高效的CdS/Ti-Fe2O3异质结光阳极:研究Z型电荷迁移机制增强光电化学水氧化活性

近年来以Z型机制为转移的光催化体系成微光电化学分解水领域的研究热点.相比较传统的异质结,Z型异质结能够保留具有高氧化能力与高还原能力的位点,从而提高光电化学效率.其中,证明电荷的Z型迁移机制成为研究人员努力的方向,比较有效的证明方法包括自由基捕获、XPS分析和检测还原位点等.对于Z型异质结,界面电场处电荷的迁移行为是至关重要的,但目前常用的证明手段对界面电场处电荷的迁移行为研究还比较少.因此,本文精心设计了CdS/Ti-Fe₂O₃异质结光阳极来探索光电化学分解水中的电荷转移行为.采用开尔文探针测试、表面光电压谱测试和瞬态光电压谱测试等光物理测试手段监测CdS/Ti-Fe₂O₃Z型异质结光阳极界面电场中光生电荷的迁移行为.其中,开尔文探针和表面光电压测量表明,CdS/Ti-Fe₂O₃界面驱动力有利于激发电子快速迁移至CdS;由于Z型异质结是一个双光子的过程,因此在瞬态光电压的过程中采取了双光束策略,即用不同波长的光分别从两个半导体侧进行照光,以充分发挥内层CdS的电子传输层的作用.结果表明,在双光束照射下界面电场增强,使得更多Ti-Fe₂O₃电子与CdS空穴结合,使得更多Ti-Fe₂O₃电子与CdS空穴结合,更多的空穴迁移到Ti-Fe₂O₃的表面去参与反应,充分证明了CdS/Ti-Fe₂O₃光阳极的Z型迁移机制.基于界面电场有效的电荷迁移与分离的分析,对Z型异质结光阳极进行了光电化学的测试,与单纯Ti-Fe₂O₃光阳极相比,CdS/Ti-Fe₂O₃光阳极表现出优异的光电化学性能.其中,25CdS/Ti-Fe₂O₃光阳极的光电流密度在1.23V(相对于标准氢电极)达到1.94 mA/cm²,比单纯Ti-Fe₂O₃光电流高出两倍.阻抗测试结果表明,CdS/Ti-Fe₂O₃光阳极能够减小电荷传输阻力,从而加快电荷分离效率,这也间接证明了Z型光阳极的成功构筑,因此,本文提供了一个有效且新颖的手段来证明光电化学分解水中光催化系统的Z型电荷转移机制.     

Ta/Al-Fe2O3薄膜电极的制备及其光电催化降解亚甲基蓝性能

采用简单的涂滴法制备出新型的Al、Ta 共掺杂的三元铁氧化物(Ta/Al-Fe₂O₃)可见光响应型光催化薄膜. 运用X射线光电子能谱(XPS)和紫外-可见(UV-Vis)光谱等手段对其进行了表征, 考察了其光电化学性能, 并研究了复合电极光电催化降解亚甲基蓝(MB)废水的反应性能. 由表面谱学分析可知, Ta 和Al 成功掺入Fe₂O₃中, Ta 会改变催化剂表面Al 和O的化学环境. 在可见光照射下的光电催化(PEC)反应中, Ta/Al-Fe₂O₃降解MB的反应速率约为Al-Fe₂O₃的2 倍, 光电催化共作用的效果优于单纯光催化作用(PC)和电催化(EC)作用的效果.结果表明, Ta掺杂有利于提高Ta/Al-Fe₂O₃薄膜的光电催化活性.     

表面钒修饰对α-Fe2O3材料光电化学性能的增强作用

对半导体材料进行表面化学修饰或改性,是提高其光催化活性、有效利用光能的一种重要措施.本文结合水热化学法、化学池沉积和后续热处理等,分别制备了未修饰α-Fe₂O₃和钒修饰的α-Fe₂O₃光电极材料.利用X射线粉末衍射(XRD)谱和紫外-可见漫反射光谱(UV-Vis-DRS)技术分析表征了材料的晶相结构、化学组成和光谱吸收等固体物理化学性能;利用光电流测量和电化学交流阻抗谱(EIS)实验技术,并基于1 mol·L^-1NaOH (pH 13.6)中的光电化学水分解反应,研究了钒修饰对α-Fe₂O₃材料光电化学性能的增强作用.结果表明,与未修饰的Fe₂O₃材料相比,钒修饰α-Fe₂O₃样品出现FeVO₄的XRD特征峰,但临界光吸收波长未发生红移;钒修饰使Fe₂O₃材料的光电流增大4-5倍、光生载流子在电极表面的复合几率降低了3/4-4/5、电极表面电荷传递速率(表观一级速率常数)明显提高.结合Fe₂O₃/溶液界面半导体能带模型和有关研究结果,分析了研究体系的界面电荷动力学传输过程以及钒修饰使α-Fe₂O₃材料光电化学性能增强的原因.     

BiVO4/CuBi2O4薄膜光电极的制备及光电性能

通过金属有机物分解法(MOD)协同光电化学沉积法, 将p型氧化物半导体CuBi₂O₄沉积在BiVO₄纳米薄膜上, 形成包覆性异质结结构, 制备了一种新型p-n异质结光阳极n-BiVO₄/p-CuBi₂O₄, 用于太阳能光电化学(Photoelectrochemical, PEC)水分解. 研究结果表明, 在1.23 V(vs. RHE)电势下, BiVO₄/CuBi₂O₄ 异质结光阳极表现出优良的PEC水氧化性能, 光电流密度达到2.8 mA/cm², 负载磷酸钴(Co-Pi)的BiVO₄/CuBi₂O₄/Co-Pi光电极, 光电流密度达到4.45 mA/cm², 分别为BiVO₄电极光电流密度的3.1倍和4.9倍. X射线衍射(XRD)、 紫外-可见吸收光谱(UV-Vis)、 电化学阻抗谱(EIS)和能级结构图等结果也证实, BiVO₄/CuBi₂O₄和BiVO₄/CuBi₂O₄/Co-Pi复合电极材料在内建电场和能带弯曲作用下, 光吸收特性增强, 载流子界面转移电阻减小, 具有良好的光电化学性能与稳定性.     

热处理气氛对α-Fe2O3光阳极光电化学性能影响研究

分别在空气和氮气中对水热制备的薄膜进行热处理获得了纳米棒状α-Fe₂O₃光阳极。对样品分别进行了X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见吸收光谱和光电化学性能测试。与空气热处理获得的α-Fe₂O₃Air光阳极相比,氮气气氛热处理获得的α-Fe₂O₃光阳极正面光照电流密度显著提升达到0.42mA·cm^-2。正面光照下,α-Fe2O3N2光阳极的体内电荷分离效率ηbulk和表面电荷注入效率ηsurface都有较大增加,说明N2热处理明显增加了α-Fe₂O₃膜的载流子浓度,增强了体内载流子的传输和表面载流子注入效率。     

Cobalt oxide and carbon modified hematite nanorod arrays for improved photoelectrochemical water splitting

Given the proper band gap, low cost and good stability, hematite(α-Fe_2O_3) has been considered as a promising candidate for photoelectrochemical(PEC) water splitting, however suffers from the sluggish surface water oxidation reaction kinetics. In this study, a simple dip-coating process was used to modify the surface of α-Fe_2O_3 nanorod arrays with cobalt oxide(CoO_x) and carbon(C) for the improved PEC performance, with a photocurrent density at 1.6 V(vs. reversible hydrogen electrode, RHE) increased from 0.10 mA/cm~2 for the pristine α-Fe_2O_3 to 0.37 mA/cm~2 for the CoO_x/C modified α-Fe_2O_3 nanorods. As revealed by electrochemical analysis, thanks to the synergistic effect of CoO_x and C, the PEC enhancement could be attributed to the enhanced charge transfer ability, decreased surface charge recombination, and accelerated water oxidation reaction kinetics. This study serves as a good example for improving PEC water splitting performance via a simple method.     

原位光沉积制备Z型α-Fe2O3/g-C3N4异质结及其可见光驱动光解水产氢性能

采用原位光沉积-煅烧法制得了Z型α-Fe₂O₃/g-C₃N₄异质结复合光催化剂。分别采用透射电子显微镜、X射线衍射、X射线光电子能谱、紫外可见漫反射光谱、荧光光谱以及电化学测试对样品进行了表征,并考察了可见光下光解水产氢活性。结果表明:当α-Fe₂O₃的负载量为2.9%时,α-Fe₂O₃/g-C₃N₄复合光催化剂具有最优的产氢催化活性,产氢速率高达1841.9μmol·g^-1·h^-1,约为g-C₃N₄的3.3倍。光催化性能的提高主要归因于3方面:(1)高温煅烧过程中α-Fe₂O₃的形成,有效促进了氮化碳片层的热剥离,增大了比表面积,从而为光催化反应提供了更多反应活性位;(2)超细α-Fe₂O₃颗粒(5~8 nm)高度均匀地分散在g-C₃N₄表面,并且与其紧密结合,形成了高质量的Z型异质结;(3)Z型异质结不仅有效抑制地了光生载流子的复合,同时极大地保留了g-C₃N₄导带电子的强还原性和α-Fe₂O₃价带空穴的强氧化性。     

Ti和乳酸共改性α-Fe2O3光阳极光电化学性能研究

采用一步水热后在氮气中进行热处理的方法制备了Ti和乳酸共改性的纳米花状α-Fe₂O₃光阳极。对样品分别进行了X射线衍射、扫描电镜、X射线光电子能谱、紫外-可见吸收光谱和光电化学性能测试。与乳酸改性的纳米片状α-Fe₂O₃光阳极相比,最优的Ti与乳酸共改性样品0.075LA-Fe2O3-0.75Ti光阳极的光电流密度从0.55mA·cm^-2提高到1.39mA·cm^-2。Ti改性明显减少了0.075LA-Fe₂O₃膜的表面态,增加了表面载流子注入效率;同时Ti的掺入也增加了电极体内载流子浓度,增强了体内载流子的传输效率。     

纳米Al2O3包覆富锂锰基正极材料Li1.2Ni0.13Co0.13Mn0.54O2的性能研究

采用纳米三氧化二铝(Al₂O₃)对富锂锰基正极材料Li_1.2Ni_0.13Co_0.13Mn_0.54O₂进行表面均匀包覆, 并考察了最优纳米Al₂O₃包覆量下材料的电化学性能. 扫描电子显微镜(SEM)和透射电子显微镜(TEM)显示了纳米Al₂O₃对富锂锰基正极材料表面均匀包覆, X射线衍射分析(XRD)结果表明包覆后富锂材料依然具有良好的层状结构. 恒流充/放电循环测试发现, 包覆后的Li_1.2Ni_0.13Co_0.13Mn_0.54O₂材料的首次放电比容量为249.7 mA·h/g, 循环100次后的容量保持率为89.5%, 与未包覆的Li_1.2Ni_0.13Co_0.13Mn_0.54O₂材料相比, 容量保持率提升约13%. 循环伏安(CV)和电化学阻抗(EIS)测试结果表明, 纳米Al₂O₃包覆可有效抑制材料极化, 降低界面阻抗和电荷转移阻抗, 进而提升富锂锰基正极材料的电化学性能.     

Enhanced electrochemical performance and mechanism study of AgLi1/3Sn2/3O2 for lithium storage

AgLi_1/3Sn_2/3O₂ with delafossite structure is prepared by treating Li₂SnO₃ with molten AgNO₃ and it exhibits improved electrochemical performance compared to Li₂SnO₃.     

A Facile Route to Synthesize Sheet-like Na2Ti3O7 with Improved Sodium Storage Properties

A high purity sheet-like Na₂Ti₃O₇ material was synthesized by a new facile solid-state method with hollow sphere TiO₂ as titanium source. X^-Ray diffraction(XRD) measurement proves that no impurity phase existed when the sample was heated at 900 ℃. Charge/discharge measurement was performed in a potential range of 0.01-2.5 V at different current-rates(C-rates). The initial charge/discharge capacities are 191/424 mA·h/g at 0.1 C and still remain as high as 101 mA·h/g after 50 cycles. CV test proves that the large irreversible capacity in the initial cycle results from the formation of the solid electrolyte interface(SEI). However, the electrode presents an increased initial coulombic efficiency in a 1 mol/L NaPF₆ electrolyte compared to that in a 1 mol/L NaClO₄ electrolyte.     

全有机S型异质结PDI-Ala/S-C3N4光催化剂增强光催化性能

Organic photocatalysts have attracted attention owing to their suitable redox band positions, low cost, high chemical stability, and good tunability of their framework and electronic structure. As a novel organic photocatalyst, PDI-Ala (N, N'-bis(propionic acid)-perylene-3, 4, 9, 10-tetracarboxylic diimide) has strong visible-light response, low valence band position, and strong oxidation ability. However, the low photogenerated charge transfer rate and high carrier recombination rate limit its application. Due to the aromatic heterocyclic structure of g-C₃N₄ and large delocalized π bond in the planar structure of PDI-Ala, g-C₃N₄ and PDI-Ala can be tightly combined through π–π interactions and N―C bond. The band structure of sulfur-doped g-C₃N₄ (S-C₃N₄) matched well with PDI-Ala than that with g-C₃N₄. The electron delocalization effect, internal electric field, and newly formed chemical bond jointly promote the separation and migration of photogenerated carriers between PDI-Ala and S-C₃N₄. To this end, a novel step-scheme (S-scheme) heterojunction photocatalyst comprising organic semiconductor PDI-Ala and S-C₃N₄ was prepared by an in situ self-assembly strategy. Meanwhile, PDI-Ala was self-assembled by transverse hydrogen bonding and longitudinal π–π stacking. The crystal structure, morphology, valency, optical properties, stability, and energy band structure of the PDI-Ala/S-C₃N₄ photocatalysts were systematically analyzed and studied by various characterization methods such as X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, ultraviolet visible diffuse reflectance spectroscopy, electrochemical impedance spectroscopy, and Mott-Schottky curve. The work functions and interface coupling characteristics were determined using density functional theory. The photocatalytic activities of the synthesized photocatalyst for H₂O₂ production and the degradation of tetracycline (TC) and p-nitrophenol (PNP) under visible-light irradiation are discussed. The PDI-Ala/S-C₃N₄ S-scheme heterojunction with band matching and tight interface bonding accelerates the intermolecular electron transfer and broadens the visible-light response range of the heterojunction. In addition, in the processes of the PDI-Ala/S-C₃N₄ photocatalytic degradation reaction, a variety of active species (h⁺, ·O₂^-, and H₂O₂) were produced and accumulated. Therefore, the PDI-Ala/S-C₃N₄ heterojunction exhibited enhanced photocatalytic performance in the degradation of TC, PNP, and H₂O₂ production. Under visible-light irradiation, the optimum 30%PDI-Ala/S-C₃N₄ removed 90% of TC within 90 min. In addition, 30%PDI-Ala/S-C₃N₄ displayed the highest H₂O₂ evolution rate of 28.3 μmol·h^-1·g^-1, which was 2.9 and 1.6 times higher than those of PDI-Ala and S-C₃N₄, respectively. These results reveal that the all organic photocatalyst comprising PDI-based supramolecular and S-C₃N₄ can be efficiently applied for the degradation of organic pollutants and production of H₂O₂. This work not only provides a novel strategy for the design of all organic S-scheme heterojunctions but also provides a new insight and reference for understanding the structure–activity relationship of heterostructure catalysts with effective interface bonding.      

Pd/Co3O4纳米颗粒负载于Al2O3纳米片高效催化甲烷燃烧

We report an efficient catalyst composed of ternary components prepared by inlaying Pd/Co₃O₄ nanoparticles in alkaline Al₂O₃ nanosheets for catalytic oxidation of methane. Pd/Co₃O₄ inlaid in alkaline Al₂O₃ exhibited a higher ability to break the C-H bond of methane than Pd/Co₃O₄ supported on SiO₂, ZrO₂, CeO₂, and acidic or neutral Al₂O₃. Our results show more oxygen vacancies and higher amounts of surface adsorbed oxygen on the surface of Pd/Co₃O₄/alkaline Al₂O₃ than on other catalysts, which is responsible for methane activation and conversion. Further, the Pd/Co₃O₄/alkaline Al₂O₃ catalyst can almost restore to its initial value in the absence of water when 5% (volume fraction) vapor water was cut off, although a decrease in activity occurred when water vapor was introduced to the reaction system. Even under a condition similar to the exhaust of a lean-burn natural gas engine, the catalytic performance of the Pd/Co₃O₄/alkaline Al₂O₃ catalyst is excellent, that is, methane could be completely converted when the sample temperature in the reaction atmosphere was ramped to 400℃.     

反蛋白石结构ZnO@PDA用于增强光催化产H2O2性能

利用太阳能驱动生产高能量密度的H₂O₂太阳能燃料引起了广泛关注,但目前光催化剂缓慢的动力学限制了其实际应用。本文制备一种聚多巴胺(PDA)改性的反蛋白石结构ZnO(ZnO@PDA)光催化剂,用于可持续性的光催化产H₂O₂。由于电子的转移,因此当PDA与ZnO接触后,会在界面处形成一个从PDA指向ZnO的内建电场。在内建电场和能带弯曲的驱动下,ZnO导带中的光生电子与PDA最高占据分子轨道(HOMO)中的空穴复合,符合梯型异质结的电荷转移和分离途径。这种独特的梯型异质结确保了有效的电子或空穴的分离并且留存下具有强氧化还原能力的光生载流子。此外,与纯ZnO相比,反蛋白石结构的ZnO@PDA具有更强的光吸收能力。实验表明,归因于光吸收能力的提高,光生载流子的有效分离和强氧化还原能力,负载0.03% (原子分数) PDA的ZnO样品具有最佳的产H₂O₂性能(1011.4 μmol·L^-1·h^-1),分别是纯ZnO和PDA的4.4和8.9倍。     

二维Z型BCN/Sn3O4复合材料的光催化还原性能

分别以直接热聚合法和水热合成法制备得到二维硼掺杂氮化碳(BCN)和四氧化三锡(Sn₃O₄)半导体材料, 采用超声复合和煅烧复合两种方法构建了BCN/Sn₃O₄复合材料. 利用 X 射线衍射(XRD)、 紫外-可见漫反射(UV-Vis)光谱、 透射电子显微镜(TEM)等手段对所制备样品进行了表征和分析, 探讨了不同复合方法对催化剂微观结构及光电性质的影响; 以可见光下光解水制氢和活化氧制过氧化氢为模型反应考察了催化剂的光催化性能. 结果表明, BCN与Sn₃O₄能够形成二维面-面复合结构, 相比于超声复合法, 直接煅烧法更有利于有效界面的形成, 使得界面间产生Sn₃O₄到BCN的电荷迁移, 增强了BCN表面电荷密度, 并使复合材料具有更加优化的光电响应和光催化还原活性, 其中煅烧法得到的复合样品BCN/Sn₃O₄-3C(Sn₃O₄与BCN质量比为3%)表现出显著增强的光解水制氢及活化氧制过氧化氢的活性.     

微波辅助溶剂热合成In-Si共改性TiO_2的增强光催化性能

利用微波辅助溶剂热法合成了In-Si共改性的TiO2光催化剂.粉末X射线衍射(XRD)、激光拉曼(Raman)光谱、N2吸脱附(BET)、X射线光电子能谱(XPS)、光致发光(PL)光谱和紫外-可见漫反射光谱(UV-Vis DRS)等实验表明,尽管掺杂和改性后TiO2结晶度略有降低,但不影响光催化剂锐钛相的形成.Si掺杂入TiO2晶格使颗粒变小,比表面积变大.In不能进入TiO2晶格,在TiO2表面形成了In2O3.罗丹明B(RhB)降解实验显示,In-Si共改性TiO2表现出很高的紫外和可见光催化活性,Si:In:Ti的摩尔比为0.03:0.02:1的样品(IST-2)光催化活性最高,紫外光下3 min即可将RhB降解完全,可见光下120 min RhB降解率为97%,这是由材料的高表面积,In2O3-TiO2复合半导体之间高效电荷转移及染料敏化等共同作用所致.对于苯酚,光催化降解则相对缓慢,700 min内尚不能降解完全.     

基于3-羟基沙利度胺的比率型荧光探针对过氧化氢的检测

药物分子3-羟基沙利度胺作为分子胶水因其良好的生物相容性、 明确的代谢途径以及与CRBN 蛋白的特异性结合而备受关注, 但其在分析化学领域的应用却鲜有报道. 本文基于3-羟基沙利度胺的特殊荧光性能, 研究了其在化学传感器领域的新应用. 以3-羟基沙利度胺为荧光核, 设计合成了显现荧光的过氧化氢探针沙利度胺基频哪醇硼酸酯. 基于激发态分子内质子转移机理, 该探针对过氧化氢显示出特异选择性和超高灵敏度, 检出限为9.8 nmo/L, 可应用于化学实验废水、 污水及化妆品中过氧化氢的检测. 此外, 通过光谱技术和理论计算揭示了该荧光探针的识别机制.     

TiO2/Bi2O3纳米复合体的制备及可见光催化产氢性能

首先采用相分离的水解-溶剂热法制备了Bi₂O₃纳米粒子,然后利用简单的湿化学法在Bi₂O₃表面负载不同比例的TiO₂纳米颗粒,进而得到TiO₂/Bi₂O₃纳米复合体。通过气氛调控的表面光电压谱(SPS)等测试表明,表面负载适量的TiO₂后能够提高Bi₂O₃光生电荷分离。可见光催化产氢和降解污染物测试结果进一步证明,表面负载适量的TiO₂后可显著提高其可见光催化活性,其中Ti/Bi摩尔比为7%时具有最高的光催化活性。这主要归因于TiO₂具有较为合适的导带能级位置,可以接收Bi₂O₃在可见光激发下所产生的高能级电子,从而抑制光生电子-空穴对复合,并且维持了高能级电子较高的还原能力。     

水蒸气和α-Fe_2O_3对铈改性半焦脱除单质汞的影响研究

采用浸渍法制备了铈改性半焦吸附剂(Ce/SC),在小型固定床反应器上考察了水蒸气和α-Fe_2O_3对Ce/SC脱除Hg~0性能的影响,并利用X射线衍射、H2程序升温还原、X射线光电子能谱等分析手段对其机理进行了探究。结果表明,水蒸气会明显抑制Ce/SC对单质汞的脱除效率,原因是H_2O分子在活性组分CeO_2表面发生解离,部分晶格氧转化成Ce-OH官能团,从而导致其氧化活性的降低;α-Fe_2O_3的加入对Ce/SC的脱汞性能无显著影响;当水蒸气和α-Fe_2O_3同时存在时,Ce/SC的脱汞效率虽然有所降低,但是其降低幅度明显低于水蒸气单独作用时的情况,这主要是因为水蒸气与α-Fe_2O_3作用增加了其表面化学吸附氧的含量,提高了α-Fe_2O_3的氧化活性,促进单质汞的氧化和脱除。     

Al_2O_3包覆对Na_(0.44)MnO_2正极材料高温储钠性能的改善

Na_(0.44)MnO_2具有特殊的三维隧道结构和良好的化学稳定性,是一种理想的钠离子电池正极材料。本文研究了Na_(0.44)MnO_2正极材料的高温电化学性能,采用液相法对Na_(0.44)MnO_2正极材料进行Al_2O_3包覆改性,并通过电化学、形貌分析、结构分析、化学成分表征等方法研究Al_2O_3包覆的改性机制。结果表明:Al_2O_3包覆层有效地隔离了Na_(0.44)MnO_2与电解液的直接接触,缓解了高温下锰的溶解,从而维持了稳定的电极/溶液界面结构。Na_(0.44)MnO_2@Al_2O_3在55°C下的电化学性能相比未包覆Na_(0.44)MnO_2有显著提升:循环100次后容量保持率达79.2%,远高于未包覆的66.5%;在10C (1C=120 mAh·g~(-1))的大电流密度下放电比容量达到63.6 mAh·g~(-1),而未包覆的仅有12.3 mAh·g~(-1)。