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1.
Environ Sci Technol ; 58(33): 14812-14822, 2024 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-39118219

RESUMEN

The surface photochemical activity of goethite, which occurs widely in surface soils and sediments, plays a crucial role in the environmental transformation of various pollutants and natural organic matter. This study systemically investigated the mechanism of different types of surface hydroxyl groups on goethite in generating reactive oxygen species (ROSs) and Fe(III) reduction under sunlight irradiation. Surface hydroxyl groups were found to induce photoreductive dissolution of Fe(III) at the goethite-water interface to produce Fe2+(aq), while promoting the production of ROSs. Substitution of the surface hydroxyl groups on goethite by fluoride significantly inhibited the photochemical activity of goethite, demonstrating their important role in photochemical activation of goethite. The results showed that the surface hydroxyl groups (especially the terminating hydroxyl groups, ≡FeOH) led to the formation of Fe(III)-hydroxyl complexes via ligand-metal charge transfer on the goethite surface upon photoexcitation, facilitating the production of Fe2+(aq) and •OH. The bridging hydroxyl groups (≡Fe2OH) were shown to mainly catalyze the production of H2O2, leading to the subsequent light-driven Fenton reaction to produce •OH. These findings provide important insights into the activation of molecular oxygen on the goethite surface driven by sunlight in the environment, and the corresponding degradation of anthropogenic and natural organic compounds caused by the generated ROSs.


Asunto(s)
Especies Reactivas de Oxígeno , Especies Reactivas de Oxígeno/química , Oxidación-Reducción , Compuestos Férricos/química , Compuestos de Hierro/química , Hierro/química , Minerales/química , Radical Hidroxilo/química , Procesos Fotoquímicos
2.
J Colloid Interface Sci ; 677(Pt A): 282-293, 2024 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-39094489

RESUMEN

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) are attractive approaches for solving the global problem of water pollution, due to the generation of highly-active reactive oxygen species (ROS). Therefore, highly-efficient PMS activation is crucial for promoting the catalytic degradation of environmental pollutants. Here, bimetallic CoGeO2(OH)2 nanosheets with abundant surface hydroxyl groups (CGH) were synthesized via a simple hydrothermal route for PMS activation and degradation of various organic contaminants for the first time. The abundant surface hydroxyl groups (≡Co-OH/≡Ge-OH) could promptly initiate PMS to generate highly-active species: singlet oxygen (1O2), sulfate radicals (SO4·-) and hydroxyl radicals (HO•), while the asymmetric electron distribution among Co-O-Ge bonds derived from the higher electronegativity of Ge than Co further enhances the quick electron transfer to promote the redox cycle of Co2+/Co3+ and Ge2+/Ge4+, thereby achieving an outstanding catalytic capability. The optimal catalyst exhibits nearly 100 % catalytic degradation performance of dyes (Methylene blue, Rhodamine B, Methyl orange, Orange II, Methyl green) and antibiotics (Norfloxacin, Bisphenol A, Tetracycline) over a wide pH range of 3-11 and under different coexisting anion conditions (Cl-, HCO3-, NO3-, HA), suggesting the excellent adaptability for practical usage. This study could potentially lead to novel perspectives on the remediation of water areas such as groundwater and deep-water areas.

3.
Molecules ; 29(12)2024 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-38930868

RESUMEN

Ni-based catalysts have been widely used for the CO2 reforming of methane (CRM) process, but deactivation is their main problem. This study created an alternative electronic Ni-NiO-CeO2 interaction on the surface of 5 wt% Ni-5 wt% CeO2/Al2O3-MgO (5Ni5Ce(xh)/MA) catalysts to enhance catalytic potential simultaneously with coke resistance for the CRM process. The Ni-NiO-CeO2 network was developed on Al2O3-MgO through layered double hydroxide synthesis via our ammonia vapor diffusion impregnation method. The physical properties of the fresh catalysts were analyzed employing FESEM, N2 physisorption, and XRD. The chemical properties on the catalyst surface were analyzed employing H2-TPR, XPS, H2-TPD, CO2-TPD, and O2-TPD. The CRM performances of reduced catalysts were evaluated at 600 °C under ambient pressure. Carbon deposits on spent catalysts were determined quantitatively and qualitatively by TPO, FESEM, and XRD. Compared to 5 wt% Ni-5 wt% CeO2/Al2O3-MgO prepared by the traditional impregnation method, the electronic interaction of the Ni-NiO-CeO2 network with the Al2O3-MgO support was constructed along the time of ammonia diffusion treatment. The electronic interaction in the Ni-NiO-CeO2 nanostructure of the treated catalyst develops surface hydroxyl sites with an efficient pathway of OH* and O* transfer that improves catalytic activities and coke oxidation.

4.
Sensors (Basel) ; 24(11)2024 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-38894323

RESUMEN

In this work, pure phase and carbon/ZnSn(OH)6 samples were synthesized by a hydrothermal method. The composite sample's structure, morphology, and functional groups were investigated by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Subsequently, ZnSn(OH)6 samples were modified with different carbon contents, and their humidity-sensing properties were investigated. The introduction of carbon increased the specific surface area of pure ZnSn(OH)6 samples, thus significantly improving the sensors' humidity sensing response. The C10-ZnSn(OH)6 sensor exhibited a high response, up to three orders of magnitude, a humidity hysteresisof 13.5%, a fast response time of 3.2 s, and a recovery time of 24.4 s. The humidity sensor's possible humidity sensing mechanism was also analyzed using the AC complex impedance puissance method with a simulated equivalent circuit. These results revealed that ZnSn(OH)6 can effectively detect ambient humidity and that the introduction of carbon significantly improves its humidity-sensing performance. The study provides an effective strategy for understanding and designing ZnSn(OH)6-based humidity sensors.

5.
Environ Sci Technol ; 58(23): 10378-10387, 2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38805367

RESUMEN

Room temperature catalytic oxidation (RTCO) using non-noble metals has emerged as a highly promising technique for removal of formaldehyde (HCHO) under ambient conditions; however, non-noble catalysts still face the challenges related to poor water resistance and low stability under harsh conditions. In this study, we synthesized a series of layered double hydroxides (LDHs) incorporating various dual metals (MgAl, ZnAl, NiAl, NiFe, and NiTi) for formaldehyde oxidation at ambient temperature. Among the synthesized catalysts, the NiTi-LDH catalyst showed an HCHO removal efficiency and CO2 yield close to 100.0%, and exceptional water resistance and chemical stability on running 1300 min. The abundant hydroxyl groups in LDHs directly bonded with HCHO, leading to the production of CO2 and H2O, thus inhibiting the formation of CO, even in the absence of O2 and H2O. The coexistence of O2 effectively reduced the reaction barrier for H2O molecule dissociation, facilitating the formation of hydroxyl groups and their subsequent backfill on the catalyst surface. The mechanisms underlying the involvement and regeneration of hydroxyl groups in room temperature oxidation of formaldehyde were elucidated with the combined in situ DRIFTS, HCHO-TPD-MS, and DFT calculations. This work not only demonstrates the potential of LDH catalysts in environmental applications but also advances the understanding of the fundamental processes involved in room temperature oxidation of formaldehyde.


Asunto(s)
Formaldehído , Hidróxidos , Oxidación-Reducción , Temperatura , Formaldehído/química , Hidróxidos/química , Catálisis
6.
Environ Sci Technol ; 58(21): 9361-9369, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38687995

RESUMEN

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtOx/TiO2 and PtOx-y(OH)y/TiO2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtOx/TiO2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO2 was around 14 times as high as that on PtOx-y(OH)y/TiO2. Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtOx promoted strong electronic coupling of the Pt 5d orbital in PtOx and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtOx and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtOx in toluene oxidation, providing a further understanding of hydrocarbon oxidation.


Asunto(s)
Oxidación-Reducción , Platino (Metal) , Tolueno , Catálisis , Tolueno/química , Platino (Metal)/química , Titanio/química , Adsorción
7.
Environ Sci Technol ; 58(9): 4404-4414, 2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38310571

RESUMEN

Photocatalytic oxidation has gained great interest in environmental remediation, but it is still limited by its low efficiency and catalytic deactivation in the degradation of aromatic VOCs. In this study, we concurrently regulated the surface hydroxyl and oxygen vacancies by introducing Al into ZnSn layered double hydroxide (LDH). The presence of distorted Al species induced local charge redistribution, leading to the remarkable formation of oxygen vacancies. These oxygen vacancies subsequently increased the amount of surface hydroxyl and elongated its bond length. The synergistic effects of surface hydroxyl and oxygen vacancies greatly enhanced reactant adsorption-activation and facilitated charge transfer to generate •OH, •O2-, and 1O2, resulting in highly efficient oxidation and ring-opening of various aromatic VOCs. Compared with commercial TiO2, the optimized ZnSnAl-50 catalyst exhibited about 2-fold activity for the toluene and styrene degradation and 10-fold activity for the chlorobenzene degradation. Moreover, ZnSnAl-50 demonstrated exceptional stability in the photocatalytic oxidation of toluene under a wide humidity range of 0-75%. This work marvelously improves the photocatalytic efficiency, stability, and adaptability through a novel strategy of surface hydroxyl and oxygen vacancies engineering.


Asunto(s)
Radical Hidroxilo , Oxígeno , Adsorción , Oxidación-Reducción , Tolueno
8.
Sci Total Environ ; 914: 169717, 2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38163606

RESUMEN

When precious nano-metals are used as environmental catalysts, it is important to tune the particle sizes and the reusability of the nano-metals for achieving their highly efficient catalytic performance at a low cost. In the present work, magnetic iron oxides (FeOx-Y) nanoparticles were pre-prepared as supports of nano-metals, where Y represented the mole percentage of Fe(III) in the total iron (Y ≥ 50 %). FeOx-Y (support), PdCl42- (Pd source) and NaBH4 (reducing agent) were added into the organic pollutant solution containing 2,2',4,4'-tetrabromodiphenyl ether (BDE47). After the NaBH4 was added, the followed reaction realized not only the rapid in-situ preparation of a Pd-loaded FeOx-Y composite catalyst (Pd-FeOx-Y), but also the ultra-fast and complete debromination of BDE47 within 30 s. Comparing the case without adding FeOx-Y, the debromination efficiency of BDE47 was much promoted in the presence of FeOx-Y. The support-induced enhancing effect on the catalytic ability of Pd nanoparticles was improved by increasing the Fe(III) content in the support, being attributed to the much more hydroxyl groups on the support surface. Considering both the catalytic and recovery abilities of Pd-FeOx-Y, Pd-FeOx-75 was the optimal choice because it could be magnetically recovered and re-used for multiple cycles with high catalytic activities. The presently developed "catalyst preparation-pollutant degradation" one-pot system could be applied to conduct complete debromination of all the PBDEs.

9.
ACS Appl Mater Interfaces ; 16(1): 454-466, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38147632

RESUMEN

Fine-tuning the dispersion of active metal species on widely used supports is a research hotspot in the catalysis community, which is vital for achieving a balance between the atomic utilization efficiency and the intrinsic activity of active sites. In this work, using bayerite Al(OH)3 as support directly or after precalcination at 200 or 550 °C, Pt/Al2O3 catalysts with distinct Pt dispersions from single atoms to clusters (ca. 2 nm) were prepared and evaluated for CO and NH3 removal. Richer surface hydroxyl groups on AlOx(OH)y support were proved to better facilitate the dispersion of Pt. However, Pt/Al2O3 with relatively lower Pt dispersion could exhibit better activity in CO/NH3 oxidation reactions. Further reaction mechanism study revealed that the Pt sites on Pt/Al2O3 with lower Pt dispersion could be activated to Pt0 species much easier under the CO oxidation condition, on which a higher CO adsorption capacity and more efficient O2 activation were achieved simultaneously. Compared to Pt single atoms, PtOx clusters could also better activate NH3 into -NH2 and -HNO species. The higher CO adsorption capacity and the more efficient NH3/O2 activation ability on Pt/Al2O3 with relatively lower Pt dispersion well explained its higher CO/NH3 oxidation activity. This study emphasizes the importance of avoiding a singular pursuit of single-atom catalyst synthesis and instead focusing on achieving the most effective Pt species on Al2O3 support for targeted reactions. This approach avoids unnecessary limitations and enables a more practical and efficient strategy for Pt catalyst fabrication in emission control applications.

10.
ACS Appl Mater Interfaces ; 15(30): 36312-36323, 2023 Aug 02.
Artículo en Inglés | MEDLINE | ID: mdl-37486250

RESUMEN

Developing visible-light-driven photocatalysts for the catalytic dehydrogenation of organics is of great significance for sustainable solar energy utilization. Here, we first report that aromatic alcohols could be efficiently split into H2 and aldehydes over TiO2 under visible-light irradiation through a ligand-to-metal charge transfer (LMCT) mechanism. A series of TiO2 catalysts with different surface contents of the hydroxyl group (-OH) have been synthesized by controlling the hydrothermal and calcination synthesis methods. An optimal H2 production rate of 18.6 µmol h-1 is obtained on TiO2 synthesized from the hydrothermal method with a high content of surface -OH. Experimental characterizations and comparison studies reveal that the surface -OH markedly influences the formation of LMCT complexes and thus changes the visible-light-driven photocatalytic performance. This work is anticipated to inspire further research endeavors in the design and fabrication of visible-light-driven photocatalyst systems based on the LMCT mechanism to realize the simultaneous synthesis of clean fuel and fine chemicals.

11.
Small ; 19(28): e2300520, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37191281

RESUMEN

Nanotechnology has delivered an amazing range of new materials such as nanowires, tubes, ribbons, belts, cages, flowers, and sheets. However, these are usually circular, cylindrical, or hexagonal in nature, while nanostructures with square geometries are comparatively rare. Here, a highly scalable method is reported for producing vertically aligned Sb-doped SnO2 nanotubes with perfectly-square geometries on Au nanoparticle covered m-plane sapphire using mist chemical vapor deposition. Their inclination can be varied using r- and a-plane sapphire, while unaligned square nanotubes of the same high structural quality can be grown on silicon and quartz. X-ray diffraction measurements and transmission electron microscopy show that they adopt the rutile structure growing in the [001] direction with (110) sidewalls, while synchrotron X-ray photoelectron spectroscopy reveals the presence of an unusually strong and thermally resilient 2D surface electron gas. This is created by donor-like states produced by the hydroxylation of the surface and is sustained at temperatures above 400 °C by the formation of in-plane oxygen vacancies. This persistent high surface electron density is expected to prove useful in gas sensing and catalytic applications of these remarkable structures. To illustrate their device potential, square SnO2 nanotube Schottky diodes and field effect transistors with excellent performance characteristics are fabricated.

12.
Environ Technol ; 44(5): 647-658, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34516339

RESUMEN

Volatile organic compounds (VOCs) have caused a serious threat to the atmosphere and human health. Therefore, it is of great significance to exploit effective catalytic materials for the safe and effective catalytic elimination of VOCs. Herein, Ag-MnOx-ACF composite catalysts were constructed via a two-step impregnation strategy and used for catalytic toluene degradation. A remarkable low-temperature catalytic activity (T100 = 50℃), excellent stability, as well as CO2 selectivity (80%) were achieved over the Ag-MnOx-ACF catalyst. A series of characterizations indicated that the unique manganese defects structure of birnessite phase manganese oxide played an essential role for toluene oxidation, which was conducive to generating surface adsorbed oxygen. The higher ratio of Mn3+/Mn4+, abundant surface adsorbed oxygen and highly dispersed Ag species were determined to significantly facilitate toluene degradation. The mechanism of efficient degradation of toluene at low temperature was proposed. O3 and H2O molecules were activated via surface hydroxyl and Mn defects on Ag-MnOx-ACF to produce sufficient •OH, enhancing the degradation performance of toluene. We provide a new idea for the catalytic oxidation of benzene VOCs at low even room temperatures.


Asunto(s)
Óxidos , Tolueno , Humanos , Temperatura , Tolueno/química , Óxidos/química , Oxidación-Reducción , Manganeso , Oxígeno , Catálisis
13.
Environ Technol ; 44(6): 739-750, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34534044

RESUMEN

In this study, expanded graphite (EG) was prepared by the oxidation and intercalation of the natural flake graphite using perchloric acid and potassium permanganate at different expansion temperatures (300, 400, 500, and 600°C), and were characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). EG prepared at 500°C was found to be highly effective for the mineralization of oxalic acid aqueous solution during ozonation at pH 3, which was ascribed to the formation of hydroxyl radicals from the surface reaction of surface hydroxyl groups on EG with ozone. The performance of expanded graphite in this catalytic system was basically unchanged after three repeated use. The presence of Cl-, SO42-, HPO42-/H2PO4- and NO3- could inhibit the degradation of oxalic acid in catalytic ozonation with EG. Degradations of oxamic acid and pyruvic acid in catalytic ozonation with EG were pH-dependent, which were lower than that of oxalic acid. The degradations of oxalic acid and oxamic acid were identified as mineralization process by the determination of TOC, while pyruvic acid may transform into organic products such as acetic acid by O3/EG. Manganese ion (Mn2+) could promote the degradation of oxalic acid by O3/EG at pH 3 because permanganate was produced by O3/EG in oxalic acid solution and then reacted with oxalic acid readily at acidic pH. Catalytic ozonation by EG exhibited great application potential for the destruction of refractory organic compounds.


Asunto(s)
Grafito , Ozono , Contaminantes Químicos del Agua , Grafito/química , Ácido Oxámico , Ácido Pirúvico , Agua , Ácido Oxálico/química , Catálisis , Ozono/química , Contaminantes Químicos del Agua/química
14.
Chemosphere ; 313: 137570, 2023 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-36563731

RESUMEN

Phyllosilicate minerals are the important components in soils and an important source of activated aluminum (Al) during soil acidification. However, the mechanisms for Al activation in phyllosilicate minerals were not understood well. In this paper, the effect of phyllosilicate surface hydroxyl groups on Al activation during acidification was studied after the minerals were modified with inorganic and organic materials. After modification of kaolinite, montmorillonite, and illite with fulvic acid (FA-), iron oxide (Fe-), Fe combined with FA (Fe-FA-), and siloxane (Si-O-), the interlayer spaces were altered. For instance, when modified with Fe, Fe entered the interlayer spaces of kaolinite and montmorillonite and changed the interlayer spaces of both minerals but did not affect that of illite. Also, the other modification methods had significant effects on the interlayer space of montmorillonite but not on kaolinite and illite. It was observed that all the modification strategies inhibited Al activation during acidification by reducing the number of hydroxyl groups on the mineral surfaces and inhibiting protonation reactions between H+ and hydroxyl groups. Nevertheless, the inhibition effect varies with the type of phyllosilicate mineral. For kaolinite (Kao), the inhibition effect of the different modification methods on Al activation during acidification followed: Fe-FA-Kao > Fe-Kao > Si-O-Kao > FA-Kao. Additionally, for montmorillonite (Mon), the inhibition effect was in the order: Si-O-Mon > Fe-Mon > Fe-FA-Mon > FA-Mon, while for illite, it was: Fe-illite > Si-O-illite ≈ Fe-FA-illite > FA-illite. Thus, the hydroxyl groups on the surfaces and edges of phyllosilicate minerals play an important role in the activation of Al from the mineral structure. Also, the protonation of hydroxyl groups may be the first step during Al activation in these minerals. The results of this study can serve as a reference for the development of new technologies to inhibit soil acidification and Al activation.


Asunto(s)
Aluminio , Caolín , Caolín/química , Arcilla , Bentonita/química , Silicatos de Aluminio/química , Adsorción , Minerales/química , Suelo , Concentración de Iones de Hidrógeno
15.
J Environ Sci (China) ; 126: 668-682, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36503792

RESUMEN

In the present study, two nanosized MnO2 with ß 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 ß-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 ß-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 ß-MnO2 than δ-MnO2, the K/ß-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.


Asunto(s)
Compuestos de Manganeso , Hollín , Óxidos , Gases , Potasio
16.
Environ Sci Technol ; 56(24): 17785-17794, 2022 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-36472936

RESUMEN

Iron (hydr)oxides as a kind of natural mineral actively participate in the transformation of organic pollutants, but there is a large knowledge gap in their impacts on photochemical processes of microplastics (MPs). This study is the first to examine the degradation of two ordinary plastic materials, polyethylene (PE) and polypropylene (PP), mediated by iron (hydr)oxides (goethite and hematite) under simulated solar light irradiation. Both iron (hydr)oxides significantly promoted the degradation of MPs (particularly PP) with a greater effect by goethite than hematite, related to hydroxyl radical (•OH) produced by iron (hydr)oxides. Under light irradiation, the surface Fe(II) phase catalyzed the production of H2O2 and promoted the release of Fe2+, leading to the subsequent light-driven Fenton reaction which produced a large amount of •OH. As the iron (hydr)oxides were modified with NaF at various concentrations, the activity of the surface Fe(II) as well as the release of Fe2+ were greatly reduced, and thus the •OH formation and MP degradation were depressed remarkably. It is worth noting that the surface hydroxyl groups (especially ≡FeOH) affected the reaction kinetics of •OH by regulating the activity of Fe species. These findings unveil the distinct impacts and intrinsic mechanisms of iron (hydr)oxides in influencing the photodegradation of MPs.


Asunto(s)
Hierro , Óxidos , Microplásticos , Plásticos , Fotólisis , Peróxido de Hidrógeno , Compuestos Férricos , Oxidación-Reducción , Compuestos Ferrosos
17.
Environ Sci Technol ; 56(15): 10916-10924, 2022 08 02.
Artículo en Inglés | MEDLINE | ID: mdl-35770877

RESUMEN

Pt/Al2O3 catalysts showing excellent activity and stability have been used in various reactions, including HCHO oxidation. Herein, we prepared Pt-Na/Al2O3 catalysts with a Pt content of 0.05 wt % to reveal the key factors determining the anchoring of Pt as well as the catalytic activity and mechanism of HCHO oxidation. Pt-Na/nano-Al2O3 (denoted as Pt-Na/nAl2O3) catalysts with 0.05 wt % Pt content could completely oxidize HCHO to CO2 at room temperature, which is the lowest Pt content used in HCHO catalytic oxidation to our knowledge. After Na addition, terminal hydroxyl groups (denoted as HO-µter) on nano-Al2O3 were transformed to doubly bridging hydroxyl groups between Na and Al (denoted as HO-µbri(Na-Al)), which atomically dispersed Pt species. Pt anchoring further promoted the regeneration of HO-µbri(Na-Al) by activating O2 and H2O, oxidizing HCHO to CO2 directly by the fast reaction step ([HCOO-] + [OH]a → CO2 + H2O). Our study revealed that the HO-µbri(Na-Al) synergistically generated by HO-µter and Na species provided anchoring sites for Pt species.


Asunto(s)
Dióxido de Carbono , Formaldehído , Catálisis , Oxidación-Reducción , Platino (Metal)
18.
Angew Chem Int Ed Engl ; 61(35): e202206077, 2022 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-35730919

RESUMEN

Manipulating the catalyst-electrolyte interface to push reactants into the inner Helmholtz plane (IHP) is highly desirable for efficient electrocatalysts, however, it has rarely been implemented due to the elusive electrochemical IHP and inherent inert catalyst surface. Here, we propose the introduction of local force fields by the surface hydroxyl group to engineer the electrochemical microenvironment and enhance alkaline hydrogen evolution activity. Taking a hydroxyl group immobilized Ni/Ni3 C heterostructure as a prototype, we reveal that the local hydrogen bond induced by the surface hydroxyl group drags 4-coordinated hydrogen-bonded H2 O molecules across the IHP to become free H2 O and thus continuously supply reactants forcatalytic sites catalytic sites. In addition, the hydroxyl group coupled with the Ni/Ni3 C heterostructure further lowers the water dissociation energy by polarization effects. As a direct outcome, hydroxyl-rich catalysts surpass Pt/C activity at high current density (500 mA cm-2 @ ≈276 mV) in alkaline medium.

19.
J Hazard Mater ; 435: 128994, 2022 08 05.
Artículo en Inglés | MEDLINE | ID: mdl-35490633

RESUMEN

Nanoplastics (NPs), which are often detected in the natural environment, are regarded as a group of emerging pollutants. Hematite is a substance that exists widely in the surface environment and has an important impact on the environmental behavior of pollutants. Clarifying the migration of NPs requires an in-depth understanding of intrinsic interaction mechanisms of NPs with iron-containing minerals. The interaction process of polystyrene nanoplastics (PSNPs) on the hematite exposed facets was systematically studied by experiments under different conditions, adsorption isotherm curves, Fourier Transform infrared (FTIR) spectroscopy and two-dimensional correlation spectroscopy (2D-COS) analyses. We found that PSNPs were adsorbed on the three exposed faces of hematite ({001}, {012}, and {100}) by electrostatic interaction, respectively, but the capacities for PSNPs were different. Adsorption models were established to explore the preferred interaction surface dependent on the exposed facets, and it was found that {012} surfaces were more favorable for PSNPs adsorption, while {001} surface has better adsorption capacity for PSNPs than {100} surface, which is due to the different density and proportion of hydroxyl groups on the exposed facets of hematite. These findings elucidated the dependence of PSNPs adsorption on the hematite facets, and illustrated t the effect of hematite on the migration of PSNPs in the environment.


Asunto(s)
Contaminantes Ambientales , Nanopartículas , Adsorción , Compuestos Férricos , Hierro , Microplásticos , Óxidos , Poliestirenos
20.
J Colloid Interface Sci ; 617: 246-256, 2022 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-35278862

RESUMEN

The mixed-valent magnetite (Fe3O4) played a critical role in H2O2-based Fenton-like system for the removal of chlorophenols, but high activity and cycle stability of the Fe3O4-based catalysts are still a huge challenge. Herein, a series of surface hydroxyl- and carboxyl-modified Ag0/Fe3O4 nanocomposite catalysts were prepared and used to activate H2O2 for degradation chlorophenols pollutants. Under the optimized condition, nearly 100% degradation ratio were achieved within 2-30 min for 2,4-dichlorophenol, 2,3-dichlorophenol, 3,4-dichlorophenol, 2,4,6-trichlorophenol, p-nitrophenol, and 98% degradation ratio for 2,5-dichlorophenol, 2,6-dichlorophenol and 3,5-dichlorophenol,. Moreover, wide pH applicability was obtained for the Ag0/Fe3O4-H2O2 system, where 95% degradation ratio of 2,4-dichlorophenol was still obtained at pH 6.0. The excellent activity of Ag0/Fe3O4 catalyst can be ascribed to the incorporation of Ag0 nanoparticles that accelerated the Fe(III)/Fe(II) transformation with the assistance of surface hydroxyl and carboxyl groups. Detailed mechanism study indicated a pseudo-second-order kinetic model, where the oxidative degradation and reductive degradation pathways coexisted in the system. The surface-modified Ag0/Fe3O4-H2O2 provide a practical catalyst system for the removal of phenol contaminants with high reaction rate, wide pH adaptability, and validity for a series of chlorophenols.


Asunto(s)
Clorofenoles , Nanocompuestos , Catálisis , Compuestos Férricos , Óxido Ferrosoférrico , Peróxido de Hidrógeno , Radical Hidroxilo , Oxidación-Reducción , Plata
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