Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用

doi:10.1016/S1872-2067(23)64442-0

催化学报 ›› 2023, Vol. 49: 180-187.DOI: 10.1016/S1872-2067(23)64442-0

• 论文 • 上一篇

Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用

夏思源^a, 李奇远^a, 张仕楠^a, 许冬^a, 林秀^a, 孙露菡^a, 许景三^b, 陈接胜^a, 李国栋^c, 李新昊^a^,^*()

^a上海交通大学化学化工学院, 变革性分子前沿科学中心, 上海 200240, 中国
^b昆士兰科技大学化学与物理学院和材料科学中心, 布里斯班昆士兰, 澳大利亚
^c吉林大学化学学院, 无机合成与制备化学国家重点实验室, 吉林长春 130012, 中国

收稿日期:2023-03-23 接受日期:2023-04-10 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: xinhaoli@sjtu.edu.cn (李新昊).
基金资助:
上海市科学技术委员会(20520711600);国家自然科学基金(22071146);国家自然科学基金(21931005);吉林大学无机合成与制备化学国家重点实验室开放课题基金(2021-1)

Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions

Si-Yuan Xia^a, Qi-Yuan Li^a, Shi-Nan Zhang^a, Dong Xu^a, Xiu Lin^a, Lu-Han Sun^a, Jingsan Xu^b, Jie-Sheng Chen^a, Guo-Dong Li^c, Xin-Hao Li^a^,^*()

^aSchool of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, China
^bSchool of Chemistry and Physics and Centre for Materials Science, Queensland University of Technology, Brisbane, Queensland 4000, Australia
^cState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, Jilin, China

Received:2023-03-23 Accepted:2023-04-10 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: xinhaoli@sjtu.edu.cn (X.-H. Li).
Supported by:
Shanghai Science and Technology Committee(20520711600);National Natural Science Foundation of China(22071146);National Natural Science Foundation of China(21931005);Open Research Fund of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2021-1)

摘要/Abstract

摘要：

作为生产尼龙6、尼龙66和聚酰胺树脂等各种聚合物的重要原材料, 环己酮和环己醇(KA oil)每年在全球的消耗量大约在100万吨. KA oil主要采用苯酚加氢法和环己烷氧化法制备, 其中苯酚加氢法可以在相对温和的反应条件下实现较高的选择性. 目前, Pt基和Pd基非均相催化剂因具有良好的可重复使用性成为加氢反应的主流催化剂, 但在实际应用中却面临着催化剂价格昂贵的问题. 因此, 减少贵金属的消耗量以降低KA oil的最终生产成本, 开发探索出更高效的方法最大程度提升贵金属纳米催化剂的活性成为核心问题. 目前, 研究者致力于通过调控催化剂的金属粒径、合金结构和催化剂孔结构来提高金属纳米催化剂的苯酚加氢活性. 近期研究发现, 酸性氧化物载体可以用来提升负载金属中心的苯酚加氢活性, 可以通过改变金属周围的微环境进一步提高金属活性.

本文通过构建尺寸可调控的Pd纳米立方体/硫掺杂碳载体异质结结构, 提出一种特殊的电子界面效应成功地提高了活性中心Pd纳米立方体的苯酚加氢活性. 在金属/半导体载体异质结中, 由金属和半导体之间所形成的肖特基势垒所驱动, 电子在金属和半导体载体的界面处发生转移直至金属和半导体载体的费米能级达到平衡, 最终在金属和半导体界面处形成由富电子侧和贫电子侧组成的电子界面. 有限元计算、密度泛函理论计算、X射线光电子能谱和紫外光电子能谱结果表明, 负载到硫掺杂碳载体上的Pd纳米立方体的电子密度和Pd纳米立方体的尺寸有着独特的线性关系. CO程序升温脱附实验结果表明, 尺寸更小的Pd纳米立方体拥有更多的表面原子, 因此苯酚转化率会随着Pd纳米立方体尺寸的减小而增加, 但根据表面原子来计算转换频率(TOF), 三种不同尺寸的未负载的Pd纳米立方体的TOF值均约为2. 将Pd纳米立方体负载到硫掺杂碳载体上之后, Pd纳米立方体/硫掺杂碳异质结的电子界面效应可显著提高负载的Pd纳米立方体的苯酚加氢活性. 相比于未负载的15, 11和5 nm Pd纳米立方体, 负载到载体上之后的Pd纳米立方体的TOF值分别被提高12倍、16倍和20倍. 理论计算和实验结果表明, 所有负载到硫掺杂碳载体上的Pd纳米立方体中的5 nm Pd纳米立方体最贫电, 且对酚类加氢反应表现出普遍性的促进作用, 与未负载的5 nm Pd纳米立方体相比可以将苯酚及其衍生物的加氢活性提高10-20倍.

关键词: 电子界面效应, 苯酚加氢, 钯纳米立方体, 肖特基异质结, 非均相催化

Abstract:

As mainstream catalysts for phenol hydrogenation with good reusability and high selectivity under mild conditions, Pt- and Pd-based heterogeneous catalysts suffer from unsatisfied catalyst costs. The structures of metals (i.e., particle sizes, alloy structures, and porosity) and the acidity of the support were optimized to boost the intrinsic activity of noble metal nanocatalysts with a maximum promoting factor of 3.3. There is considerable scope for exploring more powerful methods for boosting the mass activity of metal catalysts. Herein, we demonstrate a novel size-dependent electronic interface effect in the heterojunctions of Pd nanocubes and sulfur-doped carbon (SC) supports to enhance phenol hydrogenation activity. Theoretical calculations and experimental results indicate that the size-dependent electron deficiency of Pd nanocubes on the designed SCs as electron acceptors results in an unexpected and universal promotion of phenol hydrogenation activity, outperforming free-standing Pd nanocubes by a factor of 9-19.

Key words: Electronic interface effect, Phenol hydrogenation, Pd nanocube, Schottky heterojunction, Heterogeneous catalysis

夏思源, 李奇远, 张仕楠, 许冬, 林秀, 孙露菡, 许景三, 陈接胜, 李国栋, 李新昊. Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用[J]. 催化学报, 2023, 49: 180-187.

Si-Yuan Xia, Qi-Yuan Li, Shi-Nan Zhang, Dong Xu, Xiu Lin, Lu-Han Sun, Jingsan Xu, Jie-Sheng Chen, Guo-Dong Li, Xin-Hao Li. Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions[J]. Chinese Journal of Catalysis, 2023, 49: 180-187.

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Fig. 1. Synthesis and characterization of Pd/SC heterojunctions. (a) Synthetic process of typical Pd/SC catalysts via aging the mixture of Pd nanocubes and SC support at 150 °C. The SC support was prepared through the thermal condensation of carbon black and dibenzyl disulfide at 900 °C in a N2 atmosphere. (b-d) High-resolution TEM images of Pd-5, Pd-11, and Pd-15 nanocubes, respectively. (e) S 2p XPS spectra of the SC support. (f) High-resolution TEM image of a typical Pd-5/SC sample. (g) Electron density difference stereogram of the Pd/SC model. Red/blue areas indicate a negative/positive charge. (h) Pd 3d XPS spectra of the free-standing Pd-5 and Pd-5/SC samples.

Fig. 2. Phenol hydrogenation activity of the Pd-5/SC catalyst and controls. (a) Yields of cyclohexanone (green) and cyclohexanol (dark green) over the Pd-5/SC catalyst (Pd content: 3 wt%) at different reaction times. Reaction conditions: 20 mg Pd-5/SC catalyst (Pd 1.13 mol%), 0.5 mmol phenol, 5 mL water, 60 °C, 10 bar H2. (b) Conversions of phenol over the Pd-5, Pd-5/SC, and SC catalysts. Reaction conditions: 0.6 mg Pd-5 catalyst (Pd 1.13 mol%; reaction time: 4 h), 20 mg Pd-x/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), or 19.4 mg SC support (reaction time: 4 h); 0.5 mmol phenol; 5 mL water; 60 °C; 10 bar H2. (c) TOF values of the Pd-5 (grey circles) and Pd-5/SC (blue spheres) catalysts at different H2 pressures. (d) Corresponding Arrhenius plots of the Pd-5 (grey circles) and Pd-5/SC (blue spheres) catalysts. (e) Conversions (Con.: blue spheres) of phenol and selectivity (Sel.: green spheres) to cyclohexanone for four runs over the Pd-5/SC catalyst. (f) Size distribution and high-resolution TEM image (inset) of the used Pd-5/SC catalyst after four runs.

Fig. 3. Origin of electronic interface-promoted phenol hydrogenation activity on Pd-x/SC catalysts. (a) TOF values of the free-standing Pd-x and Pd-x/SC catalysts. Reaction conditions: 0.6 mg Pd-x catalyst (Pd 1.13 mol%; reaction time: 40 h) or 20 mg Pd-x/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), 0.5 mmol phenol, 5 mL water, 60 °C, 10 bar H2. (b) Electron distribution at the electronic interface of the Pd/SC Schottky contact model and (c) calculated numbers of electrons transferred from the Pd-x models to the same SC support model using the finite element simulation method. (d) Measured work functions (Φ) of the free-standing Pd-x and Pd-x/SC samples via ultraviolet photoelectron spectroscopy (UPS). (e) Pd 3d XPS spectra of the Pd-x/SC catalysts.

Fig. 4. Electronic interface effect on phenol hydrogenation reactions over the Pd-5/SC heterojunction. (a) The calculated adsorption energies Eads?H2 of H2 molecules on the surface of the neutral Pd model (gray) for free-standing Pd nanocubes and the electron-deficient Pd (blue, Pd-e-) model for Pd/SC heterojunctions. (b) Calculated adsorption energies Eads-phenol of pre-adsorbed phenol molecules on the surface of the neutral Pd (gray) and electron-deficient Pd (blue, Pd-e-) models and (c) the corresponding electron density difference stereograms. Red/blue areas indicate a negative/positive charge. (d) Gibbs free energy diagrams of phenol hydrogenation on the neutral Pd (gray, top) and electron-deficient Pd (blue, Pd-e-) models. (e) Promoted TOF values from the free-standing Pd-5 to Pd-5/SC catalysts for the hydrogenation of phenol and substituted phenols according to Table S9. Reaction conditions: 0.6 mg Pd-5 catalyst (Pd 1.13 mol%; reaction time: 40 h) or 20 mg Pd-5/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), 0.5 mmol substrates, 5 mL water, 60 °C, 10 bar H2.

参考文献

[1]	H. Liu, T. Jiang, B. Han, S. Liang, Y. Zhou, Science, 2009, 326, 1250-1252.
[2]	H. Tateno, S. Iguchi, Y. Miseki, K. Sayama, Angew. Chem. Int. Ed., 2018, 57, 11238-11241.
[3]	Q. Meng, M. Hou, H. Liu, J. Song, B. Han, Nat. Commun., 2017, 8, 14190.
[4]	Y. Wang, J. Yao, H. Li, D. Su, M. Antonietti, J. Am. Chem. Soc., 2011, 133, 2362-2365.
[5]	G. Yang, V. Maliekkal, X. Chen, S. Eckstein, H. Shi, D. M. Camaioni, E. Barath, G. L. Haller, Y. Liu, M. Neurock, J. A. Lercher, J. Catal., 2021, 404, 579-593.
[6]	F. Valentini, N. Santillo, C. Petrucci, D. Lanari, E. Petricci, M. Taddei, L. Vaccaro, ChemCatChem, 2018, 10, 1277-1281.
[7]	P. Zhou, S.-X. Guo, L. Li, T. Ueda, Y. Nishiwaki, L. Huang, Z. Zhang, J. Zhang, Angew. Chem. Int. Ed., 2022, e202214881.
[8]	S. Li, H. Zhao, W. Ran, J. Liu, R. Liu, Chem. Commun., 2022, 58, 10357-10360.
[9]	W.-J. Zhou, R. Wischert, K. Xue, Y.-T. Zheng, B. Albela, L. Bonneviot, J.-M. Clacens, F. De Campo, M. Pera-Titus, P. Wu, ACS Catal., 2014, 4, 53-62.
[10]	Y. Wang, J. Zhang, X. Wang, M. Antonietti, H. Li, Angew. Chem. Int. Ed., 2010, 49, 3356-3359.
[11]	S. Chen, Y. Li, Z. Wang, Y. Jin, R. Liu, X. Li, J. Catal., 2022, 411, 135-148.
[12]	C. Xu, L. Jin, X. Wang, Y. Chen, L. Dai, Carbon, 2020, 160, 287-297.
[13]	N. Singh, M.-S. Lee, S. A. Akhade, G. Cheng, D. M. Camaioni, O. Y. Gutierrez, V.-A. Glezakou, R. Rousseau, J. A. Lercher, C. T. Campbell, ACS Catal., 2018, 9, 1120-1128.
[14]	N. Singh, U. Sanyal, G. Ruehl, K. A. Stoerzinger, O. Y. Gutierrez, D. M. Camaioni, J. L. Fulton, J. A. Lercher, C. T. Campbell, J. Catal., 2020, 382, 372-384.
[15]	Y. Yoon, R. Rousseau, R. S. Weber, D. Mei, J. A. Lercher, J. Am. Chem. Soc., 2014, 136, 10287-10298.
[16]	C.-J. Lin, S.-H. Huang, N.-C. Lai, C.-M. Yang, ACS Catal., 2015, 5, 4121-4129.
[17]	B. Hu, X. Li, W. Busser, S. Schmidt, W. Xia, G. Li, X. Li, B. Peng, Chem. Eur. J, 2021, 27, 10948-10956.
[18]	C. Liu, J. Wang, P. Zhu, H. Liu, X. Zhang, Chem. Eng. J., 2022, 430, 132589.
[19]	T. K. Egner, P. Naik, Y. An, A. Venkatesh, A. J. Rossini, I. I. Slowing, V. Venditti, ChemCatChem, 2020, 12, 4160-4166.
[20]	H. Zhou, B. Han, T. Liu, X. Zhong, G. Zhuang, J. Wang, Green Chem., 2017, 19, 3585-3594.
[21]	X. Li, H. Jiang, M. Hou, Y. Liu, W. Xing, R. Chen, Chem. Eng. J., 2020, 386, 120744.
[22]	H. W. Zhang, A. J. Han, K. Okumura, L. X. Zhong, S. Z. Li, S. Jaenicke, G.-K. Chuah, J. Catal., 2018, 364, 354-365.
[23]	U. Sanyal, Y. Song, N. Singh, J. L. Fulton, J. Herranz, A. Jentys, O. Y. Gutiérrez, J. A. Lercher, ChemCatChem, 2018, 11, 575-582.
[24]	R. Wu, Q. Meng, J. Yan, H. Liu, Q. Zhu, L. Zheng, J. Zhang, B. Han, J. Am. Chem. Soc., 2022, 144, 1556-1571.
[25]	Y. Li, J. Liu, J. He, L. Wang, J. Lei, Appl. Catal. A, 2020, 591, 117409.
[26]	J. X. Zhang, H. Jiang, Y. F. Liu, R. Z. Chen, Appl. Surf. Sci., 2019, 488, 555-564.
[27]	D. Xu, S.-N. Zhang, J.-S. Chen, X.-H. Li, Chem. Rev. 2023, 123, 1-30.
[28]	R. Long, K. Mao, X. Ye, W. Yan, Y. Huang, J. Wang, Y. Fu, X. Wang, X. Wu, Y. Xie, Y. Xiong, J. Am. Chem. Soc., 2013, 135, 3200-3207.
[29]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[30]	B. Delley, J. Chem. Phys., 1990, 92, 508-517.
[31]	B. Delley, J. Chem. Phys., 2000, 113, 7756-7764.
[32]	N. Shi, B. Xi, Z. Feng, J. Liu, D. Wei, J. Liu, J. Feng, S. Xiong, Adv. Mater. Interfaces, 2019, 6, 1802088.
[33]	P. Gao, Z.-H. Xue, S.-N. Zhang, D. Xu, G.-Y. Zhai, Q.-Y. Li, J.-S. Chen, X.-H. Li, Angew. Chem. Int. Ed., 2021, 60, 20711-20716.
[34]	Q.-Y. Yu, H. Su, G.-Y. Zhai, S.-N. Zhang, L.-H. Sun, J.-S. Chen, X.-H. Li, Chem. Commun., 2021, 57, 741-744.
[35]	Y.-X. Lin, S.-N. Zhang, Z.-H. Xue, J.-J. Zhang, H. Su, T.-J. Zhao, G.-Y. Zhai, X.-H. Li, M. Antonietti, J.-S. Chen, Nat. Commun., 2019, 10, 4380.
[36]	D. Xu, X. Lin, Q.-Y. Li, S.-N. Zhang, S.-Y. Xia, G.-Y. Zhai, J.-S. Chen, X.-H. Li, J. Am. Chem. Soc., 2022, 144, 5418-5423.
[37]	H. Chen, Y. He, L. D. Pfefferle, W. Pu, Y. Wu, S. Qi, ChemCatChem, 2018, 10, 2558-2570.
[38]	A. Li, K. Shen, J. Chen, Z. Li, Y. Li, Chem. Eng. Sci., 2017, 166, 66-76.
[39]	H.-H. Wang, S.-N. Zhang, T.-J. Zhao, Y.-X. Liu, X. Liu, J. Su, X.-H. Li, J.-S. Chen, Sci. Bull., 2020, 65, 651-657.
[40]	G. Li, J. Han, H. Wang, X. Zhu, Q. Ge, ACS Catal., 2015, 5, 2009-2016.
[41]	D. Lei, K. Yu, M.-R. Li, Y. L. Wang, Q. Wang, T. Liu, P. K. Liu, L.-L. Lou, G. C. Wang, S. X. Liu, ACS Catal., 2016, 7, 421-432.
[42]	K. Murata, Y. Mahara, J. Ohyama, Y. Yamamoto, S. Arai, A. Satsuma, Angew. Chem. Int. Ed., 2017, 56, 15993-15997.
[43]	D. Gao, H. Zhou, J. Wang, S. Miao, F. Yang, G. Wang, J. Wang, X. Bao, J. Am. Chem. Soc., 2015, 137, 4288-4291.
[44]	J. Chen, J. Zhong, Y. Wu, W. Hu, P. Qu, X. Xiao, G. Zhang, X. Liu, Y. Jiao, L. Zhong, Y. Chen, ACS Catal., 2020, 10, 10339-10349.
[45]	F. F. Yang, D. Liu, Y. T. Zhao, H. Wang, J. Y. Han, Q. F. Ge, X. L. Zhu, ACS Catal., 2018, 8, 1672-1682.
[46]	S.-N. Zhang, P. Gao, L.-H. Sun, J.-S. Chen, X.-H. Li, Chem. Eur. J, 2022, 28, e202103918.

Pd纳米立方体异质结尺寸依赖的电子界面效应对苯酚加氢反应的促进作用

Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions

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[15]	张嘉熙, 黄高伟, 张琤, 何群华, 黄超, 杨旭, 宋慧宇, 梁振兴, 杜丽, 廖世军. 巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能[J]. 催化学报, 2013, 34(8): 1519-1526.