Enhanced catalytic activity of monodispersed AgPd alloy nanoparticles assembled on mesoporous graphitic carbon nitride for the hydrolytic dehydrogenation of ammonia borane under sunlight

We address the composition-controlled synthesis of monodispersed AgPd alloy nanoparticles (NPs),their assembly for the first time on mesoporous graphitic carbon nitride (mpg-C3N4),and the unprecedented catalysis of mpg-C3N4@AgPd in the hydrolytic dehydrogenation of ammonia borane (AB) at room temperature.Monodispersed AgPd alloy NPs were synthesized using a high-temperature organic-phase surfactant-assisted protocol comprising the co-reduction of silver(Ⅰ) acetate and palladium(Ⅱ) acetylacetonate in the presence of oleylamine,oleic acid,and 1-octadecene.This protocol allowed the synthesis of four different compositions of AgPd alloy NPs.The AgPd alloy NPs were then assembled on mpg-C3N4,reduced graphene oxide,and Ketjenblack using a liquid-phase self-assembly method.Among the three supports tested,the mpg-C3N4@AgPd catalysts provided the best activity because of the Mott-Schottky effect,which was driven by the favorable work function difference between mpg-C3N4 and the metal NPs.Moreover,the activity of the mpg-C3N4@AgPd catalyst was further enhanced by an acetic acid treatment (AAt),and a record initial turnover frequency of 94.1 mol(hydrogen)·mol(catalyst)-1·min-1 was obtained.Furthermore,the mpg-C3N4@Ag42Pd58-AAt catalyst also showed moderate durability for the hydrolysis of AB.This study also includes a wealth of kinetic data for the mpg-C3N4@AgPd-catalyzed hydrolysis of AB.     

Synthesis of boron carbon nitride oxide (BCNO) from urea and boric acid

A solid state synthesis of boron carbon nitride oxide (BCNO) material was carried out starting from urea and boric acid treated at 600°C. The X-ray diffraction pattern corresponded to amorphous BCNO with an interlayer distance of 3.49 Å. The material had a layered structure similar to that of graphite and hexagonal boron nitride (h-BN). Infrared spectroscopy (IR) showed bands which were similar to those typical of BN and carbon nitride. The presence of boron was also confirmed by energy dispersive spectroscopy in an amount compatible with the IR spectrum. The spectra obtained by X-ray photoelectron spectroscopy (XPS) corresponded to those of a BCNO family with a considerable content of oxygen too. The optical band gap was estimated to be 3.22 eV, typical of a wide band-gap semiconductor. The particle size was very dispersed from micro to nanosize. The material dispersed in polar solvents formed stable suspensions due to the presence of hydroxyl groups.     

具有三维网状结构的石墨相氮化碳/还原氧化石墨烯/钯复合材料的合成及可见光催化性能

石墨相氮化碳(g-C_3N_4)已经被认为是一种高效的非金属半导体光催化剂。为进一步优化其光催化性能,通过热解-水热两步法制备了三维网状结构的g-C_3N_4/还原氧化石墨烯(rGO)/钯纳米颗粒(Pd NPs)复合材料。该复合材料由大量超薄片组成,而且薄片上有大量直径约为10nm的Pd NPs。g-C_3N_4/rGO/Pd NPs复合材料展现了一个宽的可见光吸收(边~460nm),其在460~800nm波长范围内还有一个随波长增加的光吸收。经可见光(λ400nm)照射140 min后,g-C_3N_4/rGO/Pd NPs复合材料可降解90%罗丹明B(RhB)。此外,循环实验表明g-C_3N_4/rGO/Pd NPs复合材料具有良好的稳定性。因此,g-C_3N_4/rGO/Pd NPs复合材料有望成为一种高效稳定的光催化剂,在水污染处理领域具有潜在的应用价值。     

石墨相氮化碳的光催化改性及在环境污染物降解中的应用

石墨相氮化碳（g-C3N4）作为一种不含金属的绿色半导体材料,逐渐成为光催化领域的热门材料之一,在降解环境污染物方面表现出广阔的发展前景和应用潜力。首先,对g-C3N4光催化剂降解污染物的机理进行分析,并从形貌结构设计、金属/非金属掺杂、构建异质结3个方面对g-C3N4的光催化改性研究进行了阐述。其次,总结了在气体、土壤、水体3个不同环境下g-C3N4光催化剂降解污染物的应用研究。最后,对g-C3N4在包装领域的实际应用进行了展望。     

介孔石墨相氮化碳吸附材料在环境中的应用

石墨相氮化碳(Graphitic carbon nitride,g-C_3N_4)是一种由碳(C)和氮(N)元素组成的共轭聚合物材料,具有平面的三嗪聚合物(Poly(tri-s-triazine))网络结构。比起大部分其他碳材料,氮化碳是富电子体,因而赋予了其特殊的性质。然而目前对于g-C_3N_4的研究主要集中在其相关催化作用(光催化,电催化和光电催化),对于g-C_3N_4的吸附作用的研究相对很少涉及。本文探讨了g-C_3N_4材料在吸附领域中的应用,简要综述了G-C_3N_4的性质、制备方法及其作为吸附材料的应用现状,最后展望了石墨型氮化碳在吸附应用领域的未来发展方向。     

Photosynthesis of Hydrogen Peroxide Based on g‑C3N4: The Road of a Cost-Effective Clean Fuel Production

Emerging artificial photosynthesis promises to offer a competitive means for solar energy conversion and further solves the energy crisis facing the world. Hydrogen peroxide (H₂O₂), which is considered as a benign oxidant and a prospective liquid fuel, has received worldwide attention in the field of artificial photosynthesis on account of the source materials are just oxygen, water, and sunlight. Graphitic carbon nitride (g-C₃N₄)-based photocatalysts for H₂O₂ generation have attracted extensive research interest due to the intrinsic properties of g-C₃N₄. In this review, research processes for H₂O₂ generation on the basis of g-C₃N₄, including development, fabrication, merits, and disadvantages, and the state-of-the-art methods to enhance the performance are summarized after a brief introduction and the mechanism analysis of an efficient catalytic system. Also, recent applications of g-C₃N₄-based photocatalysts for H₂O₂ production are reviewed, and the significance of active sites and synthetic pathways are highlighted from the view of reducing barriers. Finally, this paper ends with some concluding remarks to reveal the issues and opportunities of g-C₃N₄-based photocatalysts for producing H₂O₂ in a high yield.     

Unravelling charge carrier dynamics in protonated g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> interfaced with carbon nanodots as co-catalysts toward enhanced photocatalytic CO<Subscript>2</Subscript> reduction: A combined experimental and first-principles DFT study

In this work,we demonstrated the successful construction of metal-free zerodimensional/two-dimensional carbon nanodot (CND)-hybridized protonated g-C3N4 (pCN) (CND/pCN) heterojunction photocatalysts by means of electrostatic attraction.We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis.The CND/pCN-3 sample with a CND content of 3 wt.％ showed the highest catalytic activity in the CO2 photoreduction process under visible and simulated solar light.Thisprocess results in the evolution of CH4 and CO.The total amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 μmol·gcatalyst-1,respectively.These values were 3.6 and 2.28 times higher,respectively,than the amounts generated when using pCN alone.The corresponding apparent quantum efficiency (AQE) was calculated to be 0.076％.Furthermore,the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles,with no significant decrease in the catalytic activity.The significant improvement in the photoactivity using CND/pCN-3 was attributed to the synergistic interaction between pCN and CNDs.This synergy allows the effective migration of photoexcited electrons from pCN to CNDs via wellcontacted heterojunction interfaces,which retards the charge recombination.This was confirmed by photoelectrochemical measurements,and steady-state and time-resolved photoluminescence analyses.The first-principles density functional theory (DFT) calculations were consistent with our experimental results,and showed that the work function of CNDs (5.56 eV) was larger than that of pCN (4.66 eV).This suggests that the efficient shuttling of electrons from the conduction band of pCN to CNDs hampers the recombination of electron-hole pairs.This significantly increased the probability of free charge carriers reducing CO2 to CH4 and CO.Overall,this study underlines the importance of understanding the charge carrier dynamics of the CND/pCN hybrid nanocomposites,in order to enhance solar energy conversion.     

固相反应法合成碳化硼纳米粉体

以六方氮化硼和炭黑(或石墨)为原料, 采用固相反应法合成了碳化硼粉体. 碳源、反应气氛和温度对粉体合成产生重要影响. 以炭黑为碳源, 在1900℃真空下保温5 h, 得到了平均粒径约为100 nm的碳化硼纳米粉体. 与商业粉体相比, 合成的粉体具有较好的烧结活性. 在2000℃/30 MPa/1 h条件下烧结, 样品的相对密度达到97.9%(商业粉体样品为93.1%), 这可归结于合成的粉体具有细小的粒径、低的氧含量和一定程度的孪晶结构.     

无机酸刻蚀多孔氮化碳的合成及光催化性能

通过合理的形貌调控使石墨相氮化碳(g-C_3N_4)低维化和多孔化,是提高其光催化活性的有效途径.采用高温煅烧方法制备了HCl、HNO_3和H_2SO_4刻蚀的g-C_3N_4,并对它们进行了结构形貌表征、形成机理探究和光催化降解罗丹明B测试,还给出了活性增强机理.结果显示:酸刻蚀g-C_3N_4具有和g-C_3N_4相同的基本晶体结构,但是呈薄片状,且表面出现了大量纳米孔,这些孔是由无机酸阻碍前驱体中N—H键参与热缩聚反应所致,按照HCl、HNO_3、H_2SO_4的顺序阻碍作用依次增强,对应的孔径依次增大,结构边缘(C)_2—N—H基团的XPS特征峰强度也依次增加;经过40 min光反应,g-C_3N_4和HCl、HNO_3、H_2SO_4刻蚀的g-C_3N_4对罗丹明B的降解率分别为45%、 56%、 52%和95%,H_2SO_4刻蚀的g-C_3N_4光催化活性最高;酸刻蚀引起的薄片和多孔结构不仅增加了g-C_3N_4的比表面积,促进了暗条件下对罗丹明B的吸附,还通过量子限域效应提高了其光吸收能力,拓宽了禁带宽度,有效促进了光生电荷的分离.因此,酸刻蚀克服了g-C_3N_4的缺点,为探寻其光催化活性的提高方法提供了有价值的启发.