Boro Bishal, Kim Nayeong, Kim Jae-Seung, Paul Ratul, Nailwal Yogendra, Choi Yuri, Seo Dong-Hwa, Mondal John, Ryu Jungki
Department of Catalysis & Fine Chemicals, CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad 500 007, India; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India.
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea; Emergent Hydrogen Technology R&D Center, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
J Colloid Interface Sci. 2023 Dec 15;652(Pt B):1784-1792. doi: 10.1016/j.jcis.2023.09.002. Epub 2023 Sep 3.
Producing hydrogen peroxide (HO) from HO and O under visible light irradiation is a promising solar-to-chemical energy conversion technology. Hydrogen peroxide has versatile applications as a green oxidant and liquid energy carrier but has been produced through energy-intensive and complex anthraquinone processes. Herein, we report the rational design of efficient and stable porous organic polymer (POP) containing redox centers, anthraquinone photocatalyst (ANQ-POP) for solar HO production. ANQ-POP is readily synthesized with stable dioxin-linkages via efficient one-pot, transition-metal-free nucleophilic aromatic substitution reactions between 1,2,3,4,5,6,7,8-octafluoro-9,10-anthraquinone (OFANQ) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). Exhibiting a fibrillar morphology, ANQ-POP boasts a high surface area of 380 m∙g and demonstrates thermal stability. With 10 % ethanol, ANQ-POP yields an HO production rate of 320 μmol g under visible light irradiation. Moreover, ANQ-POP alone can efficiently produce HO without any photosensitizers and cocatalysts. Density functional theory calculations reveal that the quinone groups of the anthraquinone moieties can serve as redox centers for HO production under light irradiation. Furthermore, unlike most conventional photocatalysts, it can produce HO using only water and air by catalyzing both oxygen reduction and evolution reactions under light irradiation. Our findings provide an efficient, eco-friendly pathway for photocatalytic production of HO under mild reaction conditions using a dioxin-derived POP-based photocatalyst.
在可见光照射下由过氧化氢（HO）和氧气生成过氧化氢（HO）是一种很有前景的太阳能到化学能的转换技术。过氧化氢作为一种绿色氧化剂和液体能量载体具有多种用途，但一直是通过能源密集型和复杂的蒽醌工艺生产的。在此，我们报告了一种含有氧化还原中心的高效稳定多孔有机聚合物（POP）——蒽醌光催化剂（ANQ-POP）用于太阳能过氧化氢生产的合理设计。ANQ-POP通过1,2,3,4,5,6,7,8-八氟-9,10-蒽醌（OFANQ）与2,3,6,7,10,11-六羟基三亚苯（HHTP）之间高效的一锅法、无过渡金属亲核芳香取代反应，以稳定的二噁英键容易地合成。ANQ-POP呈现纤维状形态，具有380 m∙g的高比表面积并表现出热稳定性。在10%乙醇存在下，ANQ-POP在可见光照射下的过氧化氢产率为320 μmol g。此外，ANQ-POP单独就能高效地生产过氧化氢，无需任何光敏剂和助催化剂。密度泛函理论计算表明，蒽醌部分的醌基团可作为光照射下过氧化氢生产的氧化还原中心。此外，与大多数传统光催化剂不同，它在光照射下通过催化氧还原和析氧反应，仅使用水和空气就能生产过氧化氢。我们的研究结果提供了一条高效、环保的途径，可在温和反应条件下使用基于二噁英衍生的POP光催化剂光催化生产过氧化氢。
