Photo-induced in-situ synthesis of Cu2O@C nanocomposite for efficient photocatalytic evolution of hydrogen
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摘要: Cu2O具有禁带窄、环境友好和储量丰富等优点,是一种理想的可见光催化剂,然而其光生载流子复合率高和稳定性差等问题限制了Cu2O在光催化领域的实际应用。为此,本文采用光诱导原位技术,以甲醇为碳源、硫酸铜为铜源,一步成功制备了超薄炭壳层包覆的Cu2O复合纳米材料(Cu2O@C)。结果显示,与常规炭包覆方法相比,光诱导原位技术避免了苛刻的反应条件及繁琐的合成步骤对Cu2O半导体结构的破坏,有效保留了Cu2O本征电子结构,使其具有优异的光催化活性及稳定性。同时,Cu2O@C的核壳结构不仅可以钝化半导体表面缺陷和促进光生载流子的分离,而且炭壳层的包覆还可以避免Cu2O纳米颗粒与溶液的直接接触,有效抑制高活性反应中间体对催化剂结构的破坏。与单独的Cu2O纳米颗粒相比,Cu2O@C复合纳米材料在可见光下的光解水产氢活性和稳定性得到显著提高,产氢速率可达1.28 mmol/(g·h),且在连续五次循环稳定性测试中,氢气生成速率无明显变化。Abstract: Cuprous oxide (Cu2O) is an ideal visible light catalyst owing to its narrow band gap, environmental benignity and abundant storage; however, the fast recombination of photogenerated charge carriers and poor stability of Cu2O has impeded its application in photocatalysis. Herein, we demonstrate that Cu2O@C nanocomposite can spontaneously evolve from a methanol aqueous solution containing cupric ions under the induction of irradiation. Compared with the traditional carbon coating method, the Cu2O@C nanocomposite obtained by the photo-induced in-situ synthesis can reserve superior original characteristics of the semiconductor under mild reaction conditions, promote the charge transfer and enhance the separation efficiency of charge carriers; in addition, the carbon shells can also effectively prevent Cu2O from photo-corrosion. As a result, the Cu2O@C nanocomposite exhibits excellent photocatalytic activity in the hydrogen evolution in comparison with the Cu2O particles; the H2 evolution rate over the Cu2O@C nanocomposite reaches 1.28 mmol/(g·h) under visible light, compared with the value of 0.065 mmol/(g·h) over Cu2O. Moreover, the Cu2O@C nanocomposite displays good cycle stability, viz., without any deactivation in the catalytic activity after five cycles.
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图 7 (a) 不同半导体光催化剂可见光下的光解水产氢性能;(b) Cu2O@C光解水产氢循环稳定性测试;(c) Cu2O@C稳定性测试前后的XRD谱图和 (d) 稳定性测试后的TEM图像
Figure 7 (a) Photocatalytic H2 evolution rate of as-prepared photocatalysts under visible light illumination; (b) Cycling stability test of photocatalytic hydrogen evolution over Cu2O@C nanocomposite; (c) XRD images of the Cu2O@C nanocomposite before and after cycling stability test; (d) TEM images after cycling stability test
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