表面原子排布激活d10电子调控p带中心作为太阳能制氢高活性位点

doi:10.1016/S1872-2067(24)60119-1

催化学报 ›› 2024, Vol. 65: 185-194.DOI: 10.1016/S1872-2067(24)60119-1

表面原子排布激活d¹⁰电子调控p带中心作为太阳能制氢高活性位点

赖珊珊^a, 苏加坤^d, 姜淑娟^a^,^*(), 张建军^c^,^*(), 宋少青^b^,^*()

^a宁波大学材料科学与化学工程学院, 浙江宁波313211
^b宁波工程学院新能源学院, 浙江宁波315336
^c中国地质大学(武汉)材料与化学学院, 湖北武汉430074
^d江西中烟工业有限责任公司技术研发中心, 江西南昌330096

收稿日期:2024-07-10 接受日期:2024-08-21 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: jiangshujuan@nbu.edu.cn (姜淑娟), zhangjianjun@cug.edu.cn (张建军), songshaoqing@nbu.edu.cn (宋少青).
基金资助:
国家自然科学基金(22372084);浙江省“尖兵”计划(2023C3016);宁波工程学院科研启动基金(2023KQ066)

Activating d¹⁰ electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H₂ by surface atomic arrangement

Shanshan Lai^a, Jiakun Su^d, Shujuan Jiang^a^,^*(), Jianjun Zhang^c^,^*(), Shaoqing Song^b^,^*()

^aSchool of Materials Science & Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China
^bSchool of New Energy, Ningbo University of Technology, Ningbo 315336, Zhejiang, China
^cLaboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, Hubei, China
^dTechnology Center, China Tobacco Jiangxi Industrial Limited Liability Company, Nanchang 330096, Jiangxi, China

Received:2024-07-10 Accepted:2024-08-21 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: jiangshujuan@nbu.edu.cn (S. Jiang), zhangjianjun@cug.edu.cn (J. Zhang), songshaoqing@nbu.edu.cn (S. Song).
Supported by:
National Natural Science Foundation of China(22372084);Jianbing Project of Zhejiang Province(2023C3016);Research Foundation from Ningbo University of Technology(2023KQ066)

摘要/Abstract

摘要：

太阳能光催化全分解水制氢能被广泛视为解决能源危机和环境问题的极具应用前景的策略. 在这一过程中, 光生电子和空穴在催化剂表面还原、氧化的活性位点上, 与*H, *OH等活性中间体发生反应, 最终生成H₂和O₂. 然而, 如果这些反应活性物种在活性位点上的化学吸附力过弱或过强, 都会导致H₂释放的活化能升高, 进而降低反应的动力学速率, 严重制约了太阳能向氢能转化的效率. 值得注意的是, d带中心(ε_d)作为关键的催化活性位点, 其位置接近费米能级, 使得可以通过调控其电子填充率来改变催化活性位点与反应中间体之间的相互作用力, 进而提高催化活性.

通常, 催化活性和d轨道上的电子占有率之间的关系呈火山图. 在这个模型中, 填充的成键轨道和部分填充的反键轨道共同为反应活性中间体提供了适宜的化学吸附强度. 然而, 当ε_d降低到费米能级以下时, 情况就发生了变化, 反键d轨道上电子占有率会增加, 导致化学吸附性能变差. 这一规律通常存在于大量具有d¹⁰电子构型的金属中, 如IB, IIB, IIIA和IVA族元素. 在表面原子排列过程中, 通过p-d_π杂化作用可以激活来自d¹⁰的共享电子. 此时, 缺电子原子的反键d轨道将接收来自*H的1s轨道或*OH的2p轨道的电子, 这种电子转移过程会导致能态的重新分布和分裂. 与此同时, 随着反键轨道上电子占有率的增加, 金属氧化物的晶格氧原子的p带中心(ε_p)将呈现出减小的趋势, 这导致H与O之间的p-s反键作用减弱, 从而使得H的吸附和解吸过程更加容易, 吸附能接近零. 另一方面, 当金属原子的ε_p上升时, O 2p_x,y的1π共振态接近费米能级, 这有利于*OH的化学吸附. 因此, 本文利用缺电子磷原子取代元素周期表中具有d¹⁰电子排布的In₂O₃中的晶格氧, 通过水热处理调节表面原子排列, 从而增强了In d¹⁰电子构型在光催化分解水制氢反应中的催化性能. 通过微观反应动力学模拟发现, 正如预期, In ε₅_p和O ε₂_p分别呈现出上升和下降的趋势, 这有利于*OH和*H中间体的化学吸附、活化以及相应的正向转化. 结合飞秒瞬态荧光吸收光谱及其拟合结果, 揭示了光生载流子的迁移路径及动力学. 与In₂O₃相比, P-In₂O₃中光生电子更容易转移到O 2p轨道, 而空穴则更易聚集于In 5p轨道. 通过在线气相色谱实时监测H₂和O₂析出的速率, 计算发现P-In₂O₃降低了H₂析出的活化能. 随后, 利用原位漫反射红外傅立叶变换光谱捕捉到反应关键中间体如*OH, *H及*O等在催化剂表面的逐渐增强的信号. 结合理论计算, 揭示了水分子在催化剂表面逐步转化的路径. 此外, In ε₄_d呈现出下降趋势, 阻止了水分解过程中H₂和O₂之间发生的逆向反应. 在AM 1.5G光照下和65 °C条件下, 优化的In₂O₃基催化剂(通过活化d¹⁰电子构型)展现出了较好的催化太阳能转化氢能效率, 达到2.23%, 这一性能超过了大多数助催化剂和包括贵金属在内的单原子催化剂.

综上, 这些发现致力于激活传统意义上因d¹⁰电子构型而难以发挥催化作用的“催化荒漠”(即那些因电子构型限制而难以发挥催化作用的材料), 突破光催化水分解正向反应能垒和动力学瓶颈, 拓展高效催化材料的探索领域, 从而推动太阳能制氢能商业化进程.

关键词: d带中心, p带中心, 局域电场, 光催化水解离, 动力学过程

Abstract:

Relationship between the activity for photocatalytic H₂O overall splitting (HOS) and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram, and specially the d¹⁰ electronic configuration in valley bottom exhibits inert activity, which seriously fetters the development of catalytic materials with great potentials. Herein, In d¹⁰ electronic configuration of In₂O₃ was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band (In ε₅_p) and descended O 2p-band (O ε₂_p) centers as efficient active sites for chemisorption to *OH and *H during forward HOS, respectively, along with a declined In 4d-band center (In ε₄_d) to inhibit its backward reaction. A stable STH efficiency of 2.23% under AM 1.5 G irradiation at 65 °C has been obtained over the activated d¹⁰ electronic configuration with a lowered activation energy for H₂ evolution, verified by femtosecond transient absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics. These findings devote to activating d¹⁰ electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS, which expands the exploration of high-efficiency catalytic materials.

Key words: d-Band center, p-Band center, Localized field, Photocatalytic water splitting, Dynamic process

赖珊珊, 苏加坤, 姜淑娟, 张建军, 宋少青. 表面原子排布激活d¹⁰电子调控p带中心作为太阳能制氢高活性位点[J]. 催化学报, 2024, 65: 185-194.

Shanshan Lai, Jiakun Su, Shujuan Jiang, Jianjun Zhang, Shaoqing Song. Activating d¹⁰ electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H₂ by surface atomic arrangement[J]. Chinese Journal of Catalysis, 2024, 65: 185-194.

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图/表 4

Fig. 1. (a) High-resolution XPS spectra of O 2p for In2O3 and P2-In2O3?x. (b) High-resolution XPS spectra of In 3d for In2O3 and P2-In2O3?x. (c) FESEM images of In2O3. (d) FESEM images of P2-In2O3?x. (e) HRTEM and TEM images (inset in e) of P2-In2O3?x. (f) Lattice fringes of P2-In2O3?x. (g) XRD patterns. (h) The derived facet proportion from texture coefficient calculation and In-P hybridization percent from XPS profiles.

Fig. 2. PDOS and band center changes for In 5p (a) and O 2p (b) before and after P introduction. The optimized adsorption structure models of *H-In2O3 (c), *OH-In2O3 (d), *H-P-In2O3?x (e) and *OH-P-In2O3?x (f). Adsorption energies of *OH on In ε5p (g) and *H on O ε2p (h) of In2O3 and P-In2O3?x, respectively. (i) The schematic diagram for the effect of the decreased O ε2p and the increased In ε5p on the adsorption of *H and *OH intermediates to active sites of In2O3 and P-In2O3?x.

Fig. 3. (a) fs-TAS of In2O3. (b) fs-TAS of P2-In2O3?x. (c) fs-TAS of In2O3 with K2Cr2O7 and CH3CH(OH)COOH as e? and h+ scavengers, respectively. Fitted transient absorption kinetics of In2O3 (d) and P2-In2O3?x (e) at 480 nm within 1000 ps decay time. (f) The proposed mechanism for charge generation, transfer and separation in space at the aids of LEF force and the tuned d- and p-band center positions.

Fig. 4. (a) Gas evolution performances of samples for 3 h under visible light irradiation. (b) AQE values at different wavelengths with UV-vis DRS plot of P2-In2O3?x. (c) STH efficiencies at different temperatures under AM 1.5 G irradiation. (d) Photocatalytic reaction activation energies of the samples calculated according to their performances at different temperatures (Figs. S6(c)?(e)). (e) Recycle stability tests of P2-In2O3?x system. (f?i) The structure models for calculating the reverse reaction of H2O splitting. (j) The calculated reaction Gibbs free energy (ΔG) on In2O3 and P-In2O3?x. (k) In situ DRIFTS patterns during photocatalytically splitting H2O over P2-In2O3?x. (l) DFT calculations to verify the reaction barriers process of H2O splitting into H2 on O ε2p and O2 on In ε5p of P-In2O3?x.

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表面原子排布激活d¹⁰电子调控p带中心作为太阳能制氢高活性位点

Activating d¹⁰ electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H₂ by surface atomic arrangement

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