p-n heterojunction

P - n 异质结
  • 文章类型: Journal Article
    四环素持续释放到环境中极大地危害了生态系统和人类健康。能够在可见光照射下降解四环素污染物的硫化铟锌(ZnIn2S4)引起了广泛的关注,并致力于提高其催化效率。在这项工作中,我们合成了一个p-n异质结,NiFe2O4/ZnIn2S4,通过密度泛函理论解释了增强载流子迁徙率的内在机理。当异质结形成时,从n型NiFe2O4到p型ZnIn2S4的载流子,激发了内置电场的出现,以促进载流子的分离。2%-NiFe2O4/ZnIn2S4在四环素(TC)降解和总有机碳(TOC)去除方面表现出优异的光催化效率。与纯ZnIn2S4和NiFe2O4相比,2%-NiFe2O4/ZnIn2S4的TC降解率分别高2.0倍和16.9倍,分别。此外,2%-NiFe2O4/ZnIn2S4的饱和磁化强度为3.05emu/g,允许在磁场下快速回收催化剂。超氧自由基(O2-)和空穴(h)是驱动降解过程的主要活性物质。此外,确定了四环素在该光催化过程中的潜在反应途径,并获得了中间产物的生物富集因子和发育毒性。这项工作在废水处理方面具有巨大的潜力,并为开发磁性可回收光催化剂提供了途径。
    The persistent release of tetracycline into the environment significantly endangers both ecosystems and human health. Zinc indium sulfide (ZnIn2S4) capable to degrade tetracycline pollutants under visible light irradiation has attracted extensive attentions and great effort has been devoted to augment its catalytic efficacy. In this work, we synthesized a p-n heterojunction, NiFe2O4/ZnIn2S4, to enhance the carrier migration rate and explained the intrinsic mechanism by density functional theory. When the heterojunction was formed, carriers traversed from the n-type NiFe2O4 to the p-type ZnIn2S4, instigating the emergence of a built-in electric field to facilitate the separation of carriers. 2 %-NiFe2O4/ZnIn2S4 exhibited excellent photocatalytic efficiency in tetracycline (TC) degradation and total organic carbon (TOC) removal. Compared to pure ZnIn2S4 and NiFe2O4, the TC degradation rates of 2 %-NiFe2O4/ZnIn2S4 were 2.0 times and 16.9 times higher, respectively. Additionally, 2 %-NiFe2O4/ZnIn2S4 had a saturation magnetization intensity of 3.05 emu/g, allowing for rapid recovery of the catalyst under a magnetic field. Superoxide radicals (O2-) and holes (h+) were the primary active species driving the degradation process. Furthermore, potential reaction pathways of tetracycline in this photocatalytic process were determined and bioconcentration factor and developmental toxicity of the intermediate products were accessed. This work held great potentials for wastewater treatment and provided a pathway for the development of magnetic recyclable photocatalysts.
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  • 文章类型: Journal Article
    在本文中,我们报道了一种简便,清洁的策略来制备用于光降解有机污染物的片状Ag2O/Fe2O3双金属p-n异质结复合材料。表面形貌,晶体结构,用SEM对Ag2O/Fe2O3的化学组成和光学性质进行了表征,具有EDX光谱的高分辨率TEM图像,XRD,XPS,FT-IR和UV-visDRS分别光谱。Ag2O/Fe2O3p-n异质结的形成促进了电子的界面转移以及电荷载流子的分离。因此,合成的Ag2O/Fe2O3-3复合材料具有超高的光催化活性。在催化剂用量为0.4mgmL-1、辐照时间为60min的实验条件下,罗丹明B的降解转化率达到96.1%,分别是纯相Ag2O和Fe2O3的5.0倍和2.8倍。同时,Ag2O/Fe2O3-3的降解性能不受pH值的限制,在3-11下可以实现较高的降解效率。此外,Ag2O/Fe2O3-3对其他常见阴离子染料也表现出极好的降解能力,阳离子染料和抗生素。XPS和FT-IR光谱表明Ag2O/Fe2O3-3保留了促进电子传输和光吸收转化的碳骨架。淬火实验和EPR的分析表明·O2-,•OH和h是导致有机污染物快速降解的关键反应性氧化剂。这项工作为获得具有优异催化活性的p-n光催化剂异质结以从废水中去除有机污染物提供了新的见解。
    In this paper, we reported a facile and clean strategy to prepare the flake-like Ag2O/Fe2O3 bimetallic p-n heterojunction composites for photodegradation organic pollutants. The surface morphology, crystal structure, chemical composition and optical properties of Ag2O/Fe2O3 were characterized by SEM, high-resolution TEM images with EDX spectra, XRD, XPS, FT-IR and UV-vis DRS spectra respectively. The formation of Ag2O/Fe2O3 p-n heterojunction facilitated the interfacial transfer of electrons as well as the separation of charge carries. Hence, the as-synthesized Ag2O/Fe2O3-3 composites exhibited ultra-high photocatalytic activity. Under the experimental conditions of catalyst dosage of 0.4 mg mL-1 and irradiation time of 60 min, the degradation conversion rate of rhodamine B reached 96.1 %, which was 5.0 and 2.8 times of pure phase Ag2O and Fe2O3, respectively. Meanwhile, the degradation performance of Ag2O/Fe2O3-3 was not limited by pH, and it can achieve high degradation efficiency under 3-11. In addition, Ag2O/Fe2O3-3 also showed superb degradation ability for other common anionic dyes, cationic dyes and antibiotics. XPS and FT-IR spectra showed that Ag2O/Fe2O3-3 retained a carbon skeleton that facilitated electron transport and light absorption conversion. And the analyses of quenching experiment and EPR demonstrated •O2-, •OH and h+ were crucial reactive oxidant species contributing to the rapid organic pollutant degradation. This work provides new insights into obtaining p-n photocatalysts heterojunction with excellent catalytic activity for removing organic pollutants from wastewater.
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  • 文章类型: Journal Article
    背景:动物源性食品中的卡那霉素(KAN)残留物不断进入人体,这将对人类健康构成严重威胁,如听力损失,肾毒性和其他并发症。因此,通过可靠的技术灵敏检测KAN残留在食品质量和安全方面迫在眉睫。与传统方法受到成本和复杂性的限制相比,光电化学(PEC)生物传感器受益于一些优点,如快速响应,优异的灵敏度和良好的稳定性。在这项研究中,探讨了构建高效PEC平台实现KAN残留检测的方法。
    结果:这里,开发了一种由花状BiOI微球和氮化石墨碳(g-C3N4)纳米片组成的新型p-n异质结,以建立用于0V下KAN检测的PECaptasensor。制备的g-C3N4/BiOI异质结构不仅由于较大的比表面积而显着增强了PEC活性,而且由于强大的内部电场而大大提高了电荷分离效率。同时,使用g-C3N4/BiOI作为结合胺官能化适体捕获KAN的高效光活性材料,光电流信号显示“关闭”模式,以实现对KAN的灵敏检测。拟议的PEC适应量对KAN在5×10-9至3×10-7molL-1范围内呈线性响应,低检测限为1.31×10-9molL-1,并且令人满意的回收率(97.44-107.38%)在实际食品样品分析中获得。
    结论:这项工作提出了一种新型的基于p-n异质结的PECaptasensor,具有很强的选择性和稳定性,它允许在包括牛奶在内的动物源性食品中检测到KAN,蜂蜜和猪肉此外,检测范围满足国家标准规定的KANMRL,展示了食品分析的潜在应用。该研究为开发高效实用的抗生素残留检测生物传感器提供了新的见解。
    BACKGROUND: Kanamycin (KAN) residues in animal-derived foods continuously enter the human body, which will pose serious threats to human health such as hearing loss, nephrotoxicity and other complications. Therefore, to sensitively detect KAN residues by a reliable technology is extremely urgent in food quality and safety. Compared with traditional methods being limited by cost and complexity, photoelectrochemical (PEC) biosensors benefit from some merits such as rapid response, excellent sensitivity and good stability. In this study, the construction of a highly efficient PEC platform to realize KAN residues detection is discussed.
    RESULTS: Herein, a novel p-n heterojunction consisting of flower-like BiOI microspheres and graphite carbon nitride (g-C3N4) nanoflakes was developed to establish a PEC aptasensor for KAN detection at 0 V. The prepared g-C3N4/BiOI heterostructure showed not only significantly enhanced PEC activity due to the larger specific surface area but also greatly increased charge separation efficiency owing to the strong internal electric field. Meanwhile, using g-C3N4/BiOI as a highly efficient photoactive material for binding amine-functionalized aptamers to capture KAN, the photocurrent signals showed a \'turn off\' mode to achieve the sensitive detection of KAN. The proposed PEC aptasensor exhibited linear response for KAN from 5 × 10-9 to 3 × 10-7 mol L-1 with a low detection limit of 1.31 × 10-9 mol L-1, and satisfactory recoveries (97.44-107.38 %) were obtained in real food samples analysis.
    CONCLUSIONS: This work presented a novel p-n heterojunction-based PEC aptasensor with strong selectivity and stability, rendering it allowed to detect KAN in animal-derived foods including milk, honey and pork. Additionally, the detection range satisfied the MRLs for KAN specified by the national standards, demonstrating the potential application for food analysis. The study provides a new insight into the development of efficient and practical biosensors for antibiotic residues detection.
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  • 文章类型: Journal Article
    内置电场(BIEF)的构建和调节被认为是增强过渡金属基电催化剂析氧反应(OER)性能的有效策略。在这里,我们提出了一种策略,通过构建和增强原位异质结转化诱导的BIEF来调节镍铁层状双氢氧化物(NiFe-LDH)的电子结构。通过Ag2S@S/NiFe-LDH(p-n异质结)和Ag@S/NiFe-LDH(Mott-Schottky异质结)的设计和合成证明了这一概念。受益于Mott-Schottky异质结的较大BIEF,有效的电子转移发生在银(Ag)和NiFe-LDH之间的界面处。因此,Ag@S/NiFe-LDH表现出优异的OER性能,在1MKOH下仅需要232mV的过电位,即可实现100mAcm-2的电流密度,而Tafel的小斜率为73mVdec-1,以及出色的电催化耐久性。密度泛函理论(DFT)计算进一步验证了Mott-Schottky异质结中更强的BIEF增强了界面处的电子相互作用,降低速率确定步骤(RDS)的能量势垒,并加速OER动力学。这项工作为设计具有较大BIEF的催化剂以增强电催化活性提供了有效的策略。
    The construction and regulation of built-in electric field (BIEF) are considered effective strategies for enhancing the oxygen evolution reaction (OER) performance of transition metal-based electrocatalysts. Herein, we present a strategy to regulate the electronic structure of nickel-iron layered double hydroxide (NiFe-LDH) by constructing and enhancing the BIEF induced by in-situ heterojunction transformation. This concept is demonstrated through the design and synthesis of Ag2S@S/NiFe-LDH (p-n heterojunction) and Ag@S/NiFe-LDH (Mott-Schottky heterojunction). Benefiting from the larger BIEF of Mott-Schottky heterojunction, efficient electron transfer occurs at the interface between silver (Ag) and NiFe-LDH. As a result, Ag@S/NiFe-LDH exhibits excellent OER performance, requiring only a 232 mV overpotential at 1 M KOH to achieve a current density of 100 mA cm-2, with a small Tafel slope of 73 mV dec-1, as well as excellent electrocatalytic durability. Density functional theory (DFT) calculations further verified that stronger BIEF in Mott-Schottky heterojunction enhances the electron interaction at the interfaces, reduces the energy barrier for the rate-determining step (RDS), and accelerates the OER kinetics. This work provides an effective strategy for designing catalyst with larger BIEF to enhance electrocatalytic activity.
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  • 文章类型: Journal Article
    有机污染物检测因其潜在的环境和人类健康风险而引起广泛关注。在这项工作中,一种氮掺杂的二氧化钛/氧化银(N-TiO2/Ag2O)复合材料已被设计为有机染料的灵敏光电化学(PEC)监测平台。灵敏的测定依赖于N-TiO2/Ag2O的出色PEC性能。改善的PEC性能源于光电载流子的有效分离以及由变窄的带隙和具有N-TiO2/Ag2O的p-n结提供的扩展的光响应范围。N-TiO2/Ag2O电极的光电流密度高达2.2mA/cm2,与纯TiO2膜观察到的光电流密度相比,增加了三倍。罗丹明B(RhB)的线性检测范围,亚甲蓝(MB),甲基橙(MO)为0.2ng/mL至10μg/mL,在无偏置电压下的超灵敏检测限为0.2ng/mL。由于优异的光电流密度和对有机污染物的敏感响应,N-TiO2/Ag2OPEC传感器为检测环境有机染料提供了一种有前途的分析方法。
    Organic pollutant detection has caused widespread concern regarding due to their potential environmental and human health risks. In this work, a nitrogen-doped titanium dioxide/silver oxide (N-TiO2/Ag2O) composite has been designed as a sensitive photoelectrochemical (PEC) monitoring platform of organic dyes. Sensitive determination relies on the outstanding PEC performance of N-TiO2/Ag2O. The improved PEC performance stems from the effective separation of photocarriers and the extended light response range provided by the narrowing bandgap and a p-n junction with N-TiO2/Ag2O. The N-TiO2/Ag2O electrode exhibits a photocurrent density of up to 2.2 mA/cm2, demonstrating three times increase compared with the photocurrent density observed with the pure TiO2 film. The linear detection range for rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) is 0.2 ng/mL to 10 μg/mL with an ultrasensitive detection limit of 0.2 ng/mL without bias voltage. Due to the outstanding photocurrent density and sensitive response to organic pollutants, the N-TiO2/Ag2O PEC sensor provided a promising analytical method to detect environmental organic dyes.
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  • 文章类型: Journal Article
    快速准确地监测有害甲醛(HCHO)气体对于健康保护至关重要。然而,高功耗和湿度干扰仍然阻碍了HCHO气体传感器的应用。因此,通过静电纺丝技术,然后进行水热处理,设计了负载沸石咪唑酯骨架8(ZIF-8)的Pt-NiO/In2O3中空纳米纤维(ZPNiInHNFs),旨在实现表面改性和p-n异质结构构造的协同优势,以改善HCHO气体传感器的传感性能。ZPNiInHNF传感器的响应值为52.8至100ppmHCHO,比原始In2O3传感器增强了近4倍,在180°C的适度低温下,随着快速的响应/恢复速度(8/17s)和优良的耐湿性。这些增强的传感特性可以归因于Pt催化剂提高了催化活性,p-n异质结促进化学反应,和适当的ZIF-8负载提供疏水表面。我们的研究提出了一种有效的传感材料设计策略,以激发开发具有成本效益的传感器,以准确检测室内HCHO有害气体。
    A rapid and accurate monitoring of hazardous formaldehyde (HCHO) gas is extremely essential for health protection. However, the high-power consumption and humidity interference still hinder the application of HCHO gas sensors. Hence, zeolitic imidazolate framework-8 (ZIF-8)-loaded Pt-NiO/In2O3 hollow nanofibers (ZPNiIn HNFs) were designed via the electrospinning technique followed by hydrothermal treatment, aiming to enable a synergistic advantage of the surface modification and the construction of a p-n heterostructure to improve the sensing performance of the HCHO gas sensor. The ZPNiIn HNF sensor has a response value of 52.8 to 100 ppm HCHO, a nearly 4-fold enhancement over a pristine In2O3 sensor, at a moderately low temperature of 180 °C, along with rapid response/recovery speed (8/17 s) and excellent humidity tolerance. These enhanced sensing properties can be attributed to the Pt catalysts boosting the catalytic activity, the p-n heterojunctions facilitating the chemical reaction, and the appropriate ZIF-8 loading providing a hydrophobic surface. Our research presents an effective sensing material design strategy for inspiring the development of cost-effective sensors for the accurate detection of indoor HCHO hazardous gas.
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  • 文章类型: Journal Article
    锂-硫电池的商业应用主要受到可溶性多硫化物的不断穿梭和缓慢的氧化还原动力学的阻碍。如今,异质结的发现,它结合了具有不同性质的材料,为克服这些障碍提供了新的视角。在这里,使用具有自发内置电场(BIEF)的MnO2-ZnSp-n异质结来设计用于锂硫电池的功能涂层隔膜。MnO2纳米线为多硫化物提供了合适的吸附能力,而ZnS带来的丰富的活性位点保证了高效的转化。此外,BIEF显著促进电子和多硫化物在MnO2-ZnS界面的迁移,实现平稳的“吸附-扩散-转化”反应机制。通过同时充当吸附模块和催化位点,该BIEF允许电池利用用MnO2-ZnS异质结改性的隔膜,以在0.1C下实现1511.1mAhg-1的令人印象深刻的初始容量,并且在1000次循环后在2.0C下保持每个循环仅0.048%的容量衰减率。即使在稀薄电解液(5.4μLmg-1)中增加硫负荷至9.4mgcm-2,电池在100次循环后仍表现出6.0mAhcm-2的超高面积容量。
    The commercial application of lithium-sulfur batteries is primarily impeded by the constant shuttling of soluble polysulfides and sluggish redox kinetics. Nowadays, the discovery of the heterojunction, which combines materials with diverse properties, offers a new perspective for overcoming these obstacles. Herein, a functional coating separator for the lithium-sulfur battery is designed using a MnO2-ZnS p-n heterojunction with a spontaneous built-in electric field (BIEF). The MnO2 nanowire provides suitable adsorption capacity for polysulfides, while the abundant reactive sites brought by ZnS ensure efficient conversion. Moreover, the BIEF significantly facilitates the migration of electrons and polysulfides at the MnO2-ZnS interface, enabling a smooth \"adsorption-diffusion-conversion\" reaction mechanism. By serving as both the adsorption module and catalytic sites, this BIEF allows batteries utilizing separators modified with MnO2-ZnS heterojunction to achieve an impressive initial capacity of 1511.1 mAh g-1 at 0.1C and maintain a capacity decay rate of merely 0.048% per cycle at 2.0C after 1000 cycles. Even when increasing sulfur loading to 9.4 mg cm-2 in lean electrolyte (5.4 μL mg-1), the battery still exhibits an ultrahigh areal capacity of 6.0 mAh cm-2 after 100 cycles.
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  • 文章类型: Journal Article
    形貌和结构对气体传感器的性能起着至关重要的作用。空心结构,特别是,不仅增加了材料的比表面积,而且提高了壳内气体的碰撞频率,并在气体传感领域进行了深入的研究。以SnO2为例,制备了双壳结构的SnO2(D-SnO2)。D-SnO2@聚苯胺(PANI)(DSPx,x表示D-SnO2摩尔含量)复合材料通过原位氧化聚合法合成,并同时沉积到聚对苯二甲酸乙二醇酯(PET)基板上以制造无电极,柔性传感器。讨论了SnO2含量对室温下基于DSPx的NH3传感器传感性能的影响。结果表明,室温下20mol%D-SnO2@PANI(DSP20)传感器对100ppmNH3的响应为37.92,是原始PANI传感器的5.1倍。此外,DSP20传感器在10ppmNH3浓度下表现出快速的响应和恢复速率,响应和恢复时间分别为182s和86s。
    Morphology and structure play a crucial role in influencing the performance of gas sensors. Hollow structures, in particular, not only increase the specific surface area of the material but also enhance the collision frequency of gases within the shell, and have been studied in depth in the field of gas sensing. Taking SnO2 as an illustrative example, a dual-shell structure SnO2 (D-SnO2) was prepared. D-SnO2@Polyaniline (PANI) (DSPx, x represents D-SnO2 molar content) composites were synthesized via the in situ oxidative polymerization method, and simultaneously deposited onto a polyethylene terephthalate (PET) substrate to fabricate an electrode-free, flexible sensor. The impact of the SnO2 content on the sensing performance of the DSPx-based sensor for NH3 detection at room temperature was discussed. The results showed that the response of a 20 mol% D-SnO2@PANI (DSP20) sensor to 100 ppm NH3 at room temperature is 37.92, which is 5.1 times higher than that of a pristine PANI sensor. Moreover, the DSP20 sensor demonstrated a rapid response and recovery rate at the concentration of 10 ppm NH3, with response and recovery times of 182 s and 86 s.
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  • 文章类型: Journal Article
    二维材料MXene和一维金属氧化物半导体的结合可以提高载流子的传输速率,能有效提高传感性能。我们制备了基于MoO3纳米纤维和层状Ti3C2TxMXene的三甲胺气体传感器。使用静电纺丝和化学蚀刻方法,制备了一维MoO3纳米纤维和二维Ti3C2TxMXene纳米片,分别,并通过XPS对复合材料进行了表征,SEM,和TEM。Ti3C2TxMXene-MoO3复合材料对三甲胺气体表现出优异的室温响应特性,显示高响应(对于2ppm的三甲胺气体高达4)和快速响应恢复时间(10s/7s)。Further,我们研究了传感器可能的灵敏度机理。Ti3C2TxMXene-MoO3复合材料具有更大的比表面积和更丰富的活性位点,结合p-n异质结,有效地提高了传感器的灵敏度。由于其检出限低,稳定性高,它有可能作为呼出气生物标志物应用于三甲胺的检测系统。
    The combination of two-dimensional material MXene and one-dimensional metal oxide semiconductor can improve the carrier transmission rate, which can effectively improve sensing performance. We prepared a trimethylamine gas sensor based on MoO3 nanofibers and layered Ti3C2Tx MXene. Using electrospinning and chemical etching methods, one-dimensional MoO3 nanofibers and two-dimensional Ti3C2Tx MXene nanosheets were prepared, respectively, and the composites were characterized via XPS, SEM, and TEM. The Ti3C2Tx MXene-MoO3 composite material exhibits excellent room-temperature response characteristics to trimethylamine gas, showing high response (up to four for 2 ppm trimethylamine gas) and rapid response-recovery time (10 s/7 s). Further, we have studied the possible sensitivity mechanism of the sensor. The Ti3C2Tx MXene-MoO3 composite material has a larger specific surface area and more abundant active sites, combined with p-n heterojunction, which effectively improves the sensitivity of the sensor. Because of its low detection limit and high stability, it has the potential to be applied in the detection system of trimethylamine as a biomarker in exhaled air.
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  • 文章类型: Journal Article
    构建混合异质结光催化剂是提高光生载流子利用率和光催化活性的有效策略。为了提高光生载流子的分离距离,加速界面异质结处的有效分离,在这项工作中成功地制造了一个独特的0D-2D分层纳米结构p-n异质结。使用微乳液煅烧方法在BiVO4(BVO)纳米颗粒(n型)上原位生长BiOCl(BOC)纳米片(p型),以实现高效的可见光驱动有机染料降解。与纯BVO相比(罗丹明B(RhB)的降解率:55分钟内约为32.0%,矿化率:120分钟内24.9%),在可见光照射下,利用BVO/25%BOC异质结光催化剂,RhB降解率在55分钟内达到99.5%左右,在120分钟内矿化率为62.1%。各种表征表明,BVO/BOCp-n异质结的形成极大地促进了光生载流子分离效率。同时,清除实验和电子自旋共振测试的结果表明,·O2-和h是RhB降解的主要活性物种。此外,使用LC-MS测试提出了RhB的可能降解途径。这项工作证明,建立低维p-n异质结光催化剂是开发高效光催化剂的有前途的策略。
    The construction of hybrid heterojunction photocatalysts is an effective strategy to improve the utilization of photogenerated carriers and photocatalytic activity. To enhance the separation distance of photogenerated carriers and accelerate the effective separation at the heterojunction of the interface, a unique 0D-2D hierarchical nanostructured p-n heterojunction was successfully fabricated in this work. BiOCl (BOC) nanosheets (p-type) were in situ grown on BiVO4 (BVO) nanoparticles (n-type) using the microemulsion-calcination method for highly efficient visible-light-driven organic dye degradation. Compared with pure BVO (the degradation rate of rhodamine B (RhB): about 32.0% in 55 min, the mineralization rate: 24.9% in 120 min), the RhB degradation rate can reach about 99.5% in 55 min and the mineralization rate of 62.1% in 120 min by utilizing BVO/25%BOC heterojunction photocatalyst under visible light irradiation. Various characterizations demonstrate that the formation of BVO/BOC p-n heterojunction greatly facilitates photogenerated carriers separation efficiency. Meanwhile, the results of the scavenging experiments and electron spin resonance tests indicate that ·O2- and h+ are the prominent active species for Rh B degradation. In addition, possible degradation pathways for Rh B were proposed using LC-MS tests. This work proves that building low dimensional p-n heterojunction photocatalysts is a promising strategy for developing photocatalysts with high efficiency.
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