基于S-型光催化机制CuInS2内嵌中空凹面氮化碳光催化分解H2O制H2

doi:10.1016/S1872-2067(19)63490-X

摘要/Abstract

摘要： 光催化解离H₂O合成H₂是绿色可再生的太阳能光子能量转换策略之一.目前，增强光催化材料对太阳能光子的捕获并将之有效利用仍然是一个具有挑战性的课题.光催化解离H₂O反应包括三个过程：太阳能光子能量促使光生电子在半导体材料带隙中的跃迁；光生电子定向传输；光生电子与吸附在半导体材料表面的H₂O分子发生反应.第一过程需要强的太阳光子捕获能力以产生足够的光生载流子；第二、三过程在动力学上反映了光生载流子在各个竞争过程中能否有效利用的问题，如光生电子迁移与H₂O作用的速度很慢（~μs），而电子与空穴的复合速度快（~ps）.目前研究者很难协调半导体材料的电学和光学特性以满足光生载流子在热力学和动力学两方面的要求.g-C₃N₄是由C、N原子通过sp²杂化组成的二维π共轭体系.当g-C₃N₄结构偏离二维平面时，共轭体系的π电子由凹面迁移到凸面，促使凹、凸面形成表观电势差，有利于电子的定向传输.本文通过卷曲sp²杂化离域均三嗪体系偏离二维平面，得到空心凹面g-C₃N₄结构，便捷地优化了半导体的电子结构.将CuInS₂嵌入生长于空心g-C₃N₄的凹面，所构成的半导体光催化材料CuInS₂@C₃N₄展现了增强的光捕获能力，以及电子定向传输转移能力.结合XPS、光电流测试、电化学阻抗谱、稳态及瞬态荧光等表征手段揭示空心g-C₃N₄凹、凸面表观电势差驱动光生电子以S-型光催化作用机制从CuInS₂的Cu 2p向g-C₃N₄的N 1s的路径转移.因而，所构建的CuInS₂@C₃N₄在可见光激发下产氢效率提高到373μmol·h^-1·g^-1，其产氢效率分别是二维平面g-C₃N₄负载1 wt% Pt和3 wt% Pd效率的1.57倍和1.35倍，表明空心g-C₃N₄凹、凸面电势差可以显著地促进光生电子分离和利用率，从而提高光催化解离水制氢效率.本文可增强g-C₃N₄的可持续太阳能转换性能，也适用于其他半导体材料以替代贵金属光催化体系，降低光催化产氢技术成本，促进光催化技术的应用.

关键词: 空心氮化碳, 产氢, 太阳光吸收, 电子定向传输, 表观电势差

Abstract: It is still a great challenge to effectively optimize the electronic structure of photocatalysts for the sustainable and efficient conversion of solar energy to H₂ energy. To resolve this issue, we report on the optimization of the electronic structure of hollow-concave carbon nitride (C₃N₄) by deviating the sp²-hybridized structure of its tri-s-triazine component from the two-dimensional plane. The embedded CuInS₂ into C₃N₄ (CuInS₂@C₃N₄) demonstrates an increased light-capturing capability and the promoted directional transfer of the charge carrier. Research results reveal that the hollow structure with an apparent potential difference between the concave and convex C₃N₄ drives the directional transfer of the photoinduced electrons from the Cu 2p orbital of CuInS₂ to the N 1s orbital of C₃N₄ with the S-scheme principle. The H₂ evolution efficiency over CuInS₂@C₃N₄ is up to 373 µmol?h^-1 g^-1 under visible irradiation, which is 1.57 and 1.35 times higher than those over the bulk g-C₃N₄ with 1 wt% Pt (238 µmol?h^-1 g^-1) and g-C₃N₄ with 3 wt% Pd (276 µmol?h^-1 g^-1), respectively. This suggests that the apparent potential difference of the hollow C₃N₄ results in an efficient reaction between the photogenerated electrons and H₂O. This work supplies a new strategy for enhancing the sustainable solar conversion performance of carbon nitride, which can also be suitable for other semiconductors.

Key words: Hollow carbon nitride, Hydrogen evolution, Solar light absorption, Directional charge transfer, Apparent potential difference

罗金华, 林哲荇, 赵艳, 姜淑娟, 宋少青. 基于S-型光催化机制CuInS₂内嵌中空凹面氮化碳光催化分解H₂O制H₂[J]. 催化学报, 2020, 41(1): 122-130.

Jinhua Luo, Zhexing Lin, Yan Zhao, Shujuan Jiang, Shaoqing Song. The embedded CuInS₂ into hollow-concave carbon nitride for photocatalytic H₂O splitting into H₂ with S-scheme principle[J]. Chinese Journal of Catalysis, 2020, 41(1): 122-130.

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基于S-型光催化机制CuInS₂内嵌中空凹面氮化碳光催化分解H₂O制H₂

The embedded CuInS₂ into hollow-concave carbon nitride for photocatalytic H₂O splitting into H₂ with S-scheme principle

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