The utilization of solar energy is an epitome towards water splitting for hydrogen generation and environmental remediation. For efficient use of solar energy, photocatalysts capable of light-harvesting, with appropriate band energetics, that are inexpensive, stable, and scalable, are desired. Herein, a prototypical cyclotriphosphazene (P₃N₃)-based covalent inorganic–organic hybrid framework (CIOF) is designed with highly crosslinked aggregation that can produce hydrogen fuel from photocatalytic water splitting, as well as the degradation of industrial waste-water pollutant (rhodamine B). The P₃N₃-CIOF was synthesized by the aggregation, self-assembly, and subsequent polycondensation of hexachlorocyclotriphosphazene, tris(4-hydroxyphenyl)ethane and pyridine, in one-pot under ultrasonication. Morphology and structure of the newly synthesized P₃N₃-CIOF are characterized through scanning electron microscopy, Fourier transform infrared spectroscopy, solid-state ³¹P and ¹³C nuclear magnetic resonance spectroscopy, X-ray photoelectron microscopy, UV-visible absorbance, photoluminescence, and micro-spectrophotometry. The P₃N₃-CIOF shows selective response to the UV-visible light by emitting bright green (Ex. 365 nm), yellow (Ex. 420 nm), and red (Ex. 546 nm) colors. Moreover, the onset bandgap (2.14 eV) and the potential of the conduction band (−0.26 eV) and valence band (+1.88 eV) straddle the potential range for photocatalytic water splitting and dye degradation. The as-synthesized P₃N₃-CIOF continuously produced hydrogen fuel (24.5 μmol g⁻¹ h⁻¹) during photocatalytic water splitting for a period of 16 h, using Pt (3 wt%) and triethanolamine as the co-catalyst and holes scavenger, respectively. It also showed photodegradation ability to rhodamine B as a proxy dye to industrial waste-water pollutants. The plausible photocatalytic mechanism is also proposed based on the energetics of the photogenerated excitons, and scavenging experiments. These findings exemplify a critical first step towards photocatalytic hydrogen generation and remediation of organic pollutants through P₃N₃-CIOF, as well as motivation to engineer new materials based on aggregation-induced phenomena.

中文翻译：

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环三磷腈（P3N3）混合框架用于聚集诱导的罗丹明B的光催化氢释放和降解

太阳能的利用是水分解产生氢和环境修复的缩影。为了有效地利用太阳能，需要能够廉价，稳定且可扩展的具有适当的带能的光收集的光催化剂。在本文中，基于环三磷腈（P ₃ N ₃）的原型共价无机-有机杂化骨架（CIOF）设计为具有高度交联的聚集体，可以通过光催化水分解产生氢燃料，并降解工业废水（罗丹明B）。P ₃ N ₃通过将六氯环三磷腈，三（4-羟基苯基）乙烷和吡啶在超声波作用下一锅聚合，自组装和随后的缩聚反应合成-CIOF。通过扫描电子显微镜，傅立叶变换红外光谱，固态³¹ P和¹³ C核磁共振光谱，X射线光电子显微镜，紫外可见吸收，光致发光来表征新合成的P ₃ N ₃ -CIOF的形貌和结构。和微分光光度法。P ₃ N ₃-CIOF通过发出明亮的绿色（例如365 nm），黄色（例如420 nm）和红色（例如546 nm）颜色，显示出对紫外线可见光的选择性响应。此外，起始带隙（2.14 eV）以及导带（-0.26 eV）和价带（+1.88 eV）的电势跨越了光催化水分解和染料降解的电势范围。合成后的P ₃ N ₃ -CIOF连续产生的氢燃料（24.5μmolg ^-1 h ^-1）在光催化水分解过程中持续16 h，分别使用Pt（3 wt％）和三乙醇胺作为助催化剂和空穴清除剂。它还显示出将罗丹明B用作工业废水污染物的代用染料的光降解能力。基于光生激子的能量学和清除实验，提出了合理的光催化机理。这些发现说明了通过P ₃ N ₃ -CIOF进行光催化氢生成和有机污染物修复的关键的第一步，以及基于聚集诱导现象设计新材料的动机。