高效空穴转移助力光催化碱性甲醇-水溶液制氢

doi:10.11949/0438-1157.20240968

摘要/Abstract

摘要：

安全储氢和高效制氢是实现氢能大规模应用的关键。利用甲醇作为储氢介质，并通过光能驱动甲醇-水重整制氢以实现温和连续现场制氢是促进氢能利用的一种有效途径。然而，缓慢的空穴转移和甲醇脱氢氧化速率成为限制光催化甲醇-水溶液制氢性能的瓶颈。基于催化剂纳米结构调控，通过构筑长径纳米棒Zn_0.5Cd_0.5S（ZCS-LNR）加快光生载流子分离和迁移速率，并通过引入NaOH碱性介质，利用OH^-的快速活化和·OH的高效脱氢能力，以OH^-/·OH氧化还原对加快催化剂表面空穴转移和甲醇氧化脱氢速率，实现了高性能的碱性甲醇-水溶液制氢过程。其中ZCS-LNR催化剂在室温、1.0 W/cm²光强、4 mol/L NaOH以及CH₃OH∶H₂O体积比为1∶1的条件下可获得54.33 mmol/（g·h）的产氢速率。为实现光催化甲醇-水溶液制氢过程提供了一种高效可行的新路径。

关键词: 催化剂, 制氢, 纳米结构, 甲醇-水重整, 空穴转移

Abstract:

Safe hydrogen storage and efficient hydrogen production are critical challenges for the large-scale application of hydrogen energy. Utilizing methanol as a hydrogen storage medium and achieving mild continuous on-site hydrogen production through photo-driven methanol-water reforming is an effective approach for utilizing hydrogen energy. However, slow hole transfer kinetics and methanol dehydrogenation oxidation rate are bottlenecks that limit the performance of photocatalytic hydrogen production from methanol aqueous solution. Herein, based on the regulation of catalyst nanostructures, we constructed one-dimensional long diameter nanorod-like Zn_0.5Cd_0.5S (ZCS-LNR) photocatalyst to accelerate the photogenerated charge carrier separation and migration efficiency. By introducing NaOH alkaline medium, the rapid activation of OH^- and efficient dehydrogenation ability of ·OH are harnessed to facilitate surface hole transfer and enhance the rate of methanol oxidation dehydrogenation through the OH^-/·OH redox couple, thereby achieving high-performance hydrogen production from an alkaline methanol aqueous solution. Among them, the ZCS-LNR catalyst can obtain a hydrogen production rate of 54.33 mmol/(g·h) under the conditions of room temperature, 1.0 W/cm² light intensity, 4 mol/L NaOH and a CH₃OH/H₂O volume ratio of 1∶1. This study provides a novel feasible reaction pathway for achieving efficient photocatalytic hydrogen production from methanol aqueous solution.

Key words: catalyst, hydrogen production, nanostructure, methanol-water reforming, hole transfer

中图分类号:

TQ 134.1

万俊, 宋佳芮, 范春煌, 魏乐乐, 聂依娜, 刘琳. 高效空穴转移助力光催化碱性甲醇-水溶液制氢[J]. 化工学报, 2025, 76(3): 1064-1075.

Jun WAN, Jiarui SONG, Chunhuang FAN, Lele WEI, Yina NIE, Lin LIU. Highly efficient hole transfer for promoting photocatalytic hydrogen production from alkaline methanol aqueous solution[J]. CIESC Journal, 2025, 76(3): 1064-1075.

图/表 12

图1 萘乙烯加氢反应和质谱测试中萘乙烷裂解机理

Fig.1 The hydrogenation reduction of vinylnaphthalene with D2O as the reaction solvent, and the cleavage mechanism of products for mass spectrometry

图2 不同形貌的Zn0.5Cd0.5S纳米材料的PXRD谱图

Fig.2 PXRD patterns of synthesized Zn0.5Cd0.5S nanomaterials with different morphologies

图3 ZCS-LNR、ZCS-SNR和ZCS-NP样品的TEM照片

Fig.3 TEM images of ZCS-LNR, ZCS-SNR and ZCS-NP samples

图4 ZCS-LNR、ZCS-SNR和ZCS-NP的XPS全谱，Zn 2p、Cd 3d和S 2p的高分辨XPS谱图

Fig.4 XPS survey spectra of ZCS-LNR, ZCS-SNR and ZCS-NP， high-resolution XPS spectra of Zn 2p, Cd 3d and S 2p

表1 不同催化剂的XPS含量分析

Table 1 Analysis of the XPS content of the different catalysts

样品	Zn含量/% (原子分数)	Cd含量/% (原子分数)	Zn/Cd
ZCS-LNR	21.83	20.55	1.06
ZCS-SNR	23.97	21.95	1.09
ZCS-NP	21.10	23.16	0.91

图5 ZCS-LNR、ZCS-SNR和ZCS-NP的光吸收性能和能带结构分析

Fig.5 Light absorption and band structure analysis of ZCS-LNR, ZCS-SNR and ZCS-NP photocatalysts

图6 ZCS-LNR、ZCS-SNR和ZCS-NP催化剂的光生载流子分离性能

Fig.6 Separation performance of photogenerated charge carriers for ZCS-LNR, ZCS-SNR and ZCS-NP photocatalysts

图7 不同形貌Zn0.5Cd0.5S的碱性甲醇水溶液产氢性能，ZCS-LNR在不同反应溶剂体系中的产氢活性对比

Fig.7 Photocatalytic H2 production of Zn0.5Cd0.5S with different structures in CH3OH-NaOH-H2O system， comparison of H2 production in different reaction systems using ZCS-LNR catalyst

图8 ZCS-LNR催化剂在不同条件下的产氢活性及稳定性

Fig.8 Photocatalytic H2 production activity of ZCS-LNR catalyst under different conditions and its stability

图9 ZCS-LNR在不同溶液中的原位EPR光谱，同位素标记实验的气相色谱-质谱（GC-MS）分析(1 G=10-4 T)

Fig.9 In-situ EPR spectra of ZCS-LNR in different solution systems， gas chromatography-mass spectrometry (GC-MS) analysis for deuterium-labeled experiment

表2 萘乙烷分子离子峰和裂解碎片峰的相对丰度和rH/D

Table 2 Relative abundance and rH/D of molecular ion peak and fragmentation peak of naphthalene ethane

质荷比（m/z）	相对丰度/%	r_H/D
141	100	2.4
142	41.5	2.4
156	33.7	2.4
157	21.9
158	7.7

图10 ZCS-NP纳米颗粒和ZCS-LNR纳米棒催化剂的光生载流子迁移机理，ZCS-LNR在CH3OH-H2O和CH3OH-NaOH-H2O体系中的光催化反应机理

Fig.10 Schematic diagram of the photogenerated charge carrier transfer mechanism for ZCS-NP nanoparticles and ZCS-LNR nanorod catalysts， schematic illustration of the photocatalytic reaction mechanism for ZCS-LNR in CH3OH-H2O and CH3OH-NaOH-H2O systems

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