0D/3D direct Z-scheme heterojunctions hybridizing by MoS2 quantum dots and honeycomb conjugated triazine polymers (CTPs) for enhanced photocatalytic performance

Herein, a novel direct Z-scheme photocatalyst was accomplished by hybridization of 0D MoS₂ quantum dots (MSQDs) and 3D honeycomb-like conjugated triazine polymers (CTP) (namely, CTP-MSQD). The unique 0D/3D hierarchical structure significantly enhanced the exposure of active sites and light harvesting property, while the formed p-n junction enabled the direct strong interface coupling without the necessity of any mediators. The optimized CTP-MSQD3 exhibited continuously increased visible-light-driven photocatalytic activity and strong durability both in Cr(VI) reduction and H₂ evolution, featured a rate of 0.069 min⁻¹ and 1070 µmol/(hr∙g), respectively, which were 8 times than those of pure 3D-CTP (0.009 min⁻¹ and 129 µmol/(hr∙g)). We believe that this work provides a promising photocatalyst system that combines a 0D/3D hierarchical structure and a Z-scheme charge flow for efficient and stable photocatalytic conversion.     

Microwave-assisted continuous flow phytosynthesis of silver nanoparticle/reduced graphene oxide composites and related visible light catalytic performance

The creation of an environmentally friendly synthesis method for silver nanomaterials (AgNPs) is an urgent concern for sustainable nanotechnology development. In the present study, a novel straightforward and green method for the preparation of silver nanoparticle/reduced graphene oxide (AgNP/rGO) composites was successfully developed through the combination of phytosynthesis, continuous flow synthesis and microwave-assistance. Oriental persimmon (Diospyros kaki Thunb.) extracts were used as both plant reducing and capping agents for fast online synthesis of AgNP/rGO composites. The experimental parameters were optimized and the morphologies of the prepared materials were investigated. The characterization results reveal that spherical AgNPs were quickly synthesized and uniformly dispersed on rGO sheets using the proposed online system. Fourier transform infrared spectroscopy analysis confirmed that phenols, flavonoids, and other substances in the plant extracts played a decisive role in the synthesis of AgNP/rGO composites. Using sodium borohydride (NaBH₄) degradation of p-nitrophenol (4-NP) as a model, the catalytic activity of the prepared AgNP/rGO materials was evaluated. The complete degradation of 4-NP was achieved within 12 min through the use of AgNP/rGO materials, and the composite had a much better catalytic activity than the bare AgNPs and rGO had. Compared with the conventional chemical method, our online method is facile, fast, cost-efficient, and environmentally friendly.     

Construction of dual Z-scheme Bi2WO6/g-C3N4/black phosphorus quantum dots composites for effective bisphenol A degradation

In this work, a novel dual Z-scheme Bi₂WO₆/g-C₃N₄/black phosphorus quantum dots (Bi₂WO₆/g-C₃N₄/BPQDs) composites were fabricated and utilized towards photocatalytic degradation of bisphenol A (BPA) under visible-light irradiation. Optimizing the content of g-C₃N₄ and BPQDs in Bi₂WO₆/g-C₃N₄/BPQDs composites to a suitable mass ratio can enhance the visible-light harvesting capacity and increase the charge separation efficiency and the transfer rate of excited-state electrons and holes, resulting in much higher photocatalytic activity for BPA degradation (95.6%, at 20 mg/L in 120 min) than that of Bi₂WO₆ (63.7%), g-C₃N₄ (25.0%), BPQDs (8.5%), and Bi₂WO₆/g-C₃N₄ (79.6%), respectively. Radical trapping experiments indicated that photogenerated holes (h⁺) and superoxide radicals (•O₂⁻) played crucial roles in photocatalytic BPA degradation. Further, the possible degradation pathway and photocatalytic mechanism was proposed by analyzing the BPA intermediates. This work also demonstrated that the Bi₂WO₆/g-C₃N₄/BPQDs as effective photocatalysts was stable and have promising potential to remove environmental contaminants from real water samples.     

Functional groups assisted-photoinduced electron transfer-mediated highly fluorescent metal-organic framework quantum dot composite for selective detection of mercury (II) in water

The presence of toxic mercury (II) in water is an ever-growing problem on earth that has various harmful effect on human health and aquatic living organisms. Therefore, detection of mercury (II) in water is very much crucial and several researches are going on in this topic. Metal-organic frameworks (MOFs) are considered as an effective device for sensing of toxic heavy metal ions in water. The tunable functionalities with large surface area of highly semiconducting MOFs enhance its activity towards fluorescence sensing. In this study, we are reporting one highly selective and sensitive luminescent sensor for the detection of mercury (II) in water. A series of binary MOF composites were synthesized using in-situ solvothermal synthetic technique for fluorescence sensing of Hg²⁺ in water. The well-distributed graphitic carbon nitride quantum dots on porous zirconium-based MOF improve Hg²⁺ sensing activity in water owing to their great electronic and optical properties. The binary MOF composite (2) i.e., the sensor exhibited excellent limit of detection (LOD) value of 2.4 nmol/L for Hg²⁺. The sensor also exhibited excellent performance for mercury (II) detection in real water samples. The characterizations of the synthesized materials were done using various spectroscopic techniques and the fluorescence sensing mechanism was studied.     

One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NO_x with NH₃ and were characterized by various techniques. The results show that Fe_0.63/Cu_1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu²⁺ and monomeric Fe³⁺ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu²⁺ species act as primary active sites for SCR reaction, while monomeric Fe³⁺ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu²⁺ site, as well as the formation of highly oxidizing Fe₂O₃, thus causing deterioration of catalytic performances.     

Multi-function adsorbent-photocatalyst MXene-TiO2 composites for removal of enrofloxacin antibiotic from water

MXenes, a new family of two-dimensional transition metal carbides or nitrides, have attracted tremendous attention for various applications due to their unique properties such as good electrical conductivity, hydrophilicity, and ion intercalability. In this work, Ti₃C₂ MXene, or MX, is converted to MX-TiO₂ composites using a simple and rapid microwave hydrothermal treatment in HCl/NaCl mixture solution that induces formation of fine TiO₂ particles on the MX parent structure and imparts photocatalytic activity to the resulting MX-TiO₂ composites. The composites were used for enrofloxacin (ENR), a frequently found contaminating antibiotic, removal from water. The relative amount of the MX and TiO₂ can be controlled by controlling the hydrothermal temperature resulting in composites with tunable adsorption/photocatalytic properties. NaCl addition was found to play important role as composites synthesized without NaCl could not adsorb enrofloxacin well. Adding NaCl into the hydrothermal treatment causes sodium ions to be simultaneously intercalated into the composite structure, improving ENR adsorption greatly from 1 to 6 mg ENR/g composite. It also slows down the MX to TiO₂ conversion leading to a smaller and more uniform distribution of TiO₂ particles on the structure. MX-TiO₂/NaCl composites, which have sodium intercalated in their structures, showed both higher ENR adsorption and photocatalytic activity than composites without NaCl despite the latter having higher TiO₂ content. Adsorbed ENR on the composites can be efficiently degraded by free radicals generated from the photoexcited TiO₂ particles, leading to high photocatalytic degradation efficiency. This demonstrates the synergetic effect between adsorption and photocatalytic degradation of the synthesized compounds.     

Effect of alkaline earth metal promoter on catalytic activity of MnO2 for the complete oxidation of toluene

Herein, Na⁺ and Ca²⁺ are introduced to MnO₂ through cation-exchange method. The presence of Na⁺ and Ca²⁺ significantly enhance the catalytic activity of MnO₂ in toluene oxidation. Among them, the Ca-MnO₂ catalyst exhibits the best catalytic activity (T₅₀ = 194°C, T₉₀ = 215°C, E_a = 57.2 kJ/mol, reaction rate 8.40 × 10^?10 mol/(sec?m²) at 210°C. T₅₀ and T₉₀: the temperature of 50% and 90% toluene conversion; E_a: apparent activation energy) and possess high tolerance against 2.0 vol.% water vapor. Results reveal that the increased acidic sites of the MnO₂ sample can enhance the adsorption of gaseous toluene, and the mobility of oxygen species and the content of reactive oxygen species in the catalyst are significantly improved due to the formed oxygen vacancy. Thus these two factors result in excellent catalytic performance for toluene oxidation combining with the weak CO₂ adsorption ability.     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

In situ preparation of visible-light-driven carbon quantum dots/NaBiO3 hybrid materials for the photoreduction of Cr(VI)

In this study, different carbon quantum dots (CQDs)/NaBiO₃ hybrid materials were synthesized as photocatalysts to effectively utilize visible light for the photocatalytic degradation of contaminants effectively. These hybrid materials exhibit an enhanced photocatalytic reduction of hexavalent chromium (Cr(VI)) in the aqueous medium. Zero-dimensional nanoparticles of CQDs were embedded within the two-dimensional NaBiO₃ nanosheets by the hydrothermal process. Compared with that of the pure NaBiO₃ nanosheets, the photocatalytic performance of the hybrid catalysts was significantly high and 6 wt.% CQDs/NaBiO₃ catalyst exhibited better photocatalytic performance. We performed the first-principles density functional theory calculations to study the interfacial properties of pure NaBiO₃ nanosheets and hybrid photocatalysts, and confirmed the CQDs played an important role in the CQDs/NaBiO₃ composites. The experimental results indicated that the enhanced reduction of Cr(VI) was probably due to the high loading of CQDs (electron acceptor) on NaBiO_3, which made NaBiO₃ nanomaterials to respond in visible light and significantly improved their electron-hole separation efficiency.     

Pd/silicalite-1: An highly active catalyst for the oxidative removal of toluene

Catalytic combustion is thought as an efficient and economic pathway to remove volatile organic compounds, and its critical issue is the development of high-performance catalytic materials. In this work, we used the in situ synthesis method to prepare the silicalite-1 (S-1)-supported Pd nanoparticles (NPs). It is found that the as-prepared catalysts displayed a hexagonal prism morphology and a surface area of 390−440 m²/g. The sample (0.28Pd/S-1-H) derived after reduction at 500°C in 10 vol% H₂ showed the best catalytic activity for toluene combustion (T_50% = 180°C and T_90% = 189°C at a space velocity of 40,000 mL/(g·hr), turnover frequency (TOF_Pd) at 160°C = 3.46 × 10⁻³ sec⁻¹, and specific reaction rate at 160°C = 63.8 µmol/(g_Pd·sec)), with the apparent activation energy (41 kJ/mol) obtained over the best-performing 0.28Pd/S-1-H sample being much lower than those (51−70 kJ/mol) obtained over the other samples (0.28Pd/S-1-A derived from calcination at 500°C in air, 0.26Pd/S-1-im derived from the impregnation route, and 0.27Pd/ZSM-5-H prepared after reduction at 500°C in 10 vol% H₂). Furthermore, the 0.28Pd/S-1-H sample possessed good thermal stability and its partial deactivation due to CO₂ or H₂O introduction was reversible, but SO₂ addition resulted in an irreversible deactivation. The possible pathways of toluene oxidation over 0.28Pd/S-1-H was toluene → p-methylbenzoquinone → maleic anhydride, benzoic acid, benzaldehyde → carbon dioxide and water. We conclude that the good dispersion of Pd NPs, high adsorption oxygen species concentration, large toluene adsorption capacity, strong acidity, and more Pd⁰ species were responsible for the good catalytic performance of 0.28Pd/S-1-H.     

Promotional catalytic activity and reaction mechanism of Ag-modified Ce0.6Zr0.4O2 catalyst for catalytic oxidation of ammonia

Ce_1-xZr_xO₂ composite oxides (molar, x = 0-1.0, interval of 0.2) were prepared by a cetyltrimethylammonium bromide-assisted precipitation method. The enhancement of silver-species modification and catalytic mechanism of adsorption-transformation-desorption process were investigated over the Ag-impregnated catalysts for low-temperature selective catalytic oxidation of ammonia (NH₃-SCO). The optimal 5 wt.% Ag/Ce_0.6Zr_0.4O₂ catalyst presented good NH₃-SCO performance with >90% NH₃ conversion at temperature (T) ≥ 250°C and 89% N₂ selectivity. Despite the irregular block shape and underdeveloped specific surface area (∼60 m²/g), the naked and Ag-modified Ce_0.6Zr_0.4O₂ solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (mapping), N₂ adsorption-desorption test and X-ray diffraction (XRD). H₂ temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO₂ reducibility and synergistic Ag⁰/Ag⁺ and Ce⁴⁺/Ce³⁺ redox cycles. Besides, Ag⁺/Ag₂O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia. NH₃-temperature programmed desorption (NH₃-TPD) showed more adsorption-desorption capacity to ammonia were provided by physical, weak- and medium-strong acid sites. Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments revealed the activation of ammonia might be the control step of NH₃-SCO procedure, during which NH₃ dehydrogenation derived from NH_x-species and also internal selective catalytic reduction (i-SCR) reactions were proposed.     

Synthesis of a highly recoverable 3D MnO2/rGO hybrid aerogel for efficient adsorptive separation of pharmaceutical residue

Water contamination by non-steroidal anti-inflammatory drugs, such as acetaminophen, is an emerging ecological concern. In this study, a new three-dimensional manganese dioxide-engrafted reduced graphene oxide (3D MnO₂/rGO) hybrid aerogel was developed for acetaminophen sequestration. The synthesis involved firstly the self-assembly of GO aerogel, followed by thermal reduction and in-situ MnO₂ growth by redox-reaction. The aerogel demonstrated interlinked planes with smooth surfaces deposited with MnO₂ nanospheres and pores of 138.4 – 235.3 µm width. The influences of adsorbent dosage, initial pH, acetaminophen concentration, temperature and contact time were investigated. It was determined that the adsorption of acetaminophen occurred on uniform sorption sites in the aerogel, as suggested by the best fit of data to the Langmuir isotherm, yielding a maximum adsorption capacity of 252.87 mg/g. This highest adsorption performance of the 3D MnO₂/rGO aerogel was attained at a dosage of 0.6 g/L, initial pH of 6.2 and temperature of 40°C. The process kinetics were in-line with the pseudo-first-order and pseudo-second-order kinetics at 10 and 20 – 500 mg/L concentrations, respectively. Thermodynamic assay showed the spontaneity and endothermicity features of the 3D MnO₂/rGO-acetaminophen system. The acetaminophen adsorption mechanisms were mainly hydrogen bonding and pore entrapment. Moreover, the as-synthesised aerogel was effectively regenerated using acetone and re-utilised in four adsorption-desorption cycles. Overall, the results highly recommend the implementation of the 3D MnO₂/rGO hybrid aerogel for purification of wastewater polluted by acetaminophen residue.     

Insight into phase structure-dependent soot oxidation activity of K/MnO2 catalyst

In the present study, two nanosized MnO₂ with β and δ phase structures and potassium loaded MnO₂ catalysts with varied K loading amounts (denoted as K/MnO₂) were prepared. Temperature programmed oxidation and isothermal reactions in loose contact modes were employed to examine the soot oxidation activity of the as-prepared catalysts. Characterization results show that as compared with β-MnO₂, δ-MnO₂ has larger surface area and higher content of hydroxyl groups. Upon K loading, abundant hydroxyl groups in δ-MnO₂ effectively sequestrate K cation to form bound K species and free K species are available only at K loading above 3.0 wt.%. In contrast, the majority of K species present as free state in β-MnO₂ even at a K loading of 1.0 wt.% due to its very low hydroxyl group content. The O₂ temperature-programmed desorption (O₂-TPD) demonstrates that the catalysts with free K species exhibit strong ability in activating gaseous O₂, whereas the catalysts only having bound K display minor O₂ activation capability. As a result, despite of slightly lower activity of β-MnO₂ than δ-MnO₂, the K/β-MnO₂ catalysts exhibit substantially higher activities than K/δ-MnO₂ catalysts with identical K loadings. The finding in this study clearly demonstrates that for MnO₂ based catalysts, the enhancement of catalytic activity for soot oxidation is highly K loading amount dependent and the dependency is strongly associated with the phase structure of MnO₂.     

Effect of reduction pretreatments on PdAg/Al2O3 for HCHO and CO oxidation

PdAg/Al₂O₃ were pretreated by CO and H₂ reduction pretreatments, respectively. The reduced catalysts were tested for HCHO and CO oxidation and characterized by Brunner Emmet Teller (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and oxygen temperature programmed desorption (O₂-TPD). These results indicate that the pretreatments have effect on PdAg reconstruction, PdAg particle size and active oxygen species, which are responsible for the catalytic performance. Compared with H₂ reduction method, CO reduction is more suitable for PdAg/Al₂O₃ pretreatment. PdAg/Al₂O₃-CO exhibited better catalytic performance.     

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation

In this paper, KMnO₄ was used to pre-treat Co₃ Fe-layered double hydroxides(LDH) precursor to prepare MnO₂ decorated Co₃Fe₁O_x catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1 Mn CF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion( T₅₀ and T₉₀) were 218 and 243 ℃, respectively. The apparen...     

N/Ce doped graphene supported Pt nanoparticles for the catalytic oxidation of formaldehyde at room temperature

Pt catalysts with nitrogen-doped graphene oxide (GO) as support and CeO₂ as promoter were prepared by impregnation method,and their catalytic oxidation of formaldehyde (HCHO) at room temperature was tested.The Pt-CeO₂/N-rGO (reduced GO) with a mass fraction of 0.7% Pt and 0.8%CeO₂ exhibited an excellent catalytic performance with the 100% conversion of HCHO at room temperature.Physicochemical characterization demonstrated that nitrogendoping greatly increased the...     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

Improvement of the activity and SO2 tolerance of Sb-modified Mn/PG catalysts for NH3-SCR at a low temperature

A series of MnM/palygorskite (PG) (M = La, W, Mo, Sb, Mg) catalysts was prepared by the wetness co-impregnation method for low-temperature selective catalytic reduction (SCR) of NO with NH₃. Conversion efficiency followed the order Sb > Mo > La > W > Mg. A combination of various physico-chemical techniques was used to investigate the influence of Sb-modified Mn/PG catalysts. MnSb_0.156/PG catalyst showed highest NO conversion at low temperatures in the presence of SO₂ which reveals that addition of Sb oxides effectively enhances the SCR activity of catalysts. A SO₂ step-wise study showed that MnSb_0.156/PG catalyst displays higher durable resistance to SO₂ than Mn/PG catalyst, where the sulfating of active phase is greatly inhibited after Sb doping. Scanning electron microscopy and X-ray diffraction results showed that Sb loading enhances the dispersion of Mn oxides on the carrier surface. According to the results of characterization analyses, it is suggested that the main reason for the deactivation of Mn/PG is the formation of manganese sulfates which cause the permanent deactivation of Mn-based catalysts. For Sb-doped Mn/PG catalyst, SO_x ad-species formed were mainly combined with SbO_x rather than MnO_x. This preferential interaction between SbO_x and SO₂ effectively shields the MnO_x as active species from being sulfated by SO₂ resulting in the improvement of SO₂ tolerance on Sb-added catalyst. Multiple information support that, owing to the addition of Sb, original formed MnO_x crystallite has been completely transformed into highly dispersed amorphous phase accounting for higher SCR activity.     

CeO2形貌结构对催化湿式空气氧化苯酚性能的影响

采用水热法、沉淀法和溶胶凝胶法制备了3种不同形貌的CeO₂催化材料,并将其用于湿式空气氧化苯酚水溶液过程中,探讨了CeO₂形貌结构对催化湿式氧化苯酚水溶液性能的影响.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、程序升温还原（TPR）等手段对CeO₂催化材料进行了表征.结果表明,水热法制备的CeO₂催化材料表现出较好催化性能,主要原因是水热法合成的CeO₂呈现交错的纳米棒状结构,主要暴露（220）晶面,且沿着（220）晶向生长.在反应温度为200℃、空气压力为2MPa、苯酚初始浓度500mg/L的条件下,最终（240min）COD的去除率为95.5%.     

CeO2形貌结构对催化湿式空气氧化苯酚性能的影响

采用水热法、沉淀法和溶胶凝胶法制备了3种不同形貌的CeO₂催化材料,并将其用于湿式空气氧化苯酚水溶液过程中,探讨了CeO₂形貌结构对催化湿式氧化苯酚水溶液性能的影响.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、程序升温还原（TPR）等手段对CeO₂催化材料进行了表征.结果表明,水热法制备的CeO₂催化材料表现出较好催化性能,主要原因是水热法合成的CeO₂呈现交错的纳米棒状结构,主要暴露（220）晶面,且沿着（220）晶向生长.在反应温度为200℃、空气压力为2MPa、苯酚初始浓度500mg/L的条件下,最终（240min）COD的去除率为95.5%.