO + O2, and in situ diffuse reflectance Fourier transform infrared spectroscopy. The results show that the CMK-3 and C-FDU-15 materials possessed ordered and uniform structures. The co-adsorption capacity of NO and O2 decreased in the sequence CMK-3 (88.6 mg/g) > C-FDU-15 (71.7 mg/g) > AC (25.3 mg/g). There were two main adsorption species on CMK-3 and C-FDU-15: nitrite and nitrate. Nitrite is converted to nitrate easily. However, the adsorption species were more complex on AC, with nitrite being the main species. Moreover, CMK-3 and C-FDU-15 exhibit excellent regeneration efficiency compared with AC. The excellent NO adsorption performance of CMK-3 and C-FDU-15 was associated with their ordered mesoporous structures and high surface areas. The research provides more options for NO adsorption in the future.

Mesoporous cobalt monoxide-supported platinum nanoparticles: Superior catalysts for the oxidative removal of benzene.

Mesoporous Co3O4 (meso-Co3O4)-supported Pt (0.53 wt.% Pt/meso-Co3O4) was synthesized via the KIT-6-templating and polyvinyl alcohol (PVA)-assisted reduction routes. Mesoporous CoO (meso-CoO) was fabricated through in situ reduction of meso-Co3O4 with glycerol, and the 0.18-0.69 wt.% Pt/meso-CoO samples were generated by the PVA-assisted reduction method. Meso-Co3O4 and meso-CoO were of cubic crystal structure and the Pt nanoparticles (NPs) with a uniform size of ca. 2 nm were well distributed on the meso-Co3O4 or meso-CoO surface. The 0.56 wt% Pt/meso-CoO (0.56Pt/meso-CoO) sample performed the best in benzene combustion (T50% = 156 °C and T90% = 186 °C at a space velocity of 80,000 mL/(g h)). Introducing water vapor or CO2 with a certain concentration led to partial deactivation of 0.56 Pt/meso-CoO and such a deactivation was reversible. We think that the superior catalytic activity of 0.56 Pt/meso-CoO was intimately related to its good oxygen activation and benzene adsorption ability.

Ni-Ti Layered Double Hydroxide@Graphitic Carbon Nitride Nanosheet: A Novel Nanocomposite with High and Ultrafast Sonophotocatalytic Performance for Degradation of Antibiotics.

Pollution of water resources by antibiotics is a growing environmental concern. In this work, nanocomposites of g-C3N4@Ni-Ti layered double hydroxides (g-C3N4@Ni-Ti LDH NCs) with high surface areas were synthesized through an optimized hydrothermal method, in the presence of NH4F. Application of various characterization techniques unraveled that the prepared nanocomposites are composed of porous Ni-Ti LDH nanoparticles and hierarchical g-C3N4 nanosheets. Further, these NCs were employed for photocatalytic and sonophotocatalytic removal of amoxicillin (AMX), as a model antibiotic, from aqueous solutions. In addition, sonocatalysis was performed. It was found out that the g-C3N4@Ni-Ti LDH NCs outperform their pure g-C3N4 and Ni-Ti LDH components in photocatalytic degradation of AMX under visible light irradiation. Also, the following order was determined for efficiency of the three adopted processes: sonocatalysis < photocatalysis < sonophotocatalysis. Furthermore, variation of the sonophotocatalysis conditions specified 500 W light intensity, 9 s on/1 s off ultrasound pulse modem and 1.25 g/L g-C3N4-20@Ni-Ti LDH as the optimal conditions. In this way, optimization of the highly efficient sonophotocatalytic process resulted in 99.5% AMX degradation within 75 min. Moreover, a TOC analyzer was employed to estimate the rate of AMX degradation over the nanocomposites. In addition, formation of hydroxyl radicals (•OH) on the surface of the g-C3N4-20@Ni-Ti LDH particles was approved using the terephthalic acid probe in photoluminescence (PL) spectroscopy. No significant loss was observed in the sonophotocatalytic activity of the nanocomposites even after five consecutive runs. Also, a plausible mechanism was proposed for the sonophotocatalysis reaction. In general, our findings can be considered as a starting point for synthesis of other g-C3N4-based NCs and application of the resultant nanocomposites to environmental remediation.

Coupled Palladium-Tungsten Bimetallic Nanosheets/TiO2 Hybrids with Enhanced Catalytic Activity and Stability for the Oxidative Removal of Benzene.

Since the conventional Pd-based catalysts often suffer severe deactivation by water, development of a catalyst with good activity and moisture-resistance ability is of importance in effectively controlling emissions of volatile organic compounds (VOCs). Herein, we report the efficient synthesis of ultrathin palladium-tungsten bimetallic nanosheets with exceptionally high dispersion of tungsten species. The supported catalyst (TiO2/PdW) shows good performance for benzene oxidation, and 90% conversion is achieved at a temperature of 200 °C and a space velocity of 40 000 mL g-1 h-1. The TiO2/PdW catalyst also exhibits better water-tolerant ability than the traditional Pd/TiO2 catalyst. The high catalytic efficiency can be explained by the facile redox cycle of the active Pd2+/Pd0 couple in the close-contact PdO x-WO x-TiO2 arrangement. We propose that the reason for good tolerance to water is that the lattice oxygen of the TiO2/PdW catalyst can effectively replenish the oxygen in active PdO x sites consumed by benzene oxidation. A four-step benzene transformation mechanism promoted by the catalyst is proposed. The present work provides a useful idea for the rational design of efficient bimetallic catalysts for the removal of VOCs under the high humidity conditions.