g-C3N4及改性g-C3N4的光催化研究进展

聚合型半导体材料g-C3N4因其优异的物理性能和光电性能成为当今研究的热门材料。本文从结构分析和理论计算角度讨论了g-C3N4能够作为无金属催化剂的原因,综述了介孔g-C3N4、无机元素掺杂g-C3N4、金属负载g-C3N4、g-C3N4/金属氧化物复合物和有机改性g-C3N4等不同改性g-C3N4的制备和性质,着重分析了他们催化光解水析氢反应的机理、影响因素及研究进展,并阐述了今后的研究方向。     

硅藻土/g-C3N4/氧化石墨烯复合材料的制备及其光催化性能研究

采用半封闭一步热解方法,以三聚氰胺为前驱物制备g-C₃N₄,然后以圆筒状硅藻土(DE)为载体,合成DE/g-C₃N₄复合材料。并选取天然鳞片石墨为基本原料,运用Hummers法合成了氧化石墨烯(GO),在一定量的DE/g-C₃N₄粉末中加入不同质量分数的GO,得到DE/g-C₃N₄/GO三元复合光催化材料。通过SEM、BET、EDS、XRD、FT-IR对样品的晶体结构、形貌等进行表征,研究复合材料对罗丹明B溶液的光催化降解性能。结果表明,当GO的烯掺量为5%时,DE/g-C₃N₄/GO在可见光下,120min时,对RhB的降解率为93.74%,分别比DE/g-C₃N₄和g-C₃N₄提高了15.05%和31.03%。     

g-C3N4/BiOCl复合材料的制备及其光催化性能研究

高温缩聚法合成g-C₃N₄和水热法制备的BiOCl,在室温下通过简单的物理搅拌使片层状g-C₃N₄附着在菊花状的BiOCl上,控制g-C₃N₄的质量分数分别为5%、10%、15%、20%和25%,合成g-C₃N₄/BiOCl复合光催化剂。通过扫描电镜(SEM)、EDS能谱和BET比表面表征方法,揭示了g-C₃N₄/BiOCl复合光催化剂的微观结构;紫外-可见光(UV-Vis)结果显示g-C₃N₄/BiOCl可将光吸收范围延伸到可见光范围,其中BiOCl/CN-10具有更窄的禁带宽度;荧光光谱(PL)证实BiOCl/CN-10抑制光生载流子的复合能力最强;同时对g-C₃N₄/BiOCl降解染料废水罗丹明B(RhB)、亚甲基蓝(MB)和甲基橙(MO)的光催化能力进行了评估,结果表明g-C...     

g-C3N4基S型异质结的构建及其光催化性能研究

为了解决日益严重的环境污染和能源短缺等问题,基于半导体的光催化技术利用太阳能为环境修复和能源储存提供了一种“绿色”可持续的方案。首先介绍了g-C₃N₄的优点和局限性,以及S型半导体的优势与不足,接着介绍了g-C₃N₄基S型异质结的电子结构和光催化性质,综述了基于不同类型g-C₃N₄的S型异质结光催化材料构建和光催化性能的提升策略,并梳理了其部分应用。最后,综述了基于g-C₃N₄的S型异质结面临的挑战和未来发展趋势,有望为g-C₃N₄基S型异质结光催化材料的开发和实际应用提供重要的参考。     

可磁分离Fe3O4/g-C3N4复合材料的制备及其性能

为了利用Fe₃O₄的磁响应性及石墨相C₃N₄（g-C₃N₄）优良的光催化活性,首先采用高温热聚合法,以尿素为前驱体制备g-C₃N₄,然后采用水热法合成了可磁分离Fe₃O₄/g-C₃N₄复合材料。利用TEM、XRD、TGA、BET和振动样品磁强计（VSM）等多种测试手段表征分析Fe₃O₄/g-C₃N₄复合材料的形貌、晶型结构、比表面积、成分、饱和磁化强度等。通过模拟太阳光下Fe₃O₄/g-C₃N₄复合材料光催化吸附降解亚甲基蓝（MB）的实验,评价了Fe₃O₄/g-C₃N₄复合材料的吸附性能及光催化性能。结果表明,可磁分离Fe₃O₄/g-C₃N₄复合材料具有较大的比表面积,约为71.89 m²/g;且具有较好的磁性,饱和磁化强度为18.79 emu/g,可实现复合材料的分离回收;光照240 min时,Fe₃O₄/g-C₃N₄复合材料对MB的去除率为56.54%。所制备的Fe₃O₄/g-C₃N₄复合材料具有优良的吸附性能、光催化活性和磁性,并可通过外加磁场进行分离与回收。     

MOFs/g-C3N4复合光催化剂的研究进展

金属-有机框架材料(MOFs)和石墨相氮化碳(g-C₃N₄)在产氢、CO₂还原、Cr还原以及有机污染物降解方面表现出优异的光催化性能。将MOFs和g-C₃N₄结合构建二元或三元异质结,可以克服两种材料各自的缺点,进一步提高其材料在可见光或太阳光照射下的光催化性能。重点介绍了几种典型MOFs/g-C₃N₄复合材料的制备方法及其光催化性能,并展望了该研究领域发展前景和面临的挑战。     

WO3/g-C3N4复合光催化剂制备及其可见光催化性能

将自制层状石墨相氮化碳(g-C₃N₄)和WO₃纳米片均匀混合,经煅烧制备WO₃/g-C₃N₄复合半导体。利用XRD、SEM、TEM、UV-Vis DRS和PL对其进行表征。结果表明,g-C₃N₄呈现类石墨烯状片层结构,WO₃为纳米片状结构,且分散在g-C₃N₄表面;与WO₃复合后,UV-Vis吸收边发生了红移,拓宽了g-C₃N₄对可见光的响应。以罗丹明B(RhB)为模拟污染物,考察WO₃/g-C₃N₄的光催化降解性能。WO₃/g-C₃N₄质量比为1∶5时,表现出最佳的光催化活性,可见光照60 min后,RhB降解率可达到94.9%。光催化剂具有良好的稳定性,重复使用6次后,RhB的降解率依然达到88.9%。光催化机制研究表明,超氧自由基(·O₂?)是光催化降解RhB的主要活性物种。      

WS2/g-C3N4异质结光催化分解水制氢性能及机制

通过溶剂蒸发和二次高温煅烧石墨相碳化氮(g-C₃N₄)纳米片和WS₂纳米片混合物构建WS₂/g-C₃N₄异质结,该异质结保留g-C₃N₄和WS₂主体结构的同时,在界面处形成化学键,确保该异质结的化学稳定性和热稳定性。光催化分解水制氢实验表明,WS₂纳米片含量为3wt%时光催化制氢速率高达68.62 μmol/h,分别是g-C₃N₄纳米片和WS₂纳米片的2.53倍和15.29倍,表明异质结的构建可大幅提升g-C₃N₄的光催化性能,循环实验表明该异质结在5次循环实验后光催化性能没有明显下降,表明该异质结的稳定性较好。光电性能测试表明异质结的构建不仅提高激发电子的转移效率,同时抑制激发电子空穴的复合率,大幅提升激发电子的利用效率,致使光催化分解水制氢速率较g-C₃N₄纳米片和WS₂纳米片大幅提升。      

g-C3N4/POPs异质结制备及其可见光催化性能

光催化技术是一种极具应用前景的环境修复技术,开发高效、稳定、具有可见光响应的光催化剂是其研究的重点之一。本文采用常压溶剂热法,以1, 3, 5-三(4-氨基苯基)苯(TAPB)和2, 5-二甲氧基苯-1, 4二甲醛(DMTP)为单体合成的共轭多孔有机聚合物TAPB-DMTP POP为基底,原位负载不同比例的g-C₃N₄,制备g-C₃N₄/POPs复合光催化剂。通过XRD、FTIR、BET、TGA、UV-Vis DRS、电流-时间(i-t)和EIS等测试方法表征了g-C₃N₄/POPs的化学结构与光学特性。在可见光条件下,选择Cr(Ⅵ)为模型污染物探究了不同gC₃N₄负载量的g-C₃N₄/POPs光催化还原效率,并对pH值、催化剂用量和底物浓度等影响因素进一步探究。结果表明：在pH=2条件下,g-C₃N₄/POP-2表现出了最佳...     

g-C3N4量子点-TiO2/导电凹凸棒石复合材料的制备及其光催化性能

通过水热法在导电凹凸棒石(C-ATP)表面原位生长TiO₂纳米棒制得毛虫状结构的TiO₂/C-ATP复合材料,然后以TiO₂/C-ATP为载体,在TiO₂纳米棒表面进一步复合g-C₃N₄量子点(CNQD)成功制备了多级结构的CNQD-TiO₂/C-ATP异质结光催化材料。利用XRD、FTIR、SEM/TEM、紫外-可见吸收光谱(UV-Vis-DRS)、荧光发射光谱(PL)、BET比表面积分析仪和光电化学等技术对样品进行表征。在可见光照射下,考察了样品对盐酸四环素(TC)的光催化降解能力。结果表明:与TiO₂/C-ATP和CNQD相比,CNQD-TiO₂/C-ATP大幅提高了可见光响应、吸收能力和光生电子-空穴对的分离效率。当光照时间为120 min时,CNQD-TiO₂/C-ATP对TC去除率可达88%。      

Co@CNT复合电磁波吸收剂的制备及其吸波性能

以石墨相氮化碳(g-C₃N₄)和六水合硝酸钴为原料制备Co@CNT复合电磁波吸收剂,调节Co元素含量以提高其电磁波吸收性能。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱、扫描电镜(SEM)、能谱分析(EDS)和透射电镜(TEM)等手段表征其微结构和物相组成,使用矢量网络分析仪测量复合物电磁参数并进行Matlab模拟得到反射损耗图。结果表明,Co@CNT-1与石蜡质量比为1：3的材料,其吸波性能最优,厚度为4.1 mm时对电磁波的吸收最强,最小反射损耗(RL_min)为-45.5 dB;厚度仅为1.5 mm的材料,有效吸收带宽(RL<-10 dB)最大为4.42 GHz。     

Single Tungsten Atoms Supported on MOF‐Derived N‐Doped Carbon for Robust Electrochemical Hydrogen Evolution

Tungsten‐based catalysts are promising candidates to generate hydrogen effectively. In this work, a single‐W‐atom catalyst supported on metal–organic framework (MOF)‐derived N‐doped carbon (W‐SAC) for efficient electrochemical hydrogen evolution reaction (HER), with high activity and excellent stability is reported. High‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption fine structure (XAFS) spectroscopy analysis indicate the atomic dispersion of the W species, and reveal that the W₁N₁C₃ moiety may be the favored local structure for the W species. The W‐SAC exhibits a low overpotential of 85 mV at a current density of 10 mA cm^?2 and a small Tafel slope of 53 mV dec^?1, in 0.1 m KOH solution. The HER activity of the W‐SAC is almost equal to that of commercial Pt/C. Density functional theory (DFT) calculation suggests that the unique structure of the W₁N₁C₃ moiety plays an important role in enhancing the HER performance. This work gives new insights into the investigation of efficient and practical W‐based HER catalysts.     

Partial Sulphidation to Regulate Coordination Structure of Single Nickel Atoms on Graphitic Carbon Nitride for Efficient Solar H2 Evolution

To develop a non-precious highly efficient cocatalyst to replace Pt on graphitic carbon nitride (g-C₃N₄) for solar H₂ production is great significant, but still remains a huge challenge. The emerging single-atom catalyst presents a promising strategy for developing highly efficient non-precious cocatalyst owing to its unique adjustability of local coordination environment and electronic structure. Herein, this work presents a facile approach to achieve single Ni sites (Ni₁-N₂S) with unique local coordination structure featuring one Ni atom coordinated with two nitrogen atoms and one sulfur atom, confirmed by high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, and density functional theory calculation. Thanks to the unique electron structure of Ni₁-N₂S sites, the 1095 µmol g⁻¹ h⁻¹ of high H₂ evolution rate with 4.1% of apparent quantum yield at 420 nm are achieved. This work paves a pathway for designing a highly efficient non-precious transition metal cocatalyst for photocatalytic H₂ evolution.     

氮气压力对多孔氮化硅陶瓷显微组织和力学性能的影响

以α-Si₃N₄为原料, Y₂O₃为烧结助剂, 在三种不同的氮气压力(0.12、0.32和0.52 MPa)下烧结制备了多孔氮化硅陶瓷。研究了氮气压力对氮化硅的烧结行为、显微组织和力学性能的影响, 分别通过SEM观察显微组织并统计晶粒的长径比, 通过XRD对物相进行分析, 并对烧结试样进行三点弯曲强度测试。随着氮气压力的提高, 多孔陶瓷的线收缩率降低、气孔率提高, 这是由于低熔点的液相中N含量随氮气压力的提升而增加, 导致了液相粘度提高, 抑制陶瓷致密化。随着氮气压力的提高, 组织中的棒状β-Si₃N₄生长良好, 晶粒长径比增大, 其原因是高的液相粘度抑制了β-Si₃N₄形核, 有利于β-Si₃N₄生长。由于β-Si₃N₄棒状晶的作用, 陶瓷弯曲强度随氮气压力的升高得到改善, 但是气孔率的升高降低陶瓷的强度。在0.52 MPa的氮气压力下烧结的多孔陶瓷气孔率达58%, 弯曲强度为140 MPa。     

Embedding Ru Clusters and Single Atoms into Perovskite Oxide Boosts Nitrogen Fixation and Affords Ultrahigh Ammonia Yield Rate

Ammonia is a key chemical feedstock worldwide. Compared with the well-known Haber–Bosch method, electrocatalytic nitrogen reduction reaction (ENRR) can eventually consume less energy and have less CO₂ emission. In this study, a plasma-enhanced chemical vapor deposition method is used to anchor transition metal element onto 2D conductive material. Among all attempts, Ru single-atom and Ru-cluster-embedded perovskite oxide are discovered with promising electrocatalysis performance for ENRR (NH₃ yield rate of up to 137.5 ± 5.8 µg h⁻¹ mg_cat⁻¹ and Faradaic efficiency of unexpected 56.9 ± 4.1%), reaching the top record of Ru-based catalysts reported so far. In situ experiments and density functional theory calculations confirm that the existence of Ru clusters can regulate the electronic structure of Ru single atoms and decrease the energy barrier of the first hydrogenation step (*NN to *NNH). Anchoring Ru onto various 2D perovskite oxides (LaMO-Ru, MCr, Mn, Co, or Ni) also show boosted ENRR performance. Not only this study provides an unique strategy toward transition-metal-anchored new 2D conductive materials, but also paves the way for fundamental understanding the correlation between cluster-involved single-atom sites and catalytic performance.     

Artificial Photosynthesis with Polymeric Carbon Nitride: When Meeting Metal Nanoparticles,Single Atoms,and Molecular Complexes

Artificial photosynthesis for solar water splitting and CO₂ reduction to produce hydrogen and hydrocarbon fuels has been considered as one of the most promising ways to solve increasingly serious energy and environmental problems. As a well‐documented metal‐free semiconductor, polymeric carbon nitride (PCN) has been widely used and intensively investigated for photocatalytic water splitting and CO₂ reduction, owing to its physicochemical stability, visible‐light response, and facile synthesis. However, PCN as a photocatalyst still suffers from the fast recombination of electron‐hole pairs and poor water redox reaction kinetics, greatly restricting its activity for artificial photosynthesis. Among the various modification approaches developed so far, decorating PCN with metals in different existences of nanoparticles, single atoms and molecular complexes, has been evidently very effective to overcome these limitations to improve photocatalytic performances. In this Review article, a systematic introduction to the state‐of‐the‐art metal/PCN photocatalyst systems is given, with metals in versatility of nanoparticles, single atoms, and molecular complexes. Then, the recent processes of the metal/PCN photocatalyst systems in the applications of artificial photosynthesis, e.g., water splitting and CO₂ reduction, are reviewed. Finally, the remaining challenges and opportunities for the development of high efficiency metal/PCN photocatalyst systems are presented and prospected.     

Fe Isolated Single Atoms on S,N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction

Heteroatom‐doped Fe‐NC catalyst has emerged as one of the most promising candidates to replace noble metal‐based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular‐level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole–thiophene copolymer pyrolysis strategy to synthesize Fe‐isolated single atoms on sulfur and nitrogen‐codoped carbon (Fe‐ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe‐ISA/SNC shows a volcano‐type curve with the increase of sulfur doping. The optimized Fe‐ISA/SNC exhibits a half‐wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe‐isolated single atoms on nitrogen codoped carbon (Fe‐ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe‐ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X‐ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate‐limiting reductive release of OH* and therefore improved the overall ORR efficiency.     

Edge Coordination of Ni Single Atoms on Hard Carbon Promotes the Potassium Storage and Reversibility

Hard carbon is the most promising anode for potassium-ion batteries (PIBs) due to its low cost and abundance, but its limited storage capacity remains a major challenge. Herein, edge coordination of metal single atoms is proved to be an effective strategy for promoting potassium storage in hard carbon for the first time, taking B, N co-doped hard carbon nanotubes anchored by edge Ni-N₄-B atomic sites (Ni@BNHC) as an example. It is revealed that edge Ni-N₄-B can provide active sites for interlayer adsorption of K⁺ and that Ni atoms can facilitate the reversibility of K⁺ storage on N and B atoms. Furthermore, an unprecedentedly reversible K⁺ storage capacity of 694 mAh g⁻¹ at 0.05 A g⁻¹ is realized by introducing commercial carbon nanotubes. This work provides a new perspective for the application of single-atom engineering and the design of high-performance carbon anodes for PIBs.     

Achieving a Record‐High Yield Rate of 120.9 for N2 Electrochemical Reduction over Ru Single‐Atom Catalysts

The electrochemical reduction of N₂ into NH₃ production under ambient conditions represents an attractive prospect for the fixation of N₂. However, this process suffers from low yield rate of NH₃ over reported electrocatalysts. In this work, a record‐high activity for N₂ electrochemical reduction over Ru single atoms distributed on nitrogen‐doped carbon (Ru SAs/N‐C) is reported. At ?0.2 V versus reversible hydrogen electrode, Ru SAs/N‐C achieves a Faradaic efficiency of 29.6% for NH₃ production with partial current density of ?0.13 mA cm^?2. Notably, the yield rate of Ru SAs/N‐C reaches 120.9 , which is one order of magnitude higher than the highest value ever reported. This work not only develops a superior electrocatalyst for NH₃ production, but also provides a guideline for the rational design of highly active and robust single‐atom catalysts.