石墨相氮化碳基光催化剂研究进展

石墨相氮化碳是一种新型的非金属碳氮聚合物,具有优异的光催化性能。本文总结了近年来氮化碳光催化剂的设计与合成,对如何提高其光催化性能的相关工作进行了归纳总结,包括掺杂非金属元素和贵价金属、构建异质结、染料敏化、形貌调控等,并对石墨相氮化碳基光催化剂的后续应用和未来发展进行了展望。     

石墨相氮化碳光催化产氢性能提升策略研究进展

石墨相氮化碳(g-C3N4)因带隙窄、稳定性高、成本低、污染小等优势在光催化产氢领域受到了研究者们的广泛关注.然而,纯g-C3N4直接作为光催化剂在应用时常存在比表面积小、可见光利用效率低以及光生载流子复合过快等缺陷,导致其光催化产氢性能较不理想.因此,如何改善g-C3N4的光催化产氢性能是目前光催化领域的研究热点.该文针对g-C3N4光催化产氢性能的优化研究,系统综述了g-C3N4在形貌调节、杂原子掺杂和异质结构建三个方面的改性研究进展,归纳总结了目前存在的问题,并对今后g-C3N4产氢光催化剂的研究重点和方向做出了展望.     

三维大孔氮化碳材料的制备及其血液相容性

以粒径640 nm的单分散二氧化硅胶体晶体为模板,由四氯化碳和乙二胺回流加热制备出氮化碳的前驱物;将其填入模板的缝隙中,在氮气中热处理,形成氮化碳/二氧化硅的复合物;用氢氟酸除去二氧化硅模板,制备出三维大孔氮化碳材料. 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射 (XRD)、选区电子衍射(SAED)、元素分析、红外光谱(FT-IR)、X射线光电子能谱(XPS),对其形貌结构、元素组成、键合状态进行了形貌和结构的表征. 采用部分凝血活酶时间(APTT)、凝血酶原时间(PT)和凝血酶时间(TT)对其体外抗凝血活性作了初步的评价,发现制备的大孔氮化碳对血液不会造成促凝,说明其可能成为一种新的血液相容性材料.     

三聚氰胺热解产物的特性分析

以有机物三聚氰胺为初始原料, 在真空条件下使其热解（1 000 K）. 采用X射线衍射（XRD）、 透射电子显微镜（TEM）、 X射线光电子能谱(XPS)、 化学元素分析（EA）和傅里叶红外光谱(FT-IR) 分析样品的形貌、 成分和结构. 结果表明, 在真空条件下, 三聚氰胺全部分解, 分解产物为片层石墨相C₃N₄.      

Interaction of hydrogen with metal nitrides and imides

The pursuit of a clean and healthy environment has stimulated much effort in the development of technologies for the utilization of hydrogen-based energy. A critical issue is the need for practical systems for hydrogen storage, a problem that remains unresolved after several decades of exploration. In this context, the possibility of storing hydrogen in advanced carbon materials has generated considerable interest. But confirmation and a mechanistic understanding of the hydrogen-storage capabilities of these materials still require much work. Our previously published work on hydrogen uptake by alkali-doped carbon nanotubes cannot be reproduced by others. It was realized by us and also demonstrated by Pinkerton et al. that most of the weight gain was due to moisture, which the alkali oxide picked up from the atmosphere. Here we describe a different material system, lithium nitride, which shows potential as a hydrogen storage medium. Lithium nitride is usually employed as an electrode, or as a starting material for the synthesis of binary or ternary nitrides. Using a variety of techniques, we demonstrate that this compound can also reversibly take up large amounts of hydrogen. Although the temperature required to release the hydrogen at usable pressures is too high for practical application of the present material, we suggest that more investigations are needed, as the metal-N-H system could prove to be a promising route to reversible hydrogen storage.     

紫外光照射下钴钼杂多酸降解有机染料SRB

制备了不同配比的钴钼杂多酸（CoMox Heteropoly acids,CoMox）,在紫外光（λ≤387 nm）照射下,以有机染料酸性桃红（Sulforhodamine B,SRB）的光催化降解为探针反应,研究了CoMox杂多酸不同配比及用量和体系介质pH值对其降解行为的影响.结果表明,最佳配比的钴钼杂多酸为CoMo12,在pH=3.0,CoMo12用量为1.0 g/L时,对SRB降解效果最好.在紫外光照射下,CoMo12活化O2,3.5 h内SRB脱色率达到96%.通过紫外-可见吸收光谱（UV-vis absorption spectrum）,红外光谱（FTIR）和总有机碳（TOC）测定分析钴钼杂多酸对SRB的降解特性,同时采用苯甲酸荧光光度法跟踪测定降解过程中产生的活性氧化物种,表明CoMo12多酸对SRB的光催化降解过程主要涉及.OH氧化历程.     

多孔化改性对g-C3N4/CdS复合光催化剂制备及光催化活性的影响

以三聚氰胺盐酸盐为前驱体, 用高温缩聚方法制备多孔化改性的类石墨相氮化碳（pg-C₃N₄）材料; 用水热法制备CdS纳米中空微球, 用沉积法将pg-C₃N₄与CdS有效复合, 制备pg-C₃N₄/CdS复合光催化剂; 用X射线衍射(XRD)、 透射电子显微镜(TEM)、 Fourier变换红外光谱(FTIR)、 紫外可见光谱(UV Vis)、 荧光光谱及电化学阻抗谱对样品进行表征; 用可见光催化降解染料罗丹明B（RhB）对其光催化活性进行评价, 并给出pg-C₃N₄/CdS光催化降解RhB的机理. 结果表明： 石墨相氮化碳(g-C₃N₄)的多孔化改 性有利于其与CdS间形成紧密界面, 进而促进pg-C₃N₄/CdS光生电子 空穴的分离和传递, 有效提高了其光催化活性和稳定性.     

碳掺杂pg-C3N4的制备及其光催化性能研究

为了提高单一半导体材料的光催化活性,采用水热法制备高比表面积的多孔石墨相氮化碳(pg-C₃N₄),通过碳掺杂和金纳米粒子(AuNPs)负载对pg-C₃N₄进行改性得到Au/pg-C@C₃N₄复合纳米材料,并对复合材料的组成、微观结构和性能进行表征。结果显示,碳元素的引入并未破坏pg-C₃N₄原有的片层结构,但明显提高了pg-C₃N₄的比表面积（高达158.2 m²/g）;AuNPs引入基体后,AuNPs的等离子共振效应可显著提高基体对可见光的吸收和光生电子-空穴的分离效率;当AuNPs含量为0.5%（质量分数）时,复合纳米材料具有最佳的光催化性能（表观反应速率常数k=0.078 4 s^-1）。因此,通过碳掺杂和纳米Au负载改性pg-C₃N₄可制备高活性复合光催化剂,为今后进一步提高氮化碳基催化剂的催化活性提供了理论基础。     

CN_x薄膜的制备及电子结构

采用反应溅射方法制备了氮化碳薄膜,研究了反应气体压力、溅射功率对薄膜形成的影响,并用Ｘ射线电子能谱（ＸＰＳ） 和富里叶变换红外光谱（ＦＴＩＲ）对样品的电子结构进行了分析．结果表明：反应气体Ｎ２ 的压力太高或太低、溅射功率太大或太小,均不利于氮化碳膜的形成;在Ｎ２ 压力为８ Ｐａ、溅射功率为２００ Ｗ 时,薄膜的氮原子数分数得到最大值４１％ ;ＸＰＳ和ＦＴＩＲ分析结果揭示了膜中没有自由的Ｎ原子,所有的Ｎ原子均与Ｃ原子作用形成化学键,而且Ｃ Ｎ 单键、Ｃ Ｎ 双键、Ｃ Ｎ 三键共存．膜中Ｃ Ｈ 和Ｎ Ｈ 振动模式的存在,说明沉积在Ｓｉ 衬底上的氮化碳薄膜有较强的从空气中吸收氢的能力．     

纳米片层结构石墨相氮化碳的光催化活性及循环利用

以尿素为初始原料,用高温热解方法制备纳米片层结构的石墨相氮化碳(g-C_3N_4),并通过X射线衍射(XRD)、X光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)及Fourier变换红外光谱(FTIR)对样品的结构和形貌进行表征,用罗丹明对样品的光催化性能与循环催化性能进行测试.结果表明,g-C_3N_4纳米片具有较高的光催化活性及循环催化性能.     

TiO2光催化涂层的制备

采用溶胶-凝胶法制得了添加La2O3的改性TiO2微粉，用硅酸乙酯作粘结剂，将TiO2光催化涂层涂覆在载玻片上，讨论了TiO2含量(质量分数，下同)以及活性炭和沸石对涂层光催化活性的影响．发现：当涂层中TiO2的含量为70％时，涂层的光催化活性最好；活性炭和沸石都能提高涂层的光催化活性，且活性炭优于沸石，当活性炭的添加量为10％(质量分数)时效果最好．     

MXenes电催化析氢的研究进展

面向“碳达峰”“碳中和”国家重大战略,氢能作为一种能量密度高、无污染的绿色能源,将成为我国乃至世界未来能源战略领域发展的重中之重.电解水制氢由于其制备方法简单、制氢纯度高、制备过程无污染等优势而备受关注,但是该方法存在一个严重的缺陷,就是缺乏低成本、高效率析氢反应(HER)催化剂.MXenes是一种新兴的二维(2D)过渡金属碳化物、氮化物和碳氮化物,由于其具有极好的导电性、良好的亲水性、极大的比表面积、可调节的分子结构及多样的化学组成等优势,在析氢催化剂领域存在着潜在的巨大应用.该文总结了 MXenes制备、MXenes基电催化析氢性能调控策略及利用机器学习设计MXenes基析氢电催化剂面临的挑战和新的机遇.该文为今后开发新型高效的MXenes基析氢电催化剂,推动氢能的绿色制备提供了参考.     

掺氮TiO_2-活性炭复合吸附材料的制备与性能

通过浸渍法将制备的掺氮TiO2光催化剂负载到活性炭上制备掺氮TiO2-活性炭复合吸附材料,并对其吸附特性、可见光催化活性以及再生性能进行研究.结果表明:掺氮TiO2光催化剂具有较大的比表面积与良好的可见光吸收性能;活性炭对低浓度甲醛气体具有良好的吸附性能;掺氮TiO2的负载对活性炭颗粒的吸附性能影响甚微;掺氮TiO2-活性炭复合吸附材料具有优越的可见光再生性能,它实现了对低浓度挥发性有机化合物的吸附和光催化分解解耦,提高了活性炭的循环利用性能.     

光催化降解普萘洛尔的机理研究

普萘洛尔作为一种新型污染物，对环境和人类健康造成了很大的威胁，有效的去除普萘洛尔在环境中的残留成为日益关注的重点.本文采用密度泛函理论在B3LYP/6-31+G(d)水平上模拟了芬顿溶液中，光催化降解普萘洛尔的反应过程.研究结果表明，普萘洛尔的降解过程是羟基自由基加成在其萘环的不同碳位置上，再进行夺氢或者是C-O键断裂的反应，最后生成稳定的萘酚、对二萘酚、1,4-二萘酚和1,6-二萘酚，生成的主要产物与实验吻合，并从理论角度预测，实验中没有检测到的生成1,4-二奈酚的反应路径在理论上是可以发生的.     

石墨相氮化碳的制备及表征

采用高能球磨法, 以氮化锂和酰氯氰脲作为前驱物, 并在反应物中滴入少量丙酮制备石墨相氮化碳. 将获得物在真空条件下的管式炉中热处理, 制备出球形体材料.  XRD结果表明, 合成的样品为结晶的石墨相氮化碳.  FTIR和XPS给出合成的石墨相氮化碳内部氮原子和碳原子的主要键合状态.  通过透射电子显微镜分析可知, 合成样品主要由直径为200~300 nm的球形粒子组成.       

Bionic titania coating carbon multi-layer material derived from natural leaf and its superior photocatalytic performance

Bionic titania coating carbon multi-layer material was fabricated by employing canna leaves as substrate and carbon precursor. Titania nanocrystals were assembled and coated on the natural films. The carbonation treatment under pure N_2 atmosphere yielded the ultrathin multi-film hybrid material. The carbon layer was coated with small anatase titania crystallite(8–10 nm) and possessed a highly specific surface area of 248.3 m~2 g~(-1). Examination using UV–visible spectrophotometer(UV–vis) showed that the band gap of the multi-layer material was reduced to 2.75 eV, and the hydrogen production by photocatalytic splitting of water under visible light irradiation was about 302 μmol g~(-1) after six hour.     

Binder-free heterostructure(g-C_3N_4/PPy) based thin film on semi-flexible nickel foam via hybrid spray technique for energy storage application

A semi-flexible binder-free graphitic carbon nitride(g-C_3N_4) intercalated polypyrrole(PPy) nanocomposite thin film was prepared via hybrid electrospray technique. A homogeneous thin film was achieved by the controlled spray process. A deposited thin film illustrated the amorphous nature of composite with high surface purity and good chemical composition. The surface analysis confirmed the smoother surface with well-defined distinct phases of g-C_3N_4 and PPy matrix in the composite thin film. The electrochemical studies exhibited that a maximum areal capacity of the thin film was achieved to be 289.6 mF/cm~2 at a current density of 0.4 mA/cm~2,which is higher than that of pristine PPy(194.8 mF/cm~2). The heterostructure electrode illustrated that the life cycles of 99% could be up to 10,000 cycles with low resistance due to the synergetic effect of g-C_3N_4 and PPy matrix with strong material adhesion(hybrid spray process) on the surface. A binder-free heterostructure thin film will play a significant role in the energy storage application.     

Nano-sized graphitic carbon in authigenic tube pyrites from offshore southwest Taiwan,South China Sea,and its implication for tracing gas hydrate

Gas hydrates are a significant energy resource and are usually detected by bottom simulating reflection and submarine geochemical anomalies. Authigenic minerals are related to gas hydrates, with carbonates, sulfates and sulfides being important tracing minerals. Authigenic tubular pyrites were collected from offshore southwest Taiwan in the South China Sea, and were investigated by scanning electron microscopy(SEM) and high-resolution transmission electron microscopy (HRTEM). Authigenic tubular pyrite was composed of framboidal pyrite, within which nanosized graphitic carbon of low crystallinity was discovered. The graphitic carbon coexisted with pyrite and had a texture similar to carbon nanotubes and nanocones, indicating that they likely precipitated from carbon supersaturated C-H-O fluid. Pyrite may act as a catalyst for the conversion of CH 4 to C. The discovery of nanosized graphitic carbon in pyrite indicated it was deposited in sediments that were supersaturated with methane fluid. Thus, nanosized graphitic carbon may be another tracing species for submarine gas hydrates. The discovery of nanosized graphitic carbon deposited in a low temperature environment will enlighten our understanding of the laboratory synthesis and industrial production of graphitic carbon.     

Pt/C/聚砜型催化剂层的制备及性能研究

利用聚砜代替聚四氟乙烯,用循环伏安法,通过一步反应直接在高温裂解石墨(炭棒)电极上制备了Pt/C/聚砜型催化剂层.该催化剂层对甲醇的氧化呈现很好的电催化活性和稳定性,并系统研究了制备条件以及甲醇酸度、浓度对催化活性的影响.相对其他酸,在硫酸中电沉积所得Pt/C催化剂有更好的催化活性;催化剂的活性随甲醇溶液酸度的增加而增大;峰电流与甲醇浓度成正比.     

高温煅烧硫化镉光解水制氢

沉淀法制备的硫化镉经不同温度煅烧处理获得不同相的硫化镉光催化剂,采用X射线衍射、紫外-可见漫反射光谱表征催化剂的结构和性质.以制备的硫化镉粉体作为光催化剂,在存在空穴牺牲剂的条件下进行光解水制氢实验,研究了硫化镉晶体的相组成、牺牲剂种类和助催化剂的担载量对其光解水活性的影响.结果表明,400℃下焙烧的硫化镉具有最好的催化活性,乳酸作为牺牲剂更有利于硫化镉光解水制氢,助催化剂(铂)的担载量为0.1%时,硫化镉具有最高的光催化活性.