催化学报

催化学报 ›› 2025, Vol. 70: 363-377.DOI: 10.1016/S1872-2067(24)60236-6

• 论文 • 上一篇    下一篇

双金属NixFe2−xP修饰的RP用于增强光催化苯甲醇氧化耦合产H2

李爽, 林海莉, 贾雪梅*(), 金昕, 汪钱龙, 李馨悦, 陈士夫, 曹静*()   

  1. 淮北师范大学绿色和精准合成化学及应用教育部重点实验室, 安徽省合成化学与应用重点实验室, 化学与材料科学学院, 安徽淮北 235000
  • 收稿日期:2024-10-22 接受日期:2024-12-05 出版日期:2025-03-18 发布日期:2025-03-20
  • 通讯作者: * 电子信箱: XuemeiJia@njust.edu.cn (贾雪梅),caojing@chnu.edu.cn (曹静).
  • 基金资助:
    国家自然科学基金(22202077);国家自然科学基金(52272297);安徽省高等学校自然科学研究项目(2024AH040221);安徽省高等学校自然科学研究项目(2024AH030049);安徽省高等学校自然科学研究项目(2023AH050329);安徽省高等学校自然科学研究项目(2022AH010030);安徽省高校(专业)学科带头人培养项目(DTR2023021)

Bimetallic NixFe2-xP cocatalyst with tunable electronic structure for enhanced photocatalytic benzyl alcohol oxidation coupled with H2 evolution over red phosphorus

Shuang Li, Haili Lin, Xuemei Jia*(), Xin Jin, Qianlong Wang, Xinyue Li, Shifu Chen, Jing Cao*()   

  1. Key Laboratory of Green and Precise Synthetic and Applications, Ministry of Education; Anhui Provincial Key Laboratory of Synthetic Chemistry and Applications; College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui, China
  • Received:2024-10-22 Accepted:2024-12-05 Online:2025-03-18 Published:2025-03-20
  • Contact: * E-mail: XuemeiJia@njust.edu.cn (X. Jia),caojing@chnu.edu.cn (J. Cao).
  • Supported by:
    National Natural Science Foundation of China(22202077);National Natural Science Foundation of China(52272297);University Natural Science Research Project of Anhui Province(2024AH040221);University Natural Science Research Project of Anhui Province(2024AH030049);University Natural Science Research Project of Anhui Province(2023AH050329);University Natural Science Research Project of Anhui Province(2022AH010030);University Discipline (Professional) Leader Cultivation Project of Anhui Province(DTR2023021)

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摘要：

近年来, 过渡金属磷化物(TMPs)由于具有较低的成本和较高的燃烧热值, 已被广泛用作有效的助催化剂, 替代传统的贵金属材料应用于光催化反应过程. 特别是双金属磷化物, 因其较低的过电势、良好的导电性和丰富的活性位点, 引起了广泛关注. 尽管双金属磷化物已被证实为高效的光催化助催化剂, 但大多数研究主要集中在固定组成下调节其负载量, 忽视了对双金属磷化物中金属-金属成分的调控. 尤其是光生电子转移路径及由双金属磷化物引起的反应能垒降低机制仍不明晰. 因此, 深入探讨光生电子迁移路径与热力学调控在双金属磷化物助催化剂中的相互作用, 依然是一个巨大的挑战.

本文设计了一系列镍铁磷化物(NixFe2-xP, 0 < x < 2)助催化剂, 其结构和性能可通过调节镍与铁的原子比进行精确控制, 并负载于非金属元素红磷(RP)上, 以实现高效的光催化选择性氧化苯甲醇(BA)耦合产氢(H2). 相比于单金属磷化物Ni2P和Fe2P助催化剂调控的RP, 双金属磷化物NixFe2-xP助催化剂调控的RP表现出更优异的光催化氧化还原活性. 特别是, 由Ni1.25Fe0.75P调控的RP展现出最佳的光催化性能. 具体而言, Ni1.25Fe0.75P/RP复合材料在苯甲醛(BAD)生成速率方面达到10.75 μmol g−1 h−1, 分别比纯RP (0.175 μmol g−1 h−1)、Ni2P/RP (2.45 μmol g−1 h−1)和Fe2P/RP (0.65 μmol g−1 h−1)高出约61.4倍、4.39倍和16.5倍. 上述Ni1.25Fe0.75P助催化剂显著提升RP光催化氧化还原性能的原因主要归因于其组分调控带来的多重效应. 首先, 双金属磷化物提供了丰富的活性位点, 促进了反应物分子的吸附和活化, 从而有效降低了反应能垒. 其次, 优化的电子结构增强了对光生载流子的有效分离, 减少了电子-空穴对的复合几率, 进一步提升了光催化效率. 此外, 一系列非原位和原位表征以及理论模拟计算结果进一步验证了Ni1.25Fe0.75P具备较好的导电性和较低的过电势. 这些特性不仅使其能够提供强大的吸附能力和丰富的活性位点, 从而加速电子迁移并降低RP的反应能垒, 还显著增强了对光生电子的捕获和传输能力, 减少了电子-空穴对的复合几率, 进而大幅提高了光催化反应的整体效率.

综上所述, 本研究通过调控NixFe2-xP助催化剂的组分, 以优化NixFe2-xP助催化剂的过电势和导电性, 从而降低反应能垒, 实现高效的光催化选择性氧化BA耦合产H2, 为优化助催化剂提供了新的思路和视角, 也为设计高效复合光催化剂提供了有益的借鉴.

关键词: 双金属磷化物助催化剂, 组成调控, 红磷, 选择性氧化苯甲醇, H2

Abstract:

Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics, superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition. In this study, a series of bimetallic nickel-iron phosphide (NixFe2-xP, where 0 < x < 2) cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus (RP) for the photocatalytic selective oxidation of benzyl alcohol (BA) coupled with hydrogen production. The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H2 yield. The RP regulated by bimetallic phosphide cocatalysts (NixFe2-xP) demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts (Ni2P and Fe2P). In particular, the RP regulated by Ni1.25Fe0.75P exhibited the best photocatalytic performance. In addition, experimental and theoretical calculations further illustrated that Ni1.25Fe0.75P, with the optimized electronic structure, possessed good electrical conductivity and provided strong adsorption and abundant active sites, thereby accelerating electron migration and lowering the reaction energy barrier of RP. This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.

Key words: Bimetallic phosphides cocatalyst, Composition regulation, Red phosphorus, Selective oxidation of benzyl alcohol H2