Developing isolated single metal ion coordinated by carbon nitrides for photocatalytic H2O2 production based on Time-Dependent Density Function Theory

基于瞬态密度函数理论开发氮化碳配位的孤立单金属离子用于光催化 H2O2 生产

• 批准号: 20J13064
• 负责人: 滕 鎮遠
• 金额: $ 1.22万
• 依托单位: Shinshu University (2021)Kyushu Institute of Technology (2020)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2020
• 资助国家: 日本
• 起止时间: 2020-04-24 至 2022-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-20J13064/
• 关键词: Photocatalysis; H2O2 production; Molecular engineering; Single-atom catalyst; Population analysis; Time-dependent DFT; photocatalysis; H2O2; carbon nitride; single-atom catalyst; charge seperation

We demonstrate a polarization engineering strategy by grafting (thio)urea functional groups onto covalent triazine frameworks (CTFs), giving rise to significantly promoted charge separation/transport and obviously enhanced proton transfer. Our calculation studies reveal the performance is attributed to the prominently enhanced 2-electron oxygen reduction reaction by improved charge separation and highly concentrated holes at the thiourea site.We also a prepared a flat and uniform polycrystalline Cu3BiS3 (CBS) thin film on a molybdenum-coated glass (Mo-SLG) by spray pyrolysis deposition for generation of hydrogen peroxide (H2O2). The photoelectrochemically (PEC) synthesis proceeds by an indirect 2e－ ORR initial formation of superoxide, which is disproportionate to H2O2.We calculated the water oxidation ability and its influence on photocatalytic oxidation of CH4 over symmetrically coordinated cobalt single-atom. It is revealed that the single-cobalt-atom PCN photocatalyst with 2N and 2C coordinated Co center possesses a desired electronic configuration for one electron transfer water oxidation reaction during photocatalysis.The activation of water for boosting the mass transfer of H to form H2O2 is found to be the rate-determined step during the 2e- ORR process on triazine sites. Taking SAC_Au-KPCN as an example, the overlap of K 4s and Au 5d orbitals generated a shallow-trapped energy level for accumulation of highly-concentrated holes at Au sites, thus leading to an significantly accelerated H2O activation and a remarkably boosted activity for H2O2 production.

我们展示了一种极化工程策略，通过接枝（硫）脲官能团到共价三嗪框架（CTF），引起显着促进电荷分离/传输和显着增强质子转移。我们的计算研究表明，这一性能归因于显著增强的2-电子氧还原反应，通过改善电荷分离和高度集中的空穴在硫脲位.我们还制备了一个平坦的和均匀的多晶Cu 3BiS 3（CBS）薄膜在镀膜玻璃（Mo-SLG）上产生过氧化氢（H2 O2）的喷雾热解沉积.光电化学反应（PEC）是通过间接的2 e-ORR初始生成与H_2O_2不成比例的超氧阴离子来进行的。计算了水的氧化能力及其对对称配位钴单原子光催化氧化甲烷的影响。结果表明，具有2N和2C配位Co中心的单钴原子PCN光催化剂具有理想的电子构型，可用于水的单电子转移氧化反应.水的活化是三嗪位上2 e-ORR过程中的速率控制步骤.以SAC_Au-KPCN为例，K4 s和Au 5d轨道的重叠产生了一个浅陷阱能级，使高浓度空穴聚集在Au位，从而显著加速了H2O的活化，并显著提高了H2 O2的生成活性.

项目成果

Photoexcited single metal atom catalysts for heterogeneous photocatalytic H2O2 production: Pragmatic guidelines for predicting charge separation

用于多相光催化 H2O2 生产的光激发单金属原子催化剂：预测电荷分离的实用指南

• DOI: 10.1016/j.apcatb.2020.119589
• 发表时间: 2021-03
• 期刊: Applied Catalysis B: Environmental
• 作者: Teng Zhenyuan;Cai Wenan;Sim Wenwen;Zhang Qitao;Wang Chengyin;Su Chenliang;Ohno Teruhisa
• 通讯作者: Ohno Teruhisa

Bandgap engineering of polymetric carbon nitride copolymerized by 2,5,8-triamino-tri-s-triazine (melem) and barbituric acid for efficient nonsacrificial photocatalytic H2O2 production

2,5,8-三氨基-三均三嗪（蜜勒姆）和巴比妥酸共聚聚合氮化碳的带隙工程，用于高效非牺牲光催化 H2O2 生产

• DOI: 10.1016/j.apcatb.2020.118917
• 发表时间: 2020-08
• 期刊: Applied Catalysis B: Environmental
• 作者: Teng Zhenyuan;Cai Wenan;Liu Sixiao;Wang Chengyin;Zhang Qitao;Su Chenliang;Ohno Teruhisa
• 通讯作者: Ohno Teruhisa

Carbon nitride-based monoatomic dispersed antimony catalysts for photosynthesis of hydrogen peroxide

用于过氧化氢光合作用的氮化碳基单原子分散锑催化剂

• 发表时间: 2021
• 作者: Hwang Sung Hwa;Koga Kazunori;Hao Yuan;Attri Pankaj;Okumura Takamasa;Kamataki Kunihiro;Itagaki Naho;Shiratani Masaharu;Oh Jun-Seok;Takabayashi Susumu;Nakatani Tatsuyuki;Zhenyuan Teng; Chenliang Su; Bin Liu; Teruhisa Ohno
• 通讯作者: Zhenyuan Teng; Chenliang Su; Bin Liu; Teruhisa Ohno

Carbon nitride-based atomically dispersed antimony catalysts for photosynthesis of hydrogen peroxide

用于过氧化氢光合作用的氮化碳基原子分散锑催化剂

• 发表时间: 2021
• 作者: Daichi Iijima;Atsushi Kobayashi;Gen Morimoto;Masami Hasegawa;Seiya Abe & Masashi Murakami;Yoshikawa Daichi;Zhenyuan Teng; Chenliang Su; Bin Liu; Teruhisa Ohno
• 通讯作者: Zhenyuan Teng; Chenliang Su; Bin Liu; Teruhisa Ohno

Atomically Dispersed Antimony Boosts Oxygen Reduction and Water Oxidation

原子分散的锑促进氧还原和水氧化

• 发表时间: 2020
• 作者: Zhenyuan Teng;Teruhisa Ohno
• 通讯作者: Teruhisa Ohno