压力诱导相变原位构建BiVO4/Bi0.6Y0.4VO4型异质结增强光催化全解水性能

光催化完全分解水制氢是一个在粉末颗粒中实现多个串行物理化学步骤的复杂反应过程.这一过程在理论上具有体系简单、成本低、易操作等特点.然而,单步光激发系统中通常存在严重的光生载流子复合,这极大地制约了光催化的整体效率.利用能带结构不同的半导体合理构建异质结催化剂被认为是解决这一难题的重要途径之一.特别是近年来,S型异质结概念的提出为设计异质结结构以及分析不同半导体之间的载流子迁移问题提供了新的思路.本文以小粒径BiVO₄/Bi_0.6Y_0.4VO₄(BYV)为研究对象,首先利用"共沉淀-晶化"的方法制备了BYV固溶体纳米颗粒,随后利用压力诱导固溶体中四方相钒酸铋结构转变为单斜相,从而构建了BiVO₄/Bi_0.6Y_0.4VO₄复合光催化剂.XRD,Raman,HRTEM,HAADF-EDS的结果表明,经过高压后处理的BYV固溶体表面会出现粒径约为5 nm单斜钒酸铋纳米颗粒,实现了原位构建异质结结构.随后载流子动力学的相关表征以及Au选择性光沉积的结果表明,在光照条件下,所构建异质结中的光生电子主要分布在BYV固溶体上,而在表面形成的单斜相钒酸铋颗粒主要起到了类似"空穴"捕获的作用.这种在异质结中的载流子迁移路径符合S型异质结机理.电化学、稳态荧光光谱以及瞬态荧光光谱的表征结果表明,相比于单一固溶体,在S型异质结这种两步激发系统中所存在的载流子迁移路径能够大幅促进光生载流子分离,从而提高了小粒径BYV的光催化完全分解水性能.综上,构建S型异质结是一种解决小粒径光催化剂中载流子分离能力差的有效途径.同时,压力诱导材料晶型转变实现原位构建异质结的制备方法也为提高光生载流子分离效率提供了新的研究思路与机遇.     

S型异质结H2O2光催化剂的研究进展(英文)

随着现代经济和工业的快速发展,传统化石能源的过度开发和消耗造成了日益严重的环境污染和能源危机,极大地威胁着我们的健康和生活。我们需要开发新的可持续技术来解决日益恶化的环境和能源问题。太阳能作为一种绿色、可持续的清洁能源,在过去几十年中受到了广泛的关注。因此,开发和利用太阳能对解决当前面临的问题具有重要意义。半导体光催化技术是一种太阳能驱动的半导体材料表面催化反应过程,可利用太阳能并将其转化为其他能源,用于进一步的能量存储和应用。目前,制备高效稳定的光催化剂仍然是一个巨大的挑战。最近,为了解决传统异质结光催化剂电荷转移过程中的缺点和不足,一种新型梯形(S型)异质结概念被首次提出。S型异质结不仅有效地解决了电荷转移问题,实现了载流子的快速分离,而且保留了光催化体系最强的氧化还原能力,提高其光催化性能。到目前为止,各种S型异质结已被开发并应用于太阳能转化可用化学燃料领域以减少化石燃料的使用。此外,S型异质结也可用于降解污染物,以减少化石燃料的消耗所造成对环境恶化的影响。过氧化氢(H₂O₂)作为一种有效、多用途、绿色的氧化剂,已应用于诸多领域,包括污...     

富含光诱导氧空位Bi12O17Br2的制备及其高效光催化固氮性能(英文)

采用一步水热法制备了Bi₁₂O₁₇Br₂光催化剂,其平均微片尺寸为1.2μm,比表面积约为29 m²·g^-1。Bi₁₂O₁₇Br₂的禁带宽度为2.42 eV,能够响应可见光。值得注意的是,在光照条件下Bi₁₂O₁₇Br₂表面能够产生氧空位;光诱导氧空位不仅能促进氮气在催化剂表面的吸附,而且对吸附的氮气分子的活化起到至关重要的作用。实验结果表明在可见光照射下,Bi₁₂O₁₇Br₂光催化剂上的氨生成速率为337.6μmol·g^-1·h^-1。在可见光的驱动下,Bi₁₂O₁₇Br₂光催化剂能够实现氮气与水反应生成氨的过程。     

Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₂Ti₂O₇/TiO₂/Bi₄Ti₃O₁₂复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明：TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂     

BiOCl0.5Br0.5/BiPO4双层异质结薄膜光催化剂的一步电化学法制备及性能

采用一步电化学法在金属 Bi板上成功制备了 Bi OCl_0.5Br_0.5/Bi PO₄双层异质结薄膜,并通过多种表征手段对薄膜的晶型结构、元素组成及化合价、形貌和尺寸特征、吸光性能和荧光强度进行了表征。结果表明,制备得到的复合薄膜呈现出上层为梭子状的 Bi PO₄颗粒层分散在下层为 Bi OCl_0.5Br_0.5固溶体层的双层结构。这样的双层膜排列顺序使得光生电子和空穴在不同组分之间的界面电场作用下分别向薄膜两侧流动,促进光致载流子的分离,提高了 Bi OCl_0.5Br_0.5/Bi PO₄复合薄膜的光催化活性。活性测试结果表明,在模拟太阳光照射 120 min 后,Bi OCl_0.5Br_0.5/Bi PO₄复合薄膜对苯酚的降解率达到了 99.97%,是相同条件下制备的 Bi OCl/Bi PO₄和 Bi O...     

氧空位控制BiVO4晶面异质结的磁性和光电催化性能

在铁磁光催化剂中,大多数光生电荷具有相同的自旋状态,因此可以有效抑制光生电子和空穴的复合.利用BiVO₄{010}和{110}晶面中氧空位的形成能不同,通过晶面取向和氧空位的协同作用来调控BiVO₄的铁磁性能.在N2气氛中退火后,BiVO₄晶面异质结中氧空位的比例随着{010}/{110}晶面比例的增加而降低,因为{010}晶面上氧空位的形成能低于{110}晶面.{010}/{110}晶面比例较低的BiVO₄晶面异质结的铁磁性能优于{010}/{110}晶面比例较高的BiVO₄,因为前者颗粒尺寸更小、更立体,其比表面积和界面区域更大,所以其表面未饱和自旋对总磁矩的贡献更大.{010}/{110}比例较高的BiVO₄晶面异质结具有更大的光电流密度和光电催化产氢效率,源于BiVO₄{010}晶面比{110}晶面具有更高的电荷迁移率、更好的吸附特性和更低的能垒.并且氧空位的引入也提高了BiVO₄的制氢效率.     

超声辅助制备Cs2AgBiBr6/Bi2WO6 S型异质结用于可见光光催化CO2还原(英文)

光催化因其可以利用太阳能进行光解水产氢、CO₂还原、降解有机污染物及有机物转化而被认为是解决当前能源危机和环境问题的一种有效手段.由于光催化反应是由光激发光催化材料生成光生载流子引发的,因此理想的光催化剂应当具有宽的光响应范围、低的光生载流子复合率和足够的氧化还原能力来进行表面反应.然而单一组分的半导体材料难以同时满足宽光谱响应(即窄带隙)和强氧化还原能力(即价带更正和导带更负).通过耦合两个具有可见光响应且交错能带排布的半导体来构建S型异质结,不仅能拓宽光催化剂的光吸收范围、促进电荷分离,还同时保留了两种半导体的强氧化还原能力,是发展高效光催化材料的一种有效途径.Cs₂AgBiBr₆的导带和价带分别位于-0.65 V vs.NHE和1.60 V vs.NHE,而Bi₂WO₆.的导带和价带分别为-0.4 V vs.NHE和2.4 V vs.NHE,两者能带位置匹配.因此,本文选择Cs₂AgBiBr₆和Bi₂WO<...     

Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₄Ti₃O₁₂/TiO₂/Bi₂Ti₂O₇复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明： TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂Ti₂O₇、Bi₄Ti₃O₁₂和TiO₂三者的协同作用,有效提高了可见光吸收能力,改变了光生载流子的传输路径,降低了光生电子与空穴的复合几率,从而获得高效的光催化降解CH₃CHO性能。可见光照8 h,Bi₄Ti₃O₁₂/TiO₂/Bi₂Ti₂O₇复合纳米纤维对CH₃CHO的降解率达到87.1%。     

漂浮型Bi2WO6/C3N4/碳布S型异质结光催化材料用于高效净化水体环境(英文)

近年来,水污染成为人类生存面临的巨大危机,如何治理水污染,特别是如何有效去除水体中的抗生素和重金属存在着很多挑战.采用先进、绿色且高效的光催化技术可有效去除水污染,因而受到科研工作者的广泛关注,但粉末状光催化剂易团聚、难分离回收等问题限制了其工业应用.近年来,人们发现将粉末状光催化剂固定在柔性大表面积且电荷传导性能良好的碳布上可以有效克服上述缺点.g-C₃N₄具有高光还原活性、高稳定性和低成本的优点,因而在环境净化领域具有突出的应用潜力.但单一组分的C₃N₄/碳布仍存在氧化能力弱、光生载流子分离效率低等问题.将其与高光催化氧化活性且能带位置匹配的Bi₂WO₆共同构筑具有强内建电场和保留最大氧化还原能力的S型异质结,是一种有效策略,有望开发出高效、可回收的可见光光催化体系.本文以柔性、大的碳布为基底,通过热聚合-溶剂热法将C₃N4和富含氧空位的Bi₂WO₆原位生长在碳纤维上,制备出了富含氧空位...     

Tuning the concentration of surface/bulk oxygen vacancies in CeO2 nanorods to promote highly efficient photodegradation of organic dyes

To enhance the photodegradation ability of CeO₂ for organic dyes, an effective strategy is to introduce oxygen vacancies (V_o). In general, the introduced V_o are simultaneously present both on the surface and in the bulk of CeO₂. The surface oxygen vacancies (V_o-s) can decrease the band gap, thus enhancing light absorption to produce more photogenerated e⁻ for photodegradation. However, the bulk oxygen vacancies (V_o-b) will inhibit photocatalytic activity by increasing the recombination of photogenerated e⁻ and V_o-b. Therefore, regulating the concentrations of V_o-s to V_o-b is a breakthrough for achieving the best utilization of photogenerated e⁻ during photodegradation. We used an easy hydrothermal method to achieve tunable concentrations of V_o-s to V_o-b in CeO₂ nanorods. The optimized CeO₂ presents a 70.2% removal of rhodamine B after 120 min of ultraviolet−visible light irradiation, and a superior photodegradation performance of multiple organics. This tuning strategy for V_o also provides guidance for developing other advanced metal-oxide semiconductor photocatalysts for the photodegradation of organic dyes.     

Highly ordered Nb2O5 nanochannel film with rich oxygen vacancies for electrocatalytic N2 reduction: Inactivation and regeneration of electrode

We report the fabrication of highly ordered Nb₂O₅ nanochannel film (Nb₂O₅-NCF) onto niobium foil by an anodization method. After thermal treatment, the obtained Nb₂O₅-NCF with rich oxygen vacancies exhibits electrochemical N₂ reduction reaction (NRR) activity with an NH₃ yield rate of 2.52 × 10⁻¹⁰ mol cm^-2 s^-1 and a faradaic efficiency of 9.81% at −0.4 V (vs. RHE) in 0.1 mol/L Na₂SO₄ electrolyte (pH 3.2). During electrocatalytic NRR, the Nb₂O₅-NCF takes place electrochromism (EC), along with a crystalline phase transformation from pseudo hexagonal phase to hexagonal phase owing to H⁺ insertion. This results in the reduced NRR activity due to the decrease of oxygen vacancies of hexagonal phase Nb₂O₅, which can be readily regenerated by low-temperature thermal treatment or applying an anodic potential, showing superior recycling reproducibility.     

高催化活性2D/2D Ti3C2/Bi4O5Br2纳米片异质结的构建及其可见光催化去除NO

This study concentrated on the production of a two-dimensional and two-dimensional (2D/2D) Ti₃C₂/Bi₄O₅Br₂ heterojunction with a large interface that applied as one of the novel visible-light-induced photocatalyst via the hydrothermal method. The obtained photocatalysts enhanced the photocatalytic efficiency of the NO removal. The crystal structure and chemical state of the composites were characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that Ti₃C₂, Bi₄O₅Br₂, and Ti₃C₂/Bi₄O₅Br₂ were successfully synthesized. The experimental results of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the prepared samples had a 2D/2D nanosheet structure and large contact area. This structure facilitated the transfer of electrons and holes. The solar light absorptions of the samples were evaluated using the UV-Vis diffuse reflectance spectra (UV-Vis DRS). It was found that the absorption band of Ti₃C₂/Bi₄O₅Br₂ was wider than that of Bi₄O₅Br₂. This represents the electrons in the Ti₃C₂/Bi₄O₅Br₂ nanosheet composites were more likely to be excited. The photocatalytic experiments showed that the 2D/2D Ti₃C₂/Bi₄O₅Br₂ composite with high photocatalytic activity and stability. The photocatalytic efficiency of pure Bi₄O₅Br₂ for the NO removal was 30.5%, while for the 15%Ti₃C₂/Bi₄O₅Br₂ it was 57.6%. Moreover, the catalytic reaction happened in a short period. The concentration of NO decreased exponentially in the first 5 min, which approximately reached the final value. Furthermore, the stability of 15%Ti₃C₂/Bi₄O₅Br₂ was favorable: the catalytic rate was approximately 50.0% after five cycles of cyclic catalysis. Finally, the scavenger experiments, electron spin resonance spectroscopy (ESR), transient photocurrent response, and surface photovoltage spectrum (SPS) were applied to analyze the photocatalytic mechanism of the composite. The results indicated that the 2D/2D heterojunction Ti₃C₂/Bi₄O₅Br₂ improved the separation rate of the electrons and holes, thus enhancing the photocatalytic efficiency. In the photocatalytic reactions, the photogenerated electrons (e⁻) and superoxide radical (·O₂⁻) were critical active groups that had a significant role in the oxidative removal of NO. The in situ Fourier-transform infrared spectroscopy (in situ FTIR) showed that the photo-oxidation products were mainly NO₂⁻ and NO₃⁻. Based on the above experimental results, a possible photocatalytic mechanism was proposed. The electrons in Bi₄O₅Br₂ were excited by visible light. They jumped from the valence band (VB) of Bi₄O₅Br₂ to the conduction band (CB). Then, the photoelectrons transferred from the CB of Bi₄O₅Br₂ to the Ti₃C₂ surface, which significantly promoted the separation of the electron-hole pairs. Therefore, the photocatalytic efficiency of Ti₃C₂/Bi₄O₅Br₂ on NO was significantly improved. This study provided an effective method for preparing 2D/2D Ti₃C₂/Bi₄O₅Br₂ nanocomposites for the photocatalytic degradation of environmental pollutants, which has great potential in solving energy stress and environmental pollution.     

Hydrothermal synthesis, thermal, structural, spectroscopic and magnetic studies of the Mn5−xCox(HPO4)2(PO4)2(H2O)4 (x=1.25, 2, 2.5 and 3) finite solid solution

The Mn_5−xCo_x(HPO₄)₂(PO₄)₂(H₂O)₄ (x=1.25, 2, 2.5, 3) finite solid solution has been synthesized by mild hydrothermal conditions under autogeneous pressure. The phases crystallize in the C2/c space group with Z=4, belonging to the monoclinic system. The unit-cell parameters obtained from single crystal X-ray diffraction are: a=17.525(1), b=9.0535(6), c=9.4517(7) Å, β=96.633(5) ° being R1=0.0436, wR2=0.0454 for Mn75Co25; a=17.444(2), b=9.0093(9), c=9.400(1) Å, β=96.76(1) ° being R1=0.0381, wR2=0.0490 for Mn60Co40; a=17.433(2), b=8.9989(9), c=9.405(1) Å, β=96.662(9) ° being R1=0.0438, wR2=0.0515 for Mn50Co50 and a=17.4257(9), b=8.9869(5), c=9.3935(5) Å, β=96.685(4) ° being R1=0.0296, wR2=0.0460 for Mn40Co60. The structure consists of a three dimensional network formed by octahedral pentameric entities (Mn,Co)₅O₁₆(H₂O)₆ sharing vertices with the (PO₄)³⁻ and (HPO₄)²⁻ tetrahedra. The limit of thermal stability of these compounds is, approximately, 165 °C, near to this mean temperature the phases loose their water content in two successive steps. IR spectra show the characteristic bands of the water molecules and the phosphate and hydrogen-phosphate oxoanions. The diffuse reflectance spectra are consistent with the presence of MO₆ octahedra environments in slightly distorted octahedral geometry, except for the M(3)O₆ octahedron which presents a remarkable distortion and so a higher Dq parameter. The mean value for the Dq and B-Racah parameter for the M(1),(2)O₆ octahedra is 685 and 850 cm⁻¹, respectively. These parameters for the most distorted M(3)O₆ polyhedron are 825 and 880 cm⁻¹, respectively. The four phases exhibit antiferromagnetic couplings as the major magnetic interactions. However, a small spin canting phenomenon is observed at low temperatures for the two phases with major content in the anisotropic-Co(II) cation.     

A TEM, XRD, and crystal chemical investigation of oxygen/vacancy ordering in (Ba1−xLax)2In2O5+x, 0x0.6

A careful TEM and XRD study of the (Ba_1−xLa_x)₂In₂O_5+x, 0x0.6, ‘defect-perovskite’-type solid solution has been carried out. A well-defined structural phase transition is shown to occur between x=0.1 and 0.2 from the orthorhombic brownmillerite structure type on the low x side to a multiple twinned, tetragonal 1×1×2 perovskite-related superstructure phase on the high x side at x=0.2. This phase transition correlates with an important phase transition previously observed in electrical conductivity versus temperature measurements. The existence of additional satellite reflections close to the regions of reciprocal space was found to be typical of all (Ba_1−xLa_x)₂In₂O_5+x specimens, although their intensity relative to the parent Bragg reflections systematically reduces as x increases. As x increases beyond 0.2, the -type satellite reflections initially become weaker and rather more diffuse for x=0.3 before splitting into pairs of rather weak and somewhat diffuse incommensurate satellite reflections for x=0.4 and beyond. An interpretation in terms of oxygen vacancy ordering and associated structural relaxation is given. Additional structured diffuse scattering is also observed and a tentative explanation in terms of Ba/La ordering and associated local strain distortions put forward.