Enhanced H2O2 Production via Photocatalytic O2 Reduction over Structurally-Modified Poly(heptazine imide)
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ABSTRACT:
SUBMITTER: Sharma P
PROVIDER: S-EPMC9245186 | biostudies-literature | 2022 Jun
REPOSITORIES: biostudies-literature
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Project description:Potassium poly (heptazine imide) (K-PHI), a crystalline two-dimensional carbon-nitride material, is an active photocatalyst for water splitting. The potassium ions in K-PHI can be exchanged with other ions to change the properties of the material and eventually to design the catalysts. We report here the electronic structures of several ion-exchanged salts of K-PHI (K, H, Au, Ru, and Mg) and their feasibility as water splitting photocatalysts, which were determined by density functional theory (DFT) calculations. The DFT results are complemented by experiments where the performances in the photocatalytic hydrogen evolution reaction (HER) were recorded. We show that due to its narrow band gap, Ru-PHI is not a suitable photocatalyst. The water oxidation potentials are straddled between the band edge potentials of H-PHI, Au-PHI, and Mg-PHI; thus, these are active photocatalysts for both the oxygen and hydrogen evolution reactions, whereas K-PHI is active only for the HER. The experimental data show that these are active HER photocatalysts, in agreement with the DFT results. Furthermore, Mg-PHI has shown remarkable performance in the HER, with a rate of 539 μmol/(h·g) and a quantum efficiency of 7.14% at 410 nm light irradiation, which could be due to activation of the water molecule upon adsorption, as predicted by our DFT calculations.
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Project description:Photo-stimuli response in materials is a fascinating feature with many potential applications. A photoresponsive gel of poly(heptazine imide), PHI, termed PHIG, exhibits photochromism, photoconductivity, and photo-induced charge accumulation, and is generated using ionic liquids and PHI. Although there are several examples of ionic liquid gels that exhibit photochromism and photoconductivity, this is the first report of an ionic liquid gel that exhibits both these properties as well as charge accumulation. We conducted experimental and theoretical investigations to understand the mechanism of the photostimulus response of PHIG, especially charge accumulation. The proposed model explains both the mechanism of charge accumulation and dark photocatalysis by PHI and provides new concepts in the field of photofunctional materials.
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Project description:The photocatalytic conversion of soluble U(VI) into insoluble U(IV) is a robust strategy to harvest aqueous uranium, but remains challenging owing to the intermittent availability of solar influx and reoxidation of U(IV) without illumination. Herein, a dual platform based on K+ and cyano group co-decorated poly(heptazine imide) (K-CN-PHI) is reported that can drive persistent U(VI) extraction upon/beyond light. K-CN-PHI achieves the photocatalytic reduction of U(VI) with a reaction rate of 0.89 min-1 , being 47 times greater than that over pristine carbon nitride (PCN). This system can further be triggered by light to form long-living radicals, driving the reduction of U(VI) in the dark for over 3 d. The flexible structural K+ as counterions stabilize the electrons trapped by cyanamide groups, enabling the long lifetime of the generated radicals. The results collectively prove K-CN-PHI to be a novel and efficient photocatalyst enabling persistent U(VI) extraction around the clock, and broadening the practical applications of the photocatalytic extraction of U(VI).
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Project description:Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one-light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
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Project description:The development of heterogeneous metallaphotocatalysis is of great interest for sustainable organic synthesis. The rational design and controllable preparation of well-defined (site-isolated) metal/photo bifunctional solid catalysts to meet such goal remains a critical challenge. Herein, we demonstrate the incorporation of privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI). A variety of PHI-supported cationic bipyridyl-based Ni-catalysts (LnNi-PHI) have been prepared and fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM and XAS. The LnNi-PHI catalysts exhibit exceptional chemical stability and recyclability in diverse C-P, C-S, C-O and C-N cross-coupling reactions. The proximity and cooperativity effects in LnNi-PHI significantly enhances the photo/Ni dual catalytic activity, thus resulting in low catalyst loadings and high turnover numbers.
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Project description:Photocatalysis provides a sustainable pathway to produce the consumer chemical H2O2 from atmospheric O2 via an oxygen reduction reaction (ORR). Such an alternative is attractive to replace the cumbersome traditional anthraquinone method for H2O2 synthesis on a large scale. Carbon nitrides have shown very interesting results as heterogeneous photocatalysts in ORR because their covalent two-dimensional (2D) structure is believed to increase selectivity toward the two-electron process. However, an efficient and scalable application of carbon nitrides for this reaction is far from being achieved. Poly(heptazine imides) (PHIs) are a more powerful subgroup of carbon nitrides whose structure provides high crystallinity and a scaffold to host transition-metal single atoms. Herein, we show that PHIs functionalized with sodium and the recently reported fully protonated PHI exhibit high activity in two-electron ORR under visible light. The latter converted O2 to up to 1556 mmol L-1 h-1 g-1 H2O2 under 410 nm irradiation using inexpensive but otherwise chemically demanding glycerin as a sacrificial electron donor. We also prove that functionalization with transition metals is not beneficial for H2O2 synthesis, as the metal also catalyzes its decomposition. Transient photoluminescence spectroscopy suggests that H-PHIs exhibit higher activity due to their longer excited-state lifetime. Overall, this work highlights the high photocatalytic activity of the rarely examined fully protonated PHI and represents a step forward in the application of inexpensive covalent materials for photocatalytic H2O2 synthesis.
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Project description:The photocatalytic degradation of pollutants is an effective
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Project description:In photocatalysis, small organic molecules are converted into desired products using light responsive materials, electromagnetic radiation, and electron mediators. Substitution of low molecular weight reagents with redox active functional materials may increase the utility of photocatalysis beyond organic synthesis and environmental applications. Guided by the general principles of photocatalysis, we design hybrid nanocomposites composed of n-type semiconducting potassium poly(heptazine imide) (K-PHI), and p-type conducting poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as the redox active substrate. Electrical conductivity of the hybrid nanocomposite, possessing optimal K-PHI content, is reversibly modulated combining a series of external stimuli ranging from visible light under inert conditions and to dark conditions under an O2 atmosphere. Using a conductive polymer as the redox active substrate allows study of the photocatalytic processes mediated by semiconducting photocatalysts through electrical conductivity measurements.
| S-EPMC8048452 | biostudies-literature
Project description:Polymeric carbon nitride materials have been used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI)-a benchmark carbon nitride material in photocatalysis-by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K-PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet-triplet intersystem crossing. We utilized the K-PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1 O2 ) as a starting point to synthesis up to 25 different N-rich heterocycles.
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Project description:5-hydroxymethylfurfural (HMF) oxidation in aqueous media using visible photocatalysis is a green and sustainable route for the valorization of lignocellulosic biomass derivatives. Several semiconductors have already been applied for this purpose; however, the use of Poly(heptazine imides), which has high crystallinity and a special cation exchange property that allows the replacement of the cation held between the layers of C3N4 structure by transition metal ions (TM), remains scarce. In this study, PHI(Na) was synthesized using a melamine/NaCl method and used as precursor to prepare metal (Fe, Co, Ni, or Cu)-doped PHI catalysts. The catalysts were tested for selective oxidation of HMF to 2,5-diformylfuran (DFF) in water and O2 atmosphere under blue LED radiation. The catalytic results revealed that the 0.1 wt% PHI(Fe) catalyst is the most efficient photocatalyst while higher Fe loading (1 and 2 wt%) favors the formation of Fe3+ clusters, which are responsible for the drop in HMF oxidation. Moreover, the 0.1 wt% PHI(Fe) photocatalyst has strong oxidative power due to its efficiency in H2O2 production, thus boosting the generation of nonselective hydroxyl radicals (●OH) via different pathways that can destroy HMF. We found that using 50 mM, the highest DFF production rate (393 μmol·h-1·g-1) was obtained in an aqueous medium under visible light radiation.
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