基于Cu/TiO2/C-Wood复合材料的聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系

doi:10.11949/0438-1157.20211385

摘要/Abstract

摘要：

利用储量丰富且易获得的太阳能和海水资源为人类提供可持续的清洁能源是一项具有深远影响的探索。在本工作中，设计合成了一种自漂浮复合材料（Cu/TiO₂/C-Wood），该材料具有高效的毛细输液、全光谱太阳能光热转化及光-热协同催化能力，可通过快速的界面相转移过程实现太阳能驱动海水汽化与水蒸气催化分解制氢的一步协同增效反应。其中，具有大量微通道和极轻质量的碳化木（C-Wood）作为漂浮载体，通过毛细作用将液态水快速输送至局部升温的C-Wood表面，借助高效光热转化过程使海水汽化脱盐，同时负载等离子金属Cu的TiO₂纳米粒子作为催化活性组分触发水蒸气光-热协同催化分解制氢反应，从而实现太阳能驱动高效海水汽化催化分解制氢。实验结果表明：该复合材料在15 kW·m^-2的光照条件下，产氢速率达到179 μmol·h^-1·cm^-2（35.8 mmol·h^-1·g^-1），且在循环利用5次后产氢速率仍基本保持不变。更重要的是，通过聚光太阳能和自漂浮毛细输液条件的共同作用，可以获得海水中主要成分氯化钠对产氢性能的显著促进，从而打破了海水制氢技术一直以来面临的氯离子副作用瓶颈问题，证实了聚光太阳能驱动自漂浮高效光热协同催化体系在规模化、绿色、可持续太阳能海水制氢中的应用潜力。

关键词: 聚光太阳能, 自漂浮, 汽化, 光-热协同催化, 海水制氢

Abstract:

Utilizing abundant and readily available solar and seawater resources to provide sustainable and clean energy to mankind is a far-reaching exploration. In this work, we have designed and synthesized the self-floating solar photothermal composite (Cu/TiO₂/C-Wood) that possesses efficiently full-spectrum solar energy capture and photothermic properties for highly targeted interfacial phase transition reactions that are synergistically favorable for both seawater desalination and hydrogen production. Among them, carbonized wood with abundant microchannel and extremely light mass is used as self-floating carrier to rapidly transports liquid water to localized heating interface by capillary and photothermal effects to achieve effective seawater desalination and water steam production. The plasmonic Cu loaded TiO₂ nanoparticles as catalytic active components trigger surface-dominated photothermally catalytic hydrogen evolution of water steam, realizing the dual-function seawater desalination and synergistic hydrogen production. The hydrogen evolution rate of Cu/TiO₂/C-Wood composite is 179 μmol·h^-1·cm^-2 (35.8 mmol·h^-1·g^-1) under 15 kW·m^-2 and remains basically unchanged after being used 5 times. More importantly, the experimental results show that the main component in seawater-sodium chloride can promote the hydrogen production performance by synergistically concentrated irradiation and self-floating phase transfer process, which breaks the bottleneck of seawater hydrogen production technology, confirming the promising application potential of the self-floating two-phase photo-thermo-catalytic system in large-scale, green and sustainable solar hydrogen production from seawater.

Key words: concentrated solar energy, self-floating, evaporation, synergistic photo-thermo-catalysis, seawater hydrogen production

中图分类号:

TQ 116.2

马荣, 孙杰, 李东辉, 魏进家. 基于Cu/TiO₂/C-Wood复合材料的聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系[J]. 化工学报, 2022, 73(4): 1695-1703.

Rong MA, Jie SUN, Donghui LI, Jinjia WEI. Self-floating high-efficient evaporative catalytic seawater hydrogen production system driven by concentrated solar energy based on Cu/TiO₂/C-Wood composite[J]. CIESC Journal, 2022, 73(4): 1695-1703.

图/表 14

图1 聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系

Fig.1 Self-floating high-efficient evaporative catalytic seawater hydrogen production system driven by concentrated solar energy

图2 Cu/TiO2纳米粒子的XPS谱图全波长扫描图(a)；Cu 2p谱图(b)；CuLMM谱图(c)

Fig. 2 XPS spectra of Cu/TiO2 nanoparticles (a); high-resolution spectrum of Cu 2p (b); CuLMM spectrum (c)

图3 TiO2纳米粒子(a)和Cu/TiO2纳米粒子(b)的XRD谱图

Fig.3 XRD patterns of TiO2 (a) and Cu/TiO2 nanoparticles (b)

图4 C-Wood (a)和Cu/TiO2/C-Wood (b)的SEM图；Cu/TiO2/C-Wood的C、Ti、O和Cu的元素分布[(c)~(f)]

Fig.4 SEM images of C-Wood (a) and Cu/TiO2/C-Wood (b); Elemental mappings of Cu/TiO2/C-Wood for C, Ti, O and Cu elements [(c)—(f)]

图5 Cu/TiO2/C-Wood材料的未碳化表面(a)和碳化表面(b)的接触角图像；Cu/TiO2/C-Wood材料在模拟海水中的自漂浮电子照片(c)

Fig.5 Contact angle images of Cu/TiO2/C-Wood on non-carbonized surface (a) and carbonized surface (b); Photographs of self-floating Cu/TiO2/C-Wood on synthetic seawater (c)

图6 TiO2(a)，Cu/TiO2(b)和Cu/TiO2/C-Wood(c)的UV-VIS-IR 漫反射光谱图

Fig.6 UV-VIS-IR diffuse reflectance spectra of TiO2 (a), Cu/TiO2 (b) and Cu/TiO2/C-Wood (c)

图7 TiO2和Cu/TiO2的PL光谱图

Fig.7 PL spectra of TiO2 and Cu/TiO2

图8 Cu/TiO2纳米粒子掺杂质量与Cu/TiO2/C-Wood产氢速率的关系

Fig.8 Mass-loading of Cu/TiO2 against hydrogen evolution rate of Cu/TiO2/C-Wood

图9 本文提出的太阳能海水制氢体系循环实验

Fig.9 Cycling tests of proposed solar-driven seawater hydrogen evolution system

图10 产氢速率与光强的关系

Fig.10 Hydrogen evolution rate against irradiance

图11 Cu/TiO2/C-Wood表面温度与光强的关系

Fig.11 Surface temperature of Cu/TiO2/C-Wood against irradiance

图12 15 kW·m-2光照下添加氯化钠和不添加氯化钠时的产氢速率比较

Fig.12 Hydrogen evolution rate under 15 kW·m-2 irradiation with or without NaCl

图13 添加/不添加氯化钠条件下氢气生成量与时间的关系

Fig.13 Hydrogen evolution against reaction time under 15 kW·m-2 irradiance with/without NaCl

图14 1 kW·m-2光照下添加/不添加氯化钠时的氢气生成量与时间的关系

Fig.14 Hydrogen evolution against reaction time under 1 kW·m-2 irradiance with/without NaCl

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基于Cu/TiO₂/C-Wood复合材料的聚光太阳能驱动自漂浮高效海水汽化催化分解制氢体系

Self-floating high-efficient evaporative catalytic seawater hydrogen production system driven by concentrated solar energy based on Cu/TiO₂/C-Wood composite

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