原位构筑质子化氮化碳/碳化钛光催化制氢肖特基异质结

氢气因其具有高燃烧热、可再生性以及燃烧产物无污染等优势被认为是一种绿色可再生能源,是取代化石燃料的候选能源之一.然而,如何利用自然界中丰富的太阳能和水资源实现光分解水制氢的关键在于开发高效的光催化剂.在尺寸明确、能级带隙匹配的纳米材料间进行完美的界面复合(异质结构筑)是实现高效太阳能-氢能转换的最佳途径.石墨相氮化碳(CN)材料因其电子结构可调和化学性能稳定等特性被光催化界所关注.然而,氮化碳材料较弱的电学性能如电荷传输能力差及电子-空穴对复合率高导致其表现出较低的光催化制氢效率.基于此,我们用盐酸对氮化碳进行质子化处理,使材料表面电荷发生改变,从而实现氮化碳的电子带隙调节和电导率提升.在此基础上,将二维碳化钛原位负载于质子化的氮化碳(PCN)纳米片表面构筑肖特基结.PCN纳米片与碳化钛纳米片间的良好界面接触促进了电荷在材料界面上传输,进而加速了氮化碳材料的电荷分离,实现了氮化碳光催化剂活性的提升.Zeta电位测试结果显示,CN和PCN的表面电位分别为?9.5和27.3 mV,表明质子化处理可以有效改变材料表面电荷,并促其与碳化钛纳米片进行静电组装.该结果进一步得到了扫描电子显微镜(SEM)和原子力显微镜(AFM)的证实.改变表面电荷使氮化碳材料的能带宽度由2.53 eV(CN)减小到2.41 eV(PCN),增强了可见光区吸收.同时,PCN的光电流密度提升了约4倍,电子阻抗和激发态电子的辐射复合都显著降低.将PCN与碳化钛复合制得复合材料(PCN-x,x=10,20,40),实验结果表明5 g的PDN最佳负载碳化钛的量为20 mg(PCN-20).在标准太阳模拟器的可见光区(>420 nm),复合材料PCN-20的光催化水分解产氢量可达2181μmol·g-1,是CN催化剂的约5.5倍,PCN的2.7倍,并且经过5次产氢循环后PCN-20仍具有稳定的氢气释放速率.以上结果表明,氮化碳材料可以通过质子化处理以及与适量的碳化钛复合实现光催化产氢性能的提升,其中碳化钛在体系中起助催化剂的作用.该研究结果可为其他半导体光催化剂的性能优化以及非贵金属助催化剂的研究提供新思路.     

钙钛矿光伏电池的非辐射复合损耗及调控策略

基于金属卤化物的钙钛矿光伏电池(PSCs)具有较大的光吸收系数、长的载流子扩散距离以及较低的制备成本等优势,在过去十几年来得到了研究者的广泛关注,目前最高光电转换效率(PCE)已经达到25.5%。然而,由于载流子运输过程中存在各类非辐射复合损耗,器件的PCE仍然低于肖克利-奎伊瑟理论极限。本文围绕PSCs的结构与工作原理,着重综述了器件工作过程中常见的非辐射复合方式,具体包括缺陷辅助复合、界面诱导复合、俄歇复合和带尾复合等,这些复合方式作为影响器件效率与工作稳定性的重要因素,受到研究者的广泛关注。结合最新的研究进展,从减小钙钛矿晶体缺陷、钝化晶界缺陷、钝化表面缺陷、优化能级结构等四个方面总结概括了降低非辐射复合的常用措施和策略。最后,对PSCs的非辐射复合调控前景进行了展望。     

石墨烯-量子点复合材料的制备与应用

石墨烯因其独特的物理化学性质以及潜在的巨大应用价值引起了越来越多的研究兴趣,但其特殊的零带隙结构却限制了它在光电领域的应用。半导体量子点因其特有的量子尺寸效应而表现出迷人的光学性能,已成功应用于生物标记及电化学等领域,但电子-空穴对易复合湮灭,导致电子迁移率较低,限制了其在光电转换方面的应用。石墨烯独特的结构和电子特性使其成为优秀的导电支架,可从量子点中捕获并输运电子,实现了电子空穴对的有效分离。石墨烯-量子点复合材料不仅具有石墨烯的高电子传输性能,而且具备量子点特殊结构产生的量子尺寸效应和边缘效应,二者复合后在纳米器件和光电器件等领域极具应用潜力。本文详细总结了近年来石墨烯-量子点复合材料的制备方法,包括相转移法、静电复合、水热和溶剂热法以及电化学法和微波辅助法等,并简要介绍了相关应用领域的研究进展,以期为石墨烯基纳米复合材料的发展研究提供相关的参考与依据。     

介孔掺镧纳米晶TiO_2瞬态光伏与表面光声特性

结合瞬态光伏与表面光声技术,研究介孔掺镧nano-TiO2光生载流子分离与复合过程及其能量转换机制.结果表明:锐钛矿中两种不同光伏特性的缺陷态具有光生载流子扩散距离短,复合速度快的特点;镧掺杂增加体缺陷态对于光伏效应的贡献,但在某种程度上抑制主带隙的电荷分离;模板剂种类对于主带隙电子-空穴对的分离与复合过程,以及亚带隙无辐射跃迁引起的晶格振动均有显著的影响.结果证实了样品表面光声与瞬态光伏现象之间存在明显的能量互补关系.     

介孔掺镧纳米晶TiO2瞬态光伏与表面光声特性

结合瞬态光伏与表面光声技术, 研究介孔掺镧nano-TiO2光生载流子分离与复合过程及其能量转换机制. 结果表明: 锐钛矿中两种不同光伏特性的缺陷态具有光生载流子扩散距离短, 复合速度快的特点; 镧掺杂增加体缺陷态对于光伏效应的贡献, 但在某种程度上抑制主带隙的电荷分离; 模板剂种类对于主带隙电子-空穴对的分离与复合过程, 以及亚带隙无辐射跃迁引起的晶格振动均有显著的影响. 结果证实了样品表面光声与瞬态光伏现象之间存在明显的能量互补关系.     

聚集诱导发光材料与纳米晶复合体系动力学新进展北大核心CSCD

近期,中科院大连化物所吴凯丰研究员团队将聚集诱导发光分子(AIEgen)嫁接到纳米晶表面,并研究了这一复合体系的激发态动力学,发现这一复合体系中AIEgen的非辐射分子内运动可以得到有效抑制,这一普适性现象可用于构建各类多功能发光材料。相关工作发表于《物理化学快报》(Journal of Physical Chemistry Letters)上。传统的染料分子由于芳香环的π-π堆积通常表现出聚集诱导猝灭现象(ACQ),阻碍了这些染料分子在不良溶剂和固体发光器件中的广泛应用。AIEgen则刚好相反:在良溶剂中,各种分子内运动可耗散激发态能量,导致发光效率极低;在不良溶剂或者固态薄膜中,分子的团聚有效抑制了上述非辐射分子内运动,表现出强烈的发光行为。     

Gd-N共掺杂SrTiO3/TiO2复合纳米纤维制备及光催化性能

以静电纺丝技术制备的TiO_2纳米纤维为基质和反应物,结合一步水热法制得Gd-N共掺杂SrTiO_3/TiO_2复合纳米纤维光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射(UV-Vis DRS)和荧光光谱(PL)等方法对其微观结构、形貌和光学性能进行表征。结果表明:SrTiO_3和TiO_2形成异质结能够使光生电子和空穴得到很好的分离,而Gd-N共掺杂产生新带隙,可以拓宽光谱响应范围至可见光区,并引起晶格缺陷,成为光生电子-空穴对的浅势捕获阱。Gd-N共掺杂与异质结的协同作用有效提高了SrTiO_3/TiO_2复合纳米纤维的可见光催化活性。     

含不同杂原子共轭单元的有机光敏染料的超快发光动力学

系统研究了含有不同杂原子的共轭单元(联呋喃、联噻吩及联硒酚)的三种有机染料C210、C214和C216的超快发光动力学,双己氧基取代的三苯胺作为电子给体,氰基丙烯酸作为电子受体。详细考察了三种染料分别在不同媒介中的激发态动力学：四氢呋喃及甲苯溶液、聚甲基丙烯酸甲酯及聚苯乙烯聚合物薄膜、氧化铝及二氧化钛薄膜表面。发现在以上介质中都普遍存在动态斯托克斯位移现象,表明发生了非平衡激发态的分子内多步弛豫过程。由于扭转弛豫和电子注入过程之间的竞争作用,非平衡激发态的电子注入产率比平衡激发态的低得多。此外,由于激发态能量弛豫导致的能量损失,电子注入时间常数变化超过了一个数量级,这在未来的染料设计及器件发展中应进行控制。三种染料在平衡激发态处的电子注入效率相近,由于C210和C216加快的电子注入速率补足了它们较C214小的平衡激发态寿命。     

含不同杂原子共轭单元的有机光敏染料的超快发光动力学（英文）

系统研究了含有不同杂原子的共轭单元(联呋喃、联噻吩及联硒酚)的三种有机染料C210、C214和C216的超快发光动力学,双己氧基取代的三苯胺作为电子给体,氰基丙烯酸作为电子受体。详细考察了三种染料分别在不同媒介中的激发态动力学:四氢呋喃及甲苯溶液、聚甲基丙烯酸甲酯及聚苯乙烯聚合物薄膜、氧化铝及二氧化钛薄膜表面。发现在以上介质中都普遍存在动态斯托克斯位移现象,表明发生了非平衡激发态的分子内多步弛豫过程。由于扭转弛豫和电子注入过程之间的竞争作用,非平衡激发态的电子注入产率比平衡激发态的低得多。此外,由于激发态能量弛豫导致的能量损失,电子注入时间常数变化超过了一个数量级,这在未来的染料设计及器件发展中应进行控制。三种染料在平衡激发态处的电子注入效率相近,由于C210和C216加快的电子注入速率补足了它们较C214小的平衡激发态寿命。     

不同电子传输层的蓝光有机电致发光器件的性能研究

自从Tang等^[1]首次报道多层有机电致发光器件（OLED）以来,其在亮度和效率上有了质的飞跃,表明器件的结构对提高发光亮度和发光效率起着至关重要的作用,单层器件虽然具有制作简单的优点,但却存在明显缺点：（1）复合发光区靠近金属电极,该处缺陷很多,非辐射复合几率大,导致器件效率降低;（2）由于两种载流子注入不平衡,载流子的复合几率较低,因而影响器件的发光效率,要使发光层中具有高的载流子辐射复合效率,两种载流子的注入及传输能力应相当,否则传输快的一方就会直接穿过发光层到达对电极被猝灭,平衡电子和空穴的注入与传输可通过在电极和发光层之间加入载流子输运层或限制层制作多层器件的途径来实现,基于上述考虑,我们以PPCP为发光层（PPCP是一种荧光效率较高的蓝光材料^[2-4],对其进行深入研究尚未见有文献报道＿,设计了4种不同电子传输层（ETL)的三层 结构的OLED,为研究电子传输层对器件性能的影响,我们还制备了不含电子传输层的双层器件,结果表明,通过选择合适的ETL,OLED的发光亮度及发光效率会有很大程度的改善。     

Mn0.2Cd0.8S@CoAl LDH S-型异质结构建及其光催化析氢性能研究

构建高效、稳定的异质结光催化剂体系是实现太阳能驱动分解水制氢的有效途径。本研究通过物理混合法将Mn_0.2Cd_0.8S纳米棒与CoAl LDH纳米片进行耦合,成功制备出一种新型的Mn_0.2Cd_0.8S@CoAl LDH (MCCA) S型异质结光催化剂。光致发光光谱和光电流测试结果表明,该异质结在内建电场的作用下可以有效地加快Mn_0.2Cd_0.8S和CoAl LDH界面间光生载流子的分离和电子转移。关键的是,CoAl LDH的引入有效地抑制了光生电子与空穴的复合,从而提高了Mn_0.2Cd_0.8S的光催化产氢活性。最佳CoAl LDH负载量的MCCA-3在5 h内的产氢量为1177.9 μmol。与单独使用纯Mn_0.2Cd_0.8S纳米棒和CoAl LDH纳米片相比,这是一个显著的改进。本研究为合理设计用于光催化制氢的S型异质结光催化剂提供了一条简单有效的途径。     

缺陷工程调控石墨相氮化碳及其光催化空气净化应用进展

Since the pioneering work on polychlorinated biphenyl photodegradation by Carey in 1976, photocatalytic technology has emerged as a promising and sustainable strategy to overcome the significant challenges posed by energy crisis and environmental pollution. In photocatalysis, sunlight, which is an inexhaustible source of energy, is utilized to generate strongly active species on the surface of the photocatalyst for triggering photo-redox reactions toward the successful removal of environmental pollutants, or for water splitting. The photocatalytic performance is related to the photoabsorption, photoinduced carrier separation, and redox ability of the semiconductor employed as the photocatalyst. Apart from traditional and noble metal oxide semiconductors such as P25, bismuth-based compounds, and Pt-based compounds, 2D g-C₃N₄ is now identified to have enormous potential in photocatalysis owing to the special π-π conjugated bond in its structure. However, some inherent drawbacks of the conventional g-C₃N₄, including the insufficient visible-light absorption ability, fast recombination of photogenerated electron-hole pairs, and low quantum efficiency, decrease its photocatalytic activity and limit its application. To date, various strategies such as heterojunction fabrication, special morphology design, and element doping have been adopted to tune the physicochemical properties of g-C₃N₄. Recent studies have highlighted the potential of defect engineering for boosting the light harvesting, charge separation, and adsorption efficiency of g-C₃N₄ by tailoring the local surface microstructure, electronic structure, and carrier concentration. In this review, we summarize cutting-edge achievements related to g-C₃N₄ modified with classified non-external-caused defects (carbon vacancies, nitrogen vacancies, etc.) and external-caused defects (doping and functionalization) for optimizing the photocatalytic performance in water splitting, removal of contaminants in the gas phase and wastewater, nitrogen fixation, etc. The distinctive roles of various defects in the g-C₃N₄ skeleton in the photocatalytic process are also summarized. Moreover, the practical application of 2D g-C₃N₄ in air pollution control is highlighted. Finally, the ongoing challenges and perspectives of defective g-C₃N₄ are presented. The overarching aim of this article is to provide a useful scaffold for future research and application studies on defect-modulated g-C₃N₄.      

构建NiS2/MoSe2 S型异质结高效光催化产氢

S-scheme heterojunction is a major breakthrough in the field of photocatalysis. In this study, NiS₂ and MoSe₂ were prepared by a typical solvothermal method, and compounded by an in situ growth method to construct an S-scheme heterojunction. The obtained composite showed excellent performance in photocatalytic hydrogen evolution; the hydrogen production rate was approximately 7 mmol·h^-1·g^-1, which was 2.05 times and 2.44 times those of pure NiS₂ and MoSe₂, respectively. Through a series of characterizations, it was found that NiS₂ and MoSe₂ coupling can enhance the light absorption intensity, which is vital for the light reaction system. The efficiency of electron-hole pair separation is also among the important factors restricting photocatalytic reactions. Compared with pure NiS₂ and MoSe₂, NiS₂/MoSe₂ exhibited a higher photocurrent density, lower cathode current, and lower electrochemical impedance, which proves that the NiS₂/MoSe₂ complex can effectively promote photogenerated electron transfer. Simultaneously, the lower emission intensity of fluorescence indicated effective inhibition of electron-hole recombination in the NiS₂/MoSe₂ complex, which is favorable for the photocatalytic hydrogen evolution reaction. Further, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that MoSe₂ is an amorphous sample surrounded by the NiS₂ nanomicrosphere, which greatly increased the contact area between the two, thus increasing the active site of the reaction. Secondly, as a photosensitizer, Eosin Y (EY) effectively enhanced the absorption of light by the catalyst in the photoreaction system. Meanwhile, during sensitization, electrons were provided to the catalyst, which effectively improved the photocatalytic reaction efficiency. The establishment of S-scheme heterojunctions contributed to improving the redox capacity of the reaction system and was the most important link in the photocatalytic hydrogen reduction of aquatic products. It was also the main reason for the improvement of the hydrogen evolution effect in this study. The locations of the conduction band and valence band of NiS₂ and MoSe₂ were determined by Mott-Schottky plots and photon energy curves, and further proved the establishment of the S-scheme heterojunction. This work provides a new reference for studying the S-scheme heterojunction to effectively improve the photocatalytic hydrogen production efficiency.      

有机配体表面改性NiCo2O4纳米线用于水全分解

由于水分解在绿色能源领域的重要作用,能够在碱性介质中进行析氢(HER)和析氧(OER)反应的双功能电催化剂具有重要的应用价值。本文报道一种具有丰富缺陷的表面改性NiCo₂O₄纳米线(NWs),在碱性介质中作为一种高效的整体水裂解电催化剂。X射线光电子能谱(XPS)分析表明,Co²⁺/Co³⁺比值的增加是表面修饰NiCo₂O₄纳米线具有优异双功能电催化性能的重要原因。结果表明,在1.0 mol·L^-1 KOH溶液中,通过有机配体主导的表面改性,优化后的NiCo₂O₄纳米线在电流密度达到10 mA·cm^-2时的HER过电位仅为83 mV,OER过电位仅为280 mV。更重要的是,有机配体表面改性后的NiCo₂O₄纳米线表现出了出色的水分解性能,在2.1 V电压下达到了100 mA·cm^-2的电流密度。目前的工作凸显了提高NiCo₂O₄ NWs尖晶石结构中Co²⁺含量对促进整体水裂解的重要性。     

反蛋白石结构的g-C3N4可控合成及其优异的光催化产氢性能

The growing frustration from facing energy shortages and unbalanced environmental issues has obstructed the long-term development of human society. Semiconductor-based photocatalysis, such as water splitting, transfers solar energy to storable chemical energy and is widely considered an economic and clean solution. Although regarded as a promising photocatalyst, the low specific surface area of g-C₃N₄ crucially restrains its photocatalytic performance. The macro-mesoporous architecture provides effective channels for mass transfer and full-light utilization and improved the efficiency of the photocatalytic reaction. Herein, g-C₃N₄ with an inverse opal (IO) structure was rationally fabricated using a well-packed SiO₂ template, which displayed an ultrahigh surface area (450.2 m²·g^-1) and exhibited a higher photocatalytic H₂ evolution rate (21.22 μmol·h^-1), almost six times higher than that of bulk g-C₃N₄ (3.65 μmol·h^-1). The IO g-C₃N₄ demonstrates better light absorption capacity than bulk g-C₃N₄, primarily in the visible spectra range, owing to the multiple light scattering effect of the three-dimensional (3D) porous structure. Meanwhile, a lower PL intensity, longer emission lifetime, smaller Nyquist semicircle, and stronger photocurrent response (which synergistically give rise to the suppressed recombination of charge carriers) decrease the interfacial charge transfer resistance and boost the formation of photogenerated electron-hole pairs. Moreover, the existing N vacancies intensify the local electron density, helping increase the number of photoexcitons. The N₂ adsorption-desorption test revealed the existence of ample mesopores and macropores and high specific surface area in IO g-C₃N₄, which exposes more active edges and catalytic sites. Optical behavior, electron paramagnetic resonance, and electrochemical characterization results revealed positive factors, including enhanced light utilization, improved photogenerated charge separation, prolonged lifetime, and fortified IO g-C₃N₄ with excellent photocatalytic performance. This work provides an important contribution to the structural design and property modulation of photocatalysts.      

一维/二维W18O49/多孔g-C3N4梯形异质结构建及其光催化析氢性能研究

提高光催化分解水制氢的效率是能量转换领域的关键挑战。本研究首先合成了二维多孔氮化碳(PCN),然后在二维PCN上原位生长了一维W₁₈O₄₉ (WO),形成了一种新型的梯形(S型)异质结。该异质结可以加快界面电荷的分离和转移,赋予WO/PCN体系更好的氧化还原能力。此外,具有多孔结构的PCN提供了更多的催化活性位点。与WO和PCN相比,20% WO/PCN复合材料具有更高的H₂产率(1700 μmol·g^-1·h^-1),是PCN (30 μmol·g^-1·h^-1)的56倍。本研究提供了一种新S型光催化剂用于光催化制氢领域。     

理论计算研究二维/二维BP/g-C3N4异质结的光催化CO2还原性能

Photocatalytic reduction of CO₂ to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO₂ reduction performance. In addition, metal-free materials such as g-C₃N₄ and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C₃N₄ composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO₂ reduction reaction processes of 2D/2D BP/g-C₃N₄ composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C₃N₄. Based on the calculated work function, it is inferred that electrons transfer from g-C₃N₄ to BP owing to the higher Fermi level of g-C₃N₄ compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C₃N₄ hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C₃N₄, leaving photogenerated electrons and holes in the conduction band of g-C₃N₄ and the valence band of BP, respectively. Compared with pristine g-C₃N₄, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO₂ reduction on g-C₃N₄ and BP/g-C₃N₄ is discussed by computing the free energy of each step. It was found that CO₂ reduction on the composite occurs most readily on the g-C₃N₄ side. The reaction path on the composite is different from that on g-C₃N₄. The heterojunction reduces the maximum energy barrier for CO₂ reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C₃N₄ heterojunction is theoretically proven to be an excellent CO₂ reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C₃N₄. It also provides a theoretical basis for the design of other high-performance CO₂ reduction photocatalysts.      

二维光催化材料电子结构和性能调控策略研究进展

Two-dimensional photocatalytic materials have potential applications in the fields of environmental purification and energy conversion owing to their rich surface active sites, unique geometric structures, adjustable electronic structures, and good photocatalytic activities. At present, the main two-dimensional photocatalytic materials include metal oxides, metal composite oxides, metal hydroxides, metal sulfides, bismuth-based materials, and non-metallic photocatalytic materials. The absorption of photons in bulk materials or nanoparticles is often limited by the transmittance and reflection at the grain boundary, while the two-dimensional structure can provide a large specific surface area and abundant surface low-coordination atoms to obtain more UV visible light. In addition, the smaller atomic thickness of two-dimensional photocatalytic materials can shorten the carrier migration distance. Thus, in two-dimensional photocatalytic materials, the carriers generated in the interior migrate to the surface faster than that in the bulk materials, which can reduce the recombination of photogenerated carriers and facilitate the photocatalytic reaction. For the surface redox reaction, the two-dimensional structure can provide more abundant surface-active sites to accelerate the reaction process. Additionally, when the thickness is reduced to the atomic scale, the escape energy of atoms is relatively small, thereby increasing the surface defects, which is helpful for the adsorption and activation of target molecules. Thus, the synthesis methods and performance enhancement strategies of two-dimensional photocatalytic materials have been developed rapidly. The former strategies mainly focus on the adjustment of morphology and geometric structure characteristics, which cannot fully meet the design requirements of efficient and stable photocatalysts. The photocatalytic performance and stability can be improved by surface design to construct abundant active sites and adjust the electronic structure. Research on the reaction mechanism of photocatalysis can help us understand the demand for photocatalytic structure characteristics in different reactions, thereby guiding the design of photocatalysts. In this paper, the advances in surface design and electronic structure regulation strategies of two-dimensional photocatalytic materials are reviewed from three aspects: light absorption; charge separation; and active sites, including element doping, heterojunction design, defect construction, single atom modification, and plasmonic metal loading. The effects on the reaction mechanism for typical air pollutant purification by regulating the electronic structure of two-dimensional photocatalytic materials are summarized. Finally, the problems and challenges associated with the development of two-dimensional photocatalytic materials are analyzed and discussed.      

二维/二维FeNi-LDH/g-C3N4复合光催化剂用于促进CO2光还原反应

Photocatalytic reduction of carbon dioxide into chemical fuels is a promising route to generate renewable energy and curtail the greenhouse effect. Therefore, various photocatalysts have been intensively studied for this purpose. Among them, g-C₃N₄, a 2D metal-free semiconductor, has been a promising photocatalyst because of its unique properties, such as high chemical stability, suitable electronic structure, and facile preparation. However, pristine g-C₃N₄ suffers from low solar energy conversion efficiency, owing to its small specific surface area and extensive charge recombination. Therefore, designing g-C₃N₄ (CN) nanosheets with a large specific surface area is an effective strategy for enhancing the CO₂ reduction performance. Unfortunately, the performance of CN nanosheets remains moderate due to the aforementioned charge recombination. To counter this issue, loading a cocatalyst (especially a two-dimensional (2D) one) can enable effective electron migration and suppress electron-hole recombination during photo-irradiation. Herein, CN nanosheets with a large specific surface area (97 m²·g^-1) were synthesized by a two-step calcination method, using urea as the precursor. Following this, a 2D/2D FeNi-LDH/g-C₃N₄ hybrid photocatalyst was obtained by loading a FeNi layered double hydroxide (FeNi-LDH) cocatalyst onto CN nanosheets by a simple hydrothermal method. It was found that the production rate of methanol from photocatalytic CO₂ reduction over the FeNi-LDH/g-C₃N₄ composite is significantly higher than that of pristine CN. Following a series of characterization and analysis, it was demonstrated that the FeNi-LDH/g-C₃N₄ composite photocatalyst exhibited enhanced photo-absorption, which was ascribed to the excellent light absorption ability of FeNi-LDH. The CO₂ adsorption capacity of the FeNi-LDH/g-C₃N₄ hybrid photocatalyst improved, owing to the large specific surface area and alkaline nature of FeNi-LDH. More importantly, the introduction of FeNi-LDH on the CN nanosheet surface led to the formation of a 2D/2D heterojunction with a large contact area at the interface, which could promote the interfacial separation of charge carriers and effectively inhibit the recombination of the photogenerated electrons and holes. This subsequently resulted in the enhancement of the CO₂ photo-reduction activity. In addition, by altering the loading amount of FeNi-LDH for photocatalytic performance evaluation, it was found that the optimal loading amount was 4% (w, mass fraction), with a methanol production rate of 1.64 μmol·h^-1·g^-1 (approximately 6 times that of pure CN). This study provides an effective strategy to improve the photocatalytic CO₂ reduction activity of g-C₃N₄ by employing 2D layered double hydroxide as the cocatalyst. It also proposes a protocol for the successful design of 2D/2D photocatalysts for solar energy conversion.      

有机硫化合物在锂硫电池中的应用

锂硫电池具有理论能量密度高、环境友好和成本低等优点,有望成为替代锂离子电池的新一代储能系统。然而,锂硫电池充放电产物的绝缘性、可溶性多硫化锂的穿梭效应、硫正极体积膨胀及锂枝晶的不可控生长,严重影响了锂硫电池的实际容量发挥和循环稳定性。为解决上述问题,采用有机硫化合物来替代单质硫作为正极材料是有前途的策略。调控有机硫化合物的硫链、碳链及其相互作用,可改变其电化学反应过程,提高离子/电子电导,抑制穿梭效应。有机硫化合物作为电解液添加剂,可调控硫正极的反应过程并保护金属锂负极,作为聚合物电解质的改性链段可加速锂离子传导。本综述对有机硫化合物在锂硫电池的正极、电解液添加剂和固态电解质中的应用研究进展进行详细的阐述。将有机硫化合物的结构、反应机理和电化学性质联系起来,为解决锂硫电池存在的问题提供见解。最后,提出高性能有机硫化合物的设计合成和机理研究思路,以期实现可实用化的锂硫电池。