构筑Cu配位结构光催化葡萄糖生产C1化学品

doi:10.1016/S1872-2067(24)60098-7

催化学报 ›› 2024, Vol. 63: 234-243.DOI: 10.1016/S1872-2067(24)60098-7

构筑Cu配位结构光催化葡萄糖生产C₁化学品

孙露露^a^,¹, 刘诗阳^a^,^b^,¹, 刘太丰^c^,^*(), 雷东强^b^,^d, 罗能超^a^,^*(), 王峰^a^,^b

^a中国科学院大连化学物理研究所, 大连洁净能源国家实验室, 催化基础国家重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049
^c河南大学, 纳米杂化材料应用技术国家地方联合工程研究中心, 纳米功能材料及其应用河南省协同创新中心, 河南开封 475004
^d中国科学院电工研究所, 北京 100190

收稿日期:2024-05-07 接受日期:2024-07-01 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子信箱: ncluo@dicp.ac.cn (罗能超),tfliu@vip.henu.edu.cn (刘太丰).
作者简介:
¹共同第一作者.
基金资助:
国家重点研发项目(2022YFA1504904);国家自然科学基金(22025206);国家自然科学基金(21991090);国家自然科学基金(22172157);大连市高层次人才创新支持计划(2022RG13);大连化物所创新研究基金(DICP I202116);中国科学院青年创新促进会(2023192);榆林学院-中国科学院洁净能源创新研究院联合基金(YLU-DNL基金2021019)

Engineering the coordination structure of Cu for enhanced photocatalytic production of C₁ chemicals from glucose

Lulu Sun^a^,¹, Shiyang Liu^a^,^b^,¹, Taifeng Liu^c^,^*(), Dongqiang Lei^b^,^d, Nengchao Luo^a^,^*(), Feng Wang^a^,^b

^aState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cNational & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials Collaborative Innovation Center of Nano Functional Materials and Applications of Henan Province, Henan University, Kaifeng 475004, Henan, China
^dInstitute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2024-05-07 Accepted:2024-07-01 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: ncluo@dicp.ac.cn (N. Luo), tfliu@vip.henu.edu.cn (T. Liu).
About author:
¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2022YFA1504904);National Natural Science Foundation of China(22025206);National Natural Science Foundation of China(21991090);National Natural Science Foundation of China(22172157);Dalian Innovation Support Plan for High Level Talents(2022RG13);DICP(Grant: DICP I202116);Youth Innovation Promotion Association (YIPA) of the Chinese Academy of Sciences(2023192);Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2021019)

摘要/Abstract

摘要：

生物质精炼可以选择性生产生物质基增值化学品和燃料. 其中, 木质纤维素作为重要的废弃生物质资源, 因其储量丰富且可再生, 成为制造化学品和燃料的主要原料. 然而, 在精炼过程中, 由于木质纤维素分子官能团的相似性和化学稳定性, 生成的中间体和产物容易重新缩合, 形成腐殖质等难以利用的物质. 利用半导体光催化产生的光生空穴可在室温下活化化学键, 自由基机制通过阻止碳正离子或碳负离子的形成, 从而避免缩合反应生成腐殖质等. 此前, 我们研究团队已实现Cu/TiO₂光催化多元醇和糖类分解为CO和H₂, 其中CO选择性高达90% (Nat. Commun., 2020, 11, 1083). 然而, Cu^δ⁺容易被还原成金属Cu, 导致活性结构消失. 因此, 稳定TiO₂上原子分散的Cu^δ⁺是光催化葡萄糖分解制C₁化学品的先决条件.

本文通过浸渍-焙烧的方法制备N掺杂的Cu/N-TiO₂, 促进光催化葡萄糖分解为C₁化学品(CO和甲酸)和H₂. X射线晶体衍射和球差校正高角环形暗场扫描透射电镜结果表明, N掺杂后在Cu/N-TiO₂上形成原子级分散的Cu位点. 以CO为探针分子, 通过傅里叶变换红外光谱对光照前后Cu/TiO₂和Cu/N-TiO₂中Cu的价态进行研究. 结果表明, 光照后Cu/TiO₂中部分Cu⁺被还原为Cu⁰, 但Cu/N-TiO₂催化剂通过N掺杂能够形成稳定Cu⁺的化学环境, 从而保持Cu⁺的价态. X射线光电子能谱结果表明, Cu/N-TiO₂中晶格N的结合能降低, 这可能是由于Cu‒N键的电子相互作用所致. 紫外-可见吸收光谱结果证明N掺杂促进由N 2p构成的缺陷能级的形成. 电子顺磁共振光谱结果揭示光照后Cu/TiO₂和Cu/N-TiO₂内部的电荷转移特性, 结果表明, Cu/TiO₂中光生空穴和电子分别迁移至O^2‒和Cu; 但Cu/N-TiO₂中光生空穴倾向于转移到与Cu原子有电子相互作用的间隙N处, 光生电子迁移到Ti⁴⁺处. 在光催化葡萄糖转化反应中, Cu/N-TiO₂能实现更高效光催化葡萄糖分解, 产生H₂和增值C₁化学品, 其产量分别为Cu/TiO₂的2.1倍和1.7倍. 理论计算结果进一步表明, 高活性源于N掺杂后Cu/TiO₂的价带和缺陷能级转变为含有N 2p的能带结构, 从而产生与Cu/TiO₂不同的氧化催化位点. 此外, 光电流测试和荧光光谱测试结果也说明N掺杂能够提高光生电荷分离效率, 促进光催化葡萄糖分解. 此外, Cu/N-TiO₂也可用于其他生物质资源包括甘油醛、果糖甚至二糖纤维二糖等的光催化分解. 以甘油醛为模型分子, 证明了在Cu/N-TiO₂催化作用下, 甘油醛经历脱羰过程产生乙醇醛自由基. 葡萄糖分解过程类似脱羰机理, C‒C键断裂产生CO和H₂. HCOOH很可能来自O‒H键断裂产生的氧为中心的自由基, 在水的帮助下转化为HCOOH和阿拉伯糖.

综上, 本文通过N掺杂促进Cu/TiO₂光催化葡萄糖分解为可持续的能量载体H₂和C₁化学品, Cu配位结构的形成促进电荷分离并捕获光生空穴以氧化葡萄糖, 为设计用于光催化生物质转化的稳定的Cu基催化剂提供了参考.

关键词: 铜催化剂, 配位结构, 生物质, C-C键, 碳一化学品

Abstract:

Photocatalytic decomposition of sugars is a promising way of providing H₂, CO, and HCOOH as sustainable energy vectors. However, the production of C₁ chemicals requires the cleavage of robust C-C bonds in sugars with concurrent production of H₂, which remains challenging. Here, the photocatalytic activity for glucose decomposition to HCOOH, CO (C₁ chemicals), and H₂ on Cu/TiO₂ was enhanced by nitrogen doping. Owing to nitrogen doping, atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO₂. The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit, distinct from undoped Cu/TiO₂. Therefore, the lifetime of charge carriers is prolonged, resulting in the production of C₁ chemicals and H₂ with productivities 1.7 and 2.1 folds that of Cu/TiO₂. This work provides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.

Key words: Cu photocatalyst, Coordination structure, Biomass, C-C bond, C₁ chemicals

孙露露, 刘诗阳, 刘太丰, 雷东强, 罗能超, 王峰. 构筑Cu配位结构光催化葡萄糖生产C₁化学品[J]. 催化学报, 2024, 63: 234-243.

Lulu Sun, Shiyang Liu, Taifeng Liu, Dongqiang Lei, Nengchao Luo, Feng Wang. Engineering the coordination structure of Cu for enhanced photocatalytic production of C₁ chemicals from glucose[J]. Chinese Journal of Catalysis, 2024, 63: 234-243.

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Fig. 1. Characterization of Cu/N-TiO2 catalyst in comparison to Cu/TiO2 and N-TiO2. (a) Representative XRD patterns of Cu/TiO2 and Cu/N-TiO2. (b) Representative TEM image of Cu/N-TiO2. (c) FTIR spectra of CO adsorbed on Cu/TiO2 and Cu/N-TiO2 before and after irradiation. (d) N 1s XPS spectra of N-TiO2 and Cu/N-TiO2. (e) X-band EPR spectra of Cu/TiO2 and Cu/N-TiO2 were recorded in the dark and under irradiation in Ar and at ?196 °C.

Fig. 2. Schematic diagram and time profiles of photocatalytic glucose decomposition to H2 and C1 chemicals. (a) Schematic diagram of photocatalytic decomposition of glucose. H2, C1 chemical and intermediates production over Cu/TiO2 (b) and Cu/N-TiO2 (c). (d) Performance of photocatalytic sugars and polyols decomposition to H2 and C1 chemicals over Cu/N-TiO2. Reaction conditions: 0.1 mmol of substrate, 0.1 mmol of water, 5 mg of photocatalyst, 1 mL of MeCN, 5 W LEDs (365 ± 5 nm), Ar.

Fig. 3. DOS and the contours of CBM and VBM of Cu1/TiO2 and Cu1/N-TiO2. The DOS of Cu1/TiO2 (a) and Cu1/N-TiO2 (b). The contours of CBM and VBM of Cu1/TiO2 (c) and Cu1/N-TiO2 (d). The contours in yellow around the atoms represent partial charge density.

Fig. 4. Influence of N on the photophysical properties of Cu/TiO2. Photocurrent density (a) and steady-state PL spectra (b) of Cu/N-TiO2 in contrast to TiO2, N-TiO2 and Cu/TiO2. (c) Schematic band diagram Cu/TiO2 and Cu/N-TiO2. Time-resolved PL kinetics recorded at an emission wavelength of 400 (d), 440 (e), and 550 nm (f).

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构筑Cu配位结构光催化葡萄糖生产C₁化学品

Engineering the coordination structure of Cu for enhanced photocatalytic production of C₁ chemicals from glucose

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