- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Novel Porous Boron Nitride Nanosheet with Carbon Doping: Potential Metal-Free Photocatalyst for Visible-Light-Driven Overall Water Splitting
摘要： The band gap of hexagonal boron nitride (h-BN) is far too wide for efficiently utilizing visible light, limiting its application in photocatalysis. The present study employs first principles calculations to demonstrate that the band gap energies of porous h-BN (p-BN) can be tuned by carbon doping to levels appropriate for the absorption of visible-light, and that the conduction band and valence band match well with the potentials of both hydrogen and oxygen evolution reactions. Importantly, a strategy of carbon doping to improve the energy level of valence band maximum is also proposed. Moreover, the carbon-doped p-BN exhibits good separation between photogenerated electrons/holes and structural stability at high temperatures. The DFT results help the design of high-performance two-dimensional photocatalysts that avoid the use of metals.
关键词： metal-free catalysts,photocatalyst,porous boron nitride nanosheets,overall water splitting,band structure engineering
更新于2025-09-23 15:22:29
-
Artificial Mn4Ca-cluster with Exchangeable Solvent Molecules Mimicking the Oxygen-Evolving Center in Photosynthesis
摘要： The natural Mn4Ca-cluster in photosystem II serves as a blueprint to develop artificial water-splitting catalysts in artificial photosynthesis. Although significant advances have recently been achieved, it remains great challenges to prepare robust artificial Mn4Ca-cluster to precisely mimic the structure and function of the biological catalyst in the laboratory. Here, we report the isolation and structural characterization of two Mn4CaO4-complexes from polar solvents acetonitrile or N, N-dimethylformamide, which closely mimics the two water molecules on calcium ion, as well as, the oxidation states of the four manganese ions and the main geometric structure of the natural Mn4Ca-cluster. These new artificial Mn4Ca-complexes provide important chemical clues to understand the structure and mechanism of its biological paragon.
关键词： bioinorganic chemistry,photosynthesis,manganese,heterometallic complexes,water splitting
更新于2025-09-23 15:22:29
-
Photoelectrochemical water splitting with p-type metal oxide semiconductor photocathodes Youn Jeong Jang[a] and Jae Sung Lee*[a]
摘要： Photoelectrochemical (PEC) water splitting is a promising way to produce clean and sustainable hydrogen fuel. Solar hydrogen production using p-type metal oxide semiconductor photocathodes has not been studied as extensively as n-type metal oxide semiconductor photoanodes and p-type PV-grade non-oxide semiconductor photocathodes. Copper-based oxide photocathodes show relatively good conductivity but suffer from instability in an aqueous solution under illumination. On the other hands, Fe-based metal oxide photocathodes demonstrate more stable PEC performance, but have problems in charge separation and transport. In this mini-review article, we provide an overview of the recent progress in p-type metal oxide-based photocathodes for PEC water reduction. Although these materials are not fully developed up to their potential performance, the involved challenges have been identified and strategies to overcome the limitations have been proposed. Future research in this field should address these issues and challenges in addition to discovery of new materials.
关键词： metal oxides,p-type semiconductors,photoelectrochemical cell,photocathodes,solar water splitting
更新于2025-09-23 15:22:29
-
Promotion of Overall Water Splitting Activity Over a Wide pH Range by Interfacial Electrical Effects of Metallic NiCo-nitrides Nanoparticle/NiCo <sub/>2</sub> O <sub/>4</sub> Nanoflake/graphite Fibers
摘要： Many efforts have been made to develop bifunctional electrocatalysts to facilitate overall water splitting. Here, a fibrous bifunctional 3D electrocatalyst is reported for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) with high performance. The remarkable electrochemical performance is attributed of the catalysts to a number of factors: the metallic character of the three components (i.e., Ni3N, CoN, and NiCo2O4); the electronic structure, nanoflake-nanosphere network with abundant electroactive sites, and the electric field effect at the interfaces between different components. The oxide–nitride/graphite fibers have the lowest overpotential requirements of 71 and 183 mV at 10 mA cm?2 for HER and OER in alkaline medium, respectively. These values are comparable to those of commercial Pt/C (20 wt%) and RuO2. The electrodes also show a response to HER and OER in both neutral and acid media. Furthermore, the 3D structure can be highlighted by all-round electrodes for overall water splitting. The calculations on the changes in electrons transfer and the Femi level from oxides to oxides/nitrides reveal that the observed superb electrocatalytic performance can be attributed to the presence of Ni3N and CoN derived from the in situ nitridation of NiCo2O4.
关键词： electrocatalysts,overall water splitting,interfacial electrical effects
更新于2025-09-23 15:22:29
-
Transparent Ta3N5 Photoanodes for Efficient Oxygen Evolution toward the Development of Tandem Cells
摘要： Photoelectrochemical water splitting is regarded as a promising approach to the production of hydrogen, and the development of efficient photoelectrodes is one aspect of realizing practical systems. In this work, transparent Ta3N5 photoanodes were fabricated on n-type GaN/sapphire substrates to promote O2 evolution in tandem with a photocathode, to realize overall water splitting. Following the incorporation of an underlying GaN layer, a photocurrent of 6.3 mA cm-2 was achieved at 1.23 V vs. a reversible hydrogen electrode. The transparency of Ta3N5 to wavelengths longer than 600 nm allowed incoming solar light to be transmitted to a CuInSe2 (CIS), which absorbs up to 1100 nm. A stand-alone tandem cell with a serially-connected dual-CIS unit terminated with a Pt/Ni electrode was thus constructed for H2 evolution. This tandem cell exhibited a solar-to-hydrogen energy conversion efficiency greater than 7% at the initial stage of the reaction.
关键词： solar energy conversion,photoelectrochemistry,water splitting,photoelectrochemical tandem cell,(oxy)nitrides
更新于2025-09-23 15:22:29
-
Anti-Markovnikov Hydroazidation of Alkenes by Visible Light Photoredox Catalysis
摘要： The anti-Markovnikov hydroazidation of alkenes has been accomplished using [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as photocatalyst and trimethylsilyl azide as azidating agent. The reactions were greatly facilitated by water, whose beneficial effect can be attributed to its participation in the reaction as the hydrogen donor, as indicated by deuterium isotope experiments. The reactions can be effected under solvent free conditions in the presence of water. 4-Dimethylaminopyridine also exhibited a beneficial effect on the reactions. The present method enabled hydroazidation of several types of unactivated alkenes with good yield and high regionselectivity.
关键词： hydroazidation,water,trimethylsilyl azide,radical reactions,photoredox catalysis
更新于2025-09-23 15:22:29
-
Visible-Light-Driven Photocatalytic Z-scheme Overall Water Splitting in La5Ti2AgS5O7-based Powder Suspension System
摘要： La5Ti2CuxAg1-xS5O7 (x=0-1) is a kind of long-wavelength-responsive oxysulfide photocatalysts for hydrogen evolution, and has been demonstrated to enable the Z-scheme water splitting coupling with oxygen evolution photocatalysts (OEP) the particulate sheet. We herein report that among La5Ti2CuxAg1-xS5O7, La5Ti2AgS5O7 was found to have the highest performance on Z-scheme overall water splitting in conjunction with PtOx-WO3 as an OEP, and a triiodide/iodide (I3?/I?) redox couple as a shuttle electron mediator in powder suspension system. Loading Pt/NiS on La5Ti2AgS5O7 benefits the Z-scheme to achieve an apparent quantum yield of 0.12% at 420 nm. The finding in powder suspension system is opposite to the earlier study on photocatalyst sheet configurations in which p-type doping and the formation of a solid solution can effectively enhance the water-splitting activity. This work not only shows a La5Ti2AgS5O7-based Z-scheme water splitting photocatalyst, but also may present a better understanding for the difference between particulate sheet and powder suspension system available in an optimal strategy for water splitting.
关键词： photocatalysis,water splitting,visible light,Z-scheme,oxysulfides
更新于2025-09-23 15:22:29
-
Different approaches for the solar photocatalytic removal of micro-contaminants from aqueous environment: Titania vs. hybrid magnetic iron oxides
摘要： This work reports on the light-induced heterogeneous photodegradation of four micro-contaminants (MCs): Carbamazepine (C), Flumequine (F), Ibuprofen (I), and Sulfamethoxazole (S), using two different heterogeneous advanced oxidation processes. The first one is the semiconductor photocatalysis, run in the presence of the suspension of a home prepared TiO2 (TiO2 HP); the second one is an heterogeneous photo-Fenton process run in the presence of a hybrid magnetic nanomaterial (MB3) with an iron oxides core and an organic shell made of bio-based substances (BBS) isolated from urban biowaste. The two materials work upon two different mechanisms and were already tested (and the action mechanism hypothesized) at the lab scale under model conditions: TiO2 acts as photocatalyst through the photo-generation of hole/electron pairs able to give rise to oxidation and reduction reactions, whereas hybrid magnetic nanomaterial acts in the presence of H2O2 by a photo-Fenton like mechanism. The results evidenced the better performances of TiO2 HP (also better than the well-known reference TiO2 P25). Preliminary photodegradation experiments carried out in a pilot plant under natural solar radiation confirmed the good results obtained with TiO2 HP. Moreover, in the adopted experimental conditions, the Fe(II) leached from MB3 can be considered as responsible of the MCs degradation through a homogeneous photo-Fenton reaction, where MB3 act as iron reservoir.
关键词： TiO2,Micro-contaminants,Photo-Fenton,Photocatalysis,Water treatments,Magnetic materials.
更新于2025-09-23 15:22:29
-
Remote sensing-based water quality assessment for urban rivers: a study in linyi development area
摘要： Nowadays, urban rivers play an important role in city development and make great contributions to urban ecology. Most urban rivers are the drinking water sources and water quality is extremely critical. The current assessment method in national standard of China has multiple limitations; therefore, this paper introduces an advanced assessment, that is, Canadian Water Quality Index (CWQI). This method can help to provide comprehensive and objective water quality assessment for the urban rivers. Moreover, CWQI can prevent waste of the water resource, since current assessment is pessimistic and tent to underestimate water samples to a lower grade. Linyi development area is selected as study region and CWQI method is applied to assess two major urban rivers within the area. The water monitoring data from 2014 to 2017 is acquired in 24 parameters. Since the CWQI calculation is still based on traditional water quality measurement in parameters, there will be a huge cost when increasing research scale and accuracy. In this paper, remote sensing technique is employed to develop models of CWQI scores from satellite data. By utilizing 23 selected monitoring instances and matching satellite data, linear regression analysis shows that red band data has highest correlation with CWQI in both two urban rivers in the study region. In addition, two testing datasets with five instances for each river are used to validate the RS-based CWQI models and the results show that testing datasets can be fitted well. With the models, CWQI distribution diagrams are generated and assist both spatial and temporal analysis. Experimental results show that the proposed approach can indicate actual water quality pattern which is validated by field visit. The proposed approach in this paper has satisfying effectiveness and robustness.
关键词： Remote sensing,Urban rivers,Water quality index,Spatial temporal analysis
更新于2025-09-23 15:22:29
-
Ag2O/TiO2 nanostructures for the photocatalytic mineralization of the highly recalcitrant pollutant iopromide in pure and tap water
摘要： TiO2 was modified by the deposition of Ag2O nanoparticles to increase the photocatalytic degradation of iopromide in water under UV–C (λ = 254 nm) and UV–A/visible light irradiation (380–800 nm) using pure and tap water. Several loadings of Ag2O were deposited on TiO2, namely 0.03, 0.15, 0.25, 0.65, 1.0, 1.15, 1.35 and 1.8 wt. %. XRD, TEM, BET, ICP-OES, XPS, DRS and cathodoluminescence spectroscopy were carried out to characterize the materials, while semiconducting properties of the composite were elucidated through electrochemical and photoelectrochemical characterization. Under UV–C light irradiation, the Ag2O/TiO2 heterostructures showed higher mineralization of iopromide (up to 86%, using the 1.15 wt. % Ag2O/TiO2 material) than unmodified materials (37% for TiO2 and 14% for Ag2O), indicating a synergistic effect by the combination of both compounds in the composite. Under UV–A/visible light irradiation, mineralization achieved with the 1.15 wt. % Ag2O/TiO2 material decreased up to 65%, which was again higher than that obtained for its single components. Stability of the photocatalyst was observed through three consecutive reaction cycles under UV–A/visible light irradiation. In tap water, environmentally relevant concentrations of iopromide were tested (Co = 50 μg L?1), resulting in a high degradation rate, while mineralization dramatically decreased because of the matrix effect. Some by-products were identified by mass spectroscopy and a possible degradation path was proposed. The outstanding photocatalytic activity of the Ag2O/TiO2 materials was explained by the electron trap effect exerted by Ag2O, along with the appearance of different silver species (Ag2O, Ag2O2 and Ag°) throughout the photocatalytic reaction, enhancing the mobility of the charge carriers and thus the generation of reactive species on the photocatalyst surface.
关键词： Semiconductors,X-ray contrast media,Tap water,Photocatalysis,Composite
更新于2025-09-23 15:22:29