配体覆盖的Ir催化剂上巴豆醛加氢反应: 金属-有机物界面促进活性和选择性

doi:10.1016/S1872-2067(23)64399-2

催化学报 ›› 2023, Vol. 47: 265-277.DOI: 10.1016/S1872-2067(23)64399-2

• 论文 • 上一篇

配体覆盖的Ir催化剂上巴豆醛加氢反应: 金属-有机物界面促进活性和选择性

叶艳文¹, 胡一鸣¹, 郑万彬, 贾爱平, 王瑜^*(), 鲁继青^*()

浙江师范大学物理化学研究所, 高等催化材料教育部重点实验室, 浙江金华321004

收稿日期:2022-11-26 接受日期:2023-01-19 出版日期:2023-04-18 发布日期:2023-03-20
通讯作者: *电子信箱: yuwang@zjnu.cn (王瑜),jiqinglu@zjnu.cn (鲁继青).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(21773212);浙江师范大学自主设计项目(2021ZS06)

Hydrogenation of crotonaldehyde over ligand-capped Ir catalysts: Metal-organic interface boosts both activity and selectivity

Yan-Wen Ye¹, Yi-Ming Hu¹, Wan-Bin Zheng, Ai-Ping Jia, Yu Wang^*(), Ji-Qing Lu^*()

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, Zhejiang, China

Received:2022-11-26 Accepted:2023-01-19 Online:2023-04-18 Published:2023-03-20
Contact: *E-mail: yuwang@zjnu.cn (Y. Wang),jiqinglu@zjnu.cn (J.-Q. Lu).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21773212);self-designed scientific research project of Zhejiang Normal University(2021ZS06)

摘要/Abstract

摘要：

α,β-不饱和醇是药物和香料等精细化学品合成的重要中间体. 在工业上将α,β-不饱和醛与强还原剂如NaBH₄等反应后可合成对应的不饱和醇, 但该方法易导致环境污染等问题. α,β-不饱和醛选择性加氢制备α,β-不饱和醇是原子经济反应, 符合绿色化学要求. 但α,β-不饱和醛分子中含有共轭的C=C键和C=O键, 在热力学和动力学上皆倾向于C=C键的加氢生成饱和醛, 导致α,β-不饱和醇的选择性较低. 因此提高α,β-不饱和醛中C=O的加氢选择性具有挑战性. 巴豆醛属于典型的α,β-不饱和醛, 其选择性加氢生成巴豆醇常作为模型反应用于研究催化剂构效关系. 近年来, 通过胶体方法制备配体保护的金属纳米颗粒在选择性加氢反应中表现出较好的选择性, 可归因于配体产生的立体效应和电子效应等因素, 但配体的存在往往抑制反应物在活性金属表面的吸附, 从而导致反应活性下降. 因此, 如何克服活性-选择性的“跷跷板”瓶颈具有重要意义.

本文以十四烷基三甲基溴化铵(TTAB)为保护剂, 采用胶体法合成了Ir纳米颗粒, 并将其负载在载体六方氮化硼上, 获得一系列通过不同焙烧温度的催化剂, 通过各种表征手段研究了催化剂结构和表面性质, 并考察其在巴豆醛气相加氢反应中的性能. 热重分析、原位漫反射红外光谱结果表明, 尽管在制备过程中经过充分洗涤, 催化剂表面仍有残留的TTAB存在, 其含量随着焙烧温度的升高而减少, 至500 ^oC焙烧后彻底清除. TTAB覆盖在Ir表面, 并产生了电荷转移. 巴豆醛加氢反应结果表明, 300 ^oC焙烧的催化剂(Ir/BN-C3)具有最佳活性和选择性, 其在准稳态条件下巴豆醇的选择性为94.4%, 巴豆醇的生成转换频率(TOF)为0.02 s^-1; 而500 ^oC焙烧的催化剂(Ir/BN-C5)上, 巴豆醇的稳态选择性仅为56.2%, 巴豆醇的生成TOF为0.004 s^-1. 动力学测试结果表明, 与Ir/BN-C5相比, 巴豆醛在Ir/BN-C3催化剂上具有更高的吸附平衡常数和更高的本征反应速率常数, 表明TTAB的存在有效加强了巴豆醛在催化剂表面的吸附; 另一方面, Ir-TTAB界面活性位比Ir-Ir活性位具有更高的本征活性, 从而验证了Ir-TTAB界面在增强反应物吸附和促进反应速率方面起关键作用. 但过高的TTAB表面覆盖度(例如在100 ^oC焙烧的催化剂Ir/BN-C1中)会抑制H₂在催化剂表面的吸附, 从而使反应速率降低. 综上, 合适的热处理条件可调节有机配体在催化剂上的含量及其与活性金属间的相互作用, 从而同时提高反应活性和选择性, 突破活性-选择性的“跷跷板”瓶颈, 为高效选择性加氢催化剂的设计提供了新思路.

关键词: α,β-不饱和醛, Ir催化剂, TTAB配体, 表面残留物, 反应机理

Abstract:

Ir nanoparticles (NPs) were synthesized via a colloidal method using tetradecyltrimethyl ammonium bromide (TTAB) as the ligand, and the supported Ir/BN catalysts were employed for selective hydrogenation of crotonaldehyde (CRAL). It was found that by proper thermal treatments, the TTAB-capped Ir NPs were very active and selective for the reaction. The Ir/BN catalyst calcined at 300 °C with surface TTAB residue gave a quasi-steady state turnover frequency (TOF) for crotyl alcohol (CROL) formation of 0.02 s^-1 and a CROL selectivity of 94.4%, while that calcined at 500 °C with clean surface gave a TOF of 0.004 s^-1 and a CROL selectivity of 56.2%. The Ir-TTAB interface was essential for the enhanced performance. In-situ IR spectra along with kinetic investigation revealed that TTAB improved CRAL adsorption and strengthened C=O adsorption, which accounted for high activity and selectivity. However, high coverage of TTAB on the Ir surface suppressed the H₂ adsorption and consequently lowered the activity. Thus the findings provided useful information on the design of efficient catalysts for selective hydrogenation.

Key words: α,β-Unsaturated aldehyde, Ir catalyst, TTAB ligand, Surface residue, Reaction mechanism

叶艳文, 胡一鸣, 郑万彬, 贾爱平, 王瑜, 鲁继青. 配体覆盖的Ir催化剂上巴豆醛加氢反应: 金属-有机物界面促进活性和选择性[J]. 催化学报, 2023, 47: 265-277.

Yan-Wen Ye, Yi-Ming Hu, Wan-Bin Zheng, Ai-Ping Jia, Yu Wang, Ji-Qing Lu. Hydrogenation of crotonaldehyde over ligand-capped Ir catalysts: Metal-organic interface boosts both activity and selectivity[J]. Chinese Journal of Catalysis, 2023, 47: 265-277.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64399-2

https://www.cjcatal.com/CN/Y2023/V47/I4/265

图/表 9

参考文献

[1]	Z. M. Michalska, B. Ostaszewski, J. Zientarska, J. M. Rynkowski, J. Mol. Catal. A, 2002, 185, 279-283.
[2]	P. Reyes, G. Pecchi, J. L. G. Fierro, Langmuir, 2001, 17, 522-527.
[3]	X. Chen, Appl. Catal. A, 2003, 253, 359-369.
[4]	L. A. Saudan, Acc. Chem. Res., 2007, 40, 1309-1319.
[5]	L. Pasumansky, C. T. Goralski, B. Singaram, Org. Process Res. Dev., 2006, 10, 959-970.
[6]	J. S. Cha, Org. Process Res. Dev., 2006, 10, 1032-1053.
[7]	B. Cornils, J. Mol. Catal. A, 1999, 143, 1-10.
[8]	M. Englisch, V. S. Ranade, J. A. Lercher, J. Mol. Catal. A, 1997, 121, 69-80.
[9]	A. Dandekar, M. A. Vannice, J. Catal., 1999, 183, 344-354.
[10]	J. Silvestre-Albero, F. Rodriguez-Reinoso, A. Sepulveda-Escribano, J. Catal., 2002, 210, 127-136.
[11]	P. Concepción, A. Corma, J. Silvestre-Albero, V. Franco, J. Y. Chane-Ching, J. Am. Chem. Soc., 2004, 126, 5523-5532.
[12]	F. Ammari, J. Lamotte, R. Touroude, J. Catal., 2004, 221, 32-42.
[13]	F. Ammari, C. Milone, R. Touroude, J. Catal., 2005, 235, 1-9.
[14]	E. V. Ramos-Fernández, B. Samaranch, P. Ramírez de la Piscina, N. Homs, J. L. G. Fierro, F. Rodríguez-Reinoso, A. Sepúlveda-Escribano, Appl. Catal. A, 2008, 349, 165-169.
[15]	J. Hidalgo-Carrillo, M. A. Aramendía, A. Marinas, J. M. Marinas, F. J. Urbano, Appl. Catal. A, 2010, 385, 190-200.
[16]	X. Yang, Y. Mueanngern, Q. A. Baker, L. R. Baker, Catal. Sci. Technol., 2016, 6, 6824-6835.
[17]	M. Englisch, A. Jentys, J. A. Lercher, J. Catal., 1997, 166, 25-35.
[18]	Z. Weng, F. Zaera, ACS Catal., 2018, 8, 8513-8524.
[19]	B. A. Riguetto, C. E. C. Rodrigues, M. A. Morales, E. Baggio-Saitovitch, L. Gengembre, E. Payen, C. M. P. Marques, J. M. C. Bueno, Appl. Catal. A, 2007, 318, 70-78.
[20]	B. Li, X. Hong, J. J. Lin, G. S. Hu, Q. Yu, Y. J. Wang, M. F. Luo, J. Q. Lu, Appl. Surf. Sci., 2013, 280, 179-185.
[21]	M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, Chem. Commun., 2013, 49, 7034-7036.
[22]	P. Reyes, M. C. Aguirre, J. L. G. Fierro, G. Santori, O. Ferretti, J. Mol. Catal. A, 2002, 184, 431-441.
[23]	M. S. Ide, B. Hao, M. Neurock, R.J. Davis, ACS Catal., 2012, 2, 671-683.
[24]	B. C. Campo, M. A. Volpe, C. E. Gigola, Ind. Eng. Chem. Res., 2009, 48, 10234-10239.
[25]	J. E. Bailie, G. J. Hutchings, Chem. Commun., 1999, 2151-2152.
[26]	R. Zanella, C. Louis, S. Giorgio, R. Touroude, J. Catal., 2004, 223, 328-339.
[27]	P. Claus, Appl. Catal. A, 2005, 291, 222-229.
[28]	B. Campo, M. Volpe, S. Ivanova, R. Touroude, J. Catal., 2006, 242, 162-171.
[29]	H. Lin, J. Zheng, X. Zheng, Z. Gu, Y. Yuan, Y. Yang, J. Catal., 2015, 330, 135-144.
[30]	C. Guzmán, G. Del Angel, J. L. G. Fierro, V. Bertin, Top. Catal., 2010, 53, 1142-1144.
[31]	P. Mäki-Arvela, J. Hájek, T. Salmi, D. Y. Murzin, Appl. Catal. A, 2005, 292, 1-49.
[32]	X. Wang, Y. He, Y. Liu, J. Park, X. Liang, J. Catal., 2018, 366, 61-69.
[33]	E. Bailón-García, F. Maldonado-Hódar, A. Pérez-Cadenas, F. Carrasco-Marín, Catalysts, 2013, 3, 853-877.
[34]	G. Kennedy, L. R. Baker, G. A. Somorjai, Angew. Chem. Int. Ed., 2014, 53, 3405-3408.
[35]	X. Ning, Y. M. Xu, A. Q. Wu, C. Tang, A. P. Jia, M. F. Luo, J. Q. Lu, Appl. Surf. Sci., 2019, 463, 463-473.
[36]	Q. Yu, K. K. Bando, J. F. Yuan, C. Q. Luo, A. P. Jia, G. S. Hu, J. Q. Lu, M. F. Luo, J. Phys. Chem. C, 2016, 120, 8663-8673.
[37]	M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, ACS Catal., 2016, 6, 3600-3609.
[38]	Y. M. Xu, W. B. Zheng, Y. M. Hu, C. Tang, A. P. Jia, J. Q. Lu, J. Catal., 2020, 381, 222-233.
[39]	J. F. Yuan, C. Q. Luo, Q. Yu, A. P. Jia, G. S. Hu, J. Q. Lu, M. F. Luo, Catal. Sci. Technol., 2016, 6, 4294-4305.
[40]	Z. Niu, Y. Li, Chem. Mater., 2013, 26, 72-83.
[41]	W. Oberhauser, C. Evangelisti, A. Liscio, A. Kovtun, Y. Cao, F. Vizza, J. Catal., 2018, 368, 298-305.
[42]	B. Wu, H. Huang, J. Yang, N. Zheng, G. Fu, Angew. Chem. Int. Ed., 2012, 51, 3440-3443.
[43]	K. R. Kahsar, D. K. Schwartz, J. W. Medlin, J. Am. Chem. Soc., 2014, 136, 520-526.
[44]	L. Lu, S. Zou, B. Fang, ACS Catal., 2021, 11, 6020-6058.
[45]	S. Lin, X. X. Ye, R.S. Johnson, H. Guo, J. Phys. Chem. C, 2013, 117, 17319-17326.
[46]	Y. M. Lopez-De Jesus, A. Vicente, G. Lafaye, P. Marecot, C. T. Williams, J. Phys. Chem. C, 2008, 112, 13837-13845.
[47]	F. J. C. M. Toolenaar, A. G. T. M. Bastein, V. Ponec, J. Catal., 1983, 82, 35-44.
[48]	C. R. Guerra, J. H. Schulman, Surf. Sci., 1967, 7, 229-249.
[49]	A. Bourane, O. Dulaurent, D. Bianchi, J. Catal., 2000, 195, 406-411.
[50]	S. Ozkan, S. Sen Gursoy, Polymer Eng. Sci., 2016, 56, 995-1003.
[51]	K. M. Bratlie, H. Lee, K. Komvopoulos, P. Yang, G. A. Somorjai, Nano Lett., 2007, 7, 3097-3101.
[52]	B. Nikoobakht, M. A. El-Sayed, Langmuir, 2001, 17, 6368-6374.
[53]	Z. M. Sui, X. Chen, L. Y. Wang, L. M. Xu, W. C. Zhuang, Y. C. Chai, C. J. Yang, Phys. E, 2006, 33, 308-314.
[54]	A. Giroir-Fendler, D. Richard, P. Gallezot, Catal. Lett., 1990, 5, 175-181.
[55]	B. F. Machado, H. T. Gomes, P. Serp, P. Kalck, J. L. Figueiredo, J. L. Faria, Catal. Today, 2010, 149, 358-364.
[56]	P. Reyes, M. C. Aguirre, G. Pecchi, J. L. G. Fierro, J. Mol. Catal. A, 2000, 164, 245-251.
[57]	M. Tamura, K. Tokonami, Y. Nakagawa, K. Tomishige, ACS Sustainable Chem. Eng., 2017, 5, 3685-3697.
[58]	A. J. Bowles, W. O. George, W. F. Maddams, J. Chem. Soc. B, 1969, 810-818.
[59]	P. Reyes, M. C. Aguirre, I. Melián-Cabrera, M. López Granados, J. L. G. Fierro, J. Catal., 2002, 208, 229-237.
[60]	P. Claus, Top. Catal., 1998, 5, 51-62.
[61]	A. Jia, Y. Zhang, T. Song, Z. Zhang, C. Tang, Y. Hu, W. Zheng, M. Luo, J. Lu, W. Huang, J. Catal., 2021, 395, 10-22.
[62]	A. Jia, Y. Zhang, T. Song, Y. Hu, W. Zheng, M. Luo, J. Lu, W. Huang, Chin. J. Catal., 2021, 42, 1742-1754.

Catalyst	Ir content/wt%	Conv. ^a /%	Selectivity ^a/%				Reaction rate /μmol_CRAL g_Ir^-1 s^-1	Formation rate /μmol_CROL g_Ir^-1 s^-1	TOF_CROL ^b /× 10^-3 s^-1
Catalyst	Ir content/wt%	Conv. ^a /%	CROL	BUAL	BUOL	Others	Reaction rate /μmol_CRAL g_Ir^-1 s^-1	Formation rate /μmol_CROL g_Ir^-1 s^-1	TOF_CROL ^b /× 10^-3 s^-1
Ir/BN-C1	1.3	10.9	96.3	2.8	0.4	0.5	16.2	15.6	7.7
Ir/BN-C2	1.3	16.4	96.0	2.4	0.7	0.9	24.4	23.4	n.d.
Ir/BN-C3	1.3	28.9	94.4	3.8	1.1	0.7	43.0	40.6	20.0
Ir/BN-C4	1.3	9.1	58.2	39.7	1.5	0.6	13.5	7.86	n.d.
Ir/BN-C5	1.3	8.9	56.2	41.3	2.0	0.5	13.2	7.41	4.2
Ir/BN-IM-C3	3.0	12.3	49.0	43.7	6.0	1.3	7.93	3.88	1.9

Catalyst	Ir content/wt%	Conv. ^a /%	Selectivity ^a/%				Reaction rate /μmol_CRAL g_Ir^-1 s^-1	Formation rate /μmol_CROL g_Ir^-1 s^-1	TOF_CROL ^b /× 10^-3 s^-1
Catalyst	Ir content/wt%	Conv. ^a /%	CROL	BUAL	BUOL	Others	Reaction rate /μmol_CRAL g_Ir^-1 s^-1	Formation rate /μmol_CROL g_Ir^-1 s^-1	TOF_CROL ^b /× 10^-3 s^-1
Ir/BN-C1	1.3	10.9	96.3	2.8	0.4	0.5	16.2	15.6	7.7
Ir/BN-C2	1.3	16.4	96.0	2.4	0.7	0.9	24.4	23.4	n.d.
Ir/BN-C3	1.3	28.9	94.4	3.8	1.1	0.7	43.0	40.6	20.0
Ir/BN-C4	1.3	9.1	58.2	39.7	1.5	0.6	13.5	7.86	n.d.
Ir/BN-C5	1.3	8.9	56.2	41.3	2.0	0.5	13.2	7.41	4.2
Ir/BN-IM-C3	3.0	12.3	49.0	43.7	6.0	1.3	7.93	3.88	1.9

Catalyst	Power law rate expression CROL formation rate = k_app × 10^-9 [CRAL]^a[H₂]^b			E_a for CROL formation /kJ mol^-1	k/× 10^-7 mol g^-1 s^-1	K_CRAL/kPa^-1	K_H2 × 10^-2/kPa^-1
Catalyst	K_app	a	b	E_a for CROL formation /kJ mol^-1	k/× 10^-7 mol g^-1 s^-1	K_CRAL/kPa^-1	K_H2 × 10^-2/kPa^-1
Ir/BN-C1	0.71	0.35 ± 0.07	0.98 ± 0.06	43.8 ± 3.8	5.05	0.91	0.69
Ir/BN-C3	4.15	0.37 ± 0.02	1.05 ± 0.13	34.5 ± 4.5	18.2	0.86	0.64
Ir/BN-C5	1.25	0.61 ± 0.11	0.66 ± 0.06	40.8 ± 2.5	1.83	0.44	2.19
Ir/BN-IM-C3	1.83	0.63 ± 0.02	0.60 ± 0.02	42.3 ± 1.0	2.38	0.34	2.87

Catalyst	Power law rate expression CROL formation rate = k_app × 10^-9 [CRAL]^a[H₂]^b			E_a for CROL formation /kJ mol^-1	k/× 10^-7 mol g^-1 s^-1	K_CRAL/kPa^-1	K_H2 × 10^-2/kPa^-1
Catalyst	K_app	a	b	E_a for CROL formation /kJ mol^-1	k/× 10^-7 mol g^-1 s^-1	K_CRAL/kPa^-1	K_H2 × 10^-2/kPa^-1
Ir/BN-C1	0.71	0.35 ± 0.07	0.98 ± 0.06	43.8 ± 3.8	5.05	0.91	0.69
Ir/BN-C3	4.15	0.37 ± 0.02	1.05 ± 0.13	34.5 ± 4.5	18.2	0.86	0.64
Ir/BN-C5	1.25	0.61 ± 0.11	0.66 ± 0.06	40.8 ± 2.5	1.83	0.44	2.19
Ir/BN-IM-C3	1.83	0.63 ± 0.02	0.60 ± 0.02	42.3 ± 1.0	2.38	0.34	2.87

On Ir/BN-C5 or Ir/BN-IM-C3 catalyst
$\text{RCHO+I}{{\text{r}}_{1}}*\overset{{{\text{K}}_{\text{CRAL}}}}{\longleftrightarrow}\text{RCHO}-\text{I}{{\text{r}}_{1}}$	(1)
${{\text{H}}_{2}}+\text{I}{{\text{r}}_{2}}*\overset{{{\text{K}}_{{{\text{H}}_{2}}}}}{\longleftrightarrow}{{\text{H}}^{-}}-\text{I}{{\text{r}}_{2}}+{{\text{H}}^{+}}$	(2)
$\text{RCHO}-\text{I}{{\text{r}}_{1}}+{{\text{H}}^{-}}-\text{I}{{\text{r}}_{2}}\xrightarrow{{{\text{k}}_{1}}}\text{RC}{{\text{H}}_{2}}{{\text{O}}^{-}}-\text{I}{{\text{r}}_{1}}+\text{I}{{\text{r}}_{2}}*$	(3) RDS
$\text{RC}{{\text{H}}_{2}}{{\text{O}}^{-}}-\text{I}{{\text{r}}_{1}}+{{\text{H}}^{+}}\xrightarrow{{{\text{k}}_{2}}}\text{RC}{{\text{H}}_{2}}\text{OH}-\text{I}{{\text{r}}_{1}}$	(4)
$\text{RC}{{\text{H}}_{2}}\text{OH}-\text{I}{{\text{r}}_{1}}\overset{{{\text{K}}_{\text{CROL}}}^{-1}}{\longleftrightarrow}\text{RC}{{\text{H}}_{2}}\text{OH+I}{{\text{r}}_{1}}*$	(5)
RCHO + H₂ → RCH₂OH	overall reaction
$\text{r=k}{{\text{K}}_{\text{CRAL}}}{{\text{P}}_{\text{CRAL}}}{{\text{K}}_{{{\text{H}}_{\text{2}}}}}{{\text{P}}_{{{\text{H}}_{\text{2}}}}}\text{/ }\!\![\!\!\text{ (1+}{{\text{K}}_{\text{CRAL}}}{{\text{P}}_{\text{CRAL}}}+{{\text{K}}_{\text{CROL}}}{{\text{P}}_{\text{CROL}}}\text{)(1+}{{\text{K}}_{{{\text{H}}_{\text{2}}}}}{{\text{P}}_{{{\text{H}}_{\text{2}}}}}\text{) }\!\!]\!\!\text{ }$ Ir₁: site for CRAL (RCHO) adsorption; Ir₂: site for H₂ adsorption	rate expression
On Ir/BN-C1 or Ir/BN-C3 catalyst*
$\text{RCHO+TTAB*}\overset{{{\text{K}}_{\text{CRAL}}}}{\longleftrightarrow}\text{RCHO-TTAB}$	(1’)
${{\text{H}}_{2}}+\text{I}{{\text{r}}_{2}}*\overset{{{\text{K}}_{{{\text{H}}_{2}}}}}{\longleftrightarrow}{{\text{H}}^{-}}-\text{I}{{\text{r}}_{2}}+{{\text{H}}^{+}}$	(2’)
$\text{RCHO}-\text{TTAB}+{{\text{H}}^{-}}-\text{I}{{\text{r}}_{2}}\xrightarrow{{{\text{k}}_{1}}}\text{RC}{{\text{H}}_{2}}{{\text{O}}^{-}}-\text{TTAB}+\text{I}{{\text{r}}_{2}}*$	(e3’) RDS
$\text{RC}{{\text{H}}_{2}}{{\text{O}}^{-}}-\text{TTAB}+{{\text{H}}^{+}}\xrightarrow{{{\text{k}}_{2}}}\text{RC}{{\text{H}}_{2}}\text{OH}-\text{I}{{\text{r}}_{1}}$	(4’)
$\text{RC}{{\text{H}}_{2}}\text{OH}-\text{TTAB}\overset{{{\text{K}}_{\text{CROL}}}^{-1}}{\longleftrightarrow}\text{RC}{{\text{H}}_{2}}\text{OH+TTAB}*$	(5’)
RCHO + H₂ → RCH₂OH	overall reaction
$\text{r=k}{{\text{K}}_{\text{CRAL}}}{{\text{P}}_{\text{CRAL}}}{{\text{K}}_{{{\text{H}}_{\text{2}}}}}{{\text{P}}_{{{\text{H}}_{\text{2}}}}}\text{/ }\!\![\!\!\text{ (1+}{{\text{K}}_{\text{CRAL}}}{{\text{P}}_{\text{CRAL}}}+{{\text{K}}_{\text{CROL}}}{{\text{P}}_{\text{CROL}}}\text{)(1+}{{\text{K}}_{{{\text{H}}_{\text{2}}}}}{{\text{P}}_{{{\text{H}}_{\text{2}}}}}\text{) }\!\!]\!\!\text{ }$ TTAB: site for CRAL (RCHO) adsorption; Ir₂: site for H₂ adsorption	rate expression
^*: Eqs. (1’)-(6’) only represent those on Ir-TTAB interfacial sites.

配体覆盖的Ir催化剂上巴豆醛加氢反应: 金属-有机物界面促进活性和选择性

Hydrogenation of crotonaldehyde over ligand-capped Ir catalysts: Metal-organic interface boosts both activity and selectivity

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 9

参考文献

相关文章 15

编辑推荐

Metrics

[1]	刘润泽, 邵雪, 王畅, 戴卫理, 关乃佳. 甲醇制烃反应机理: 基础及应用研究[J]. 催化学报, 2023, 47(4): 67-92.
[2]	刘丹卿, 张丙兴, 赵国强, 陈建, 潘洪革, 孙文平. 原位电化学扫描探针显微镜技术在电催化领域的应用进展[J]. 催化学报, 2023, 47(4): 93-120.
[3]	Johannes A. Lercher. 三氧化钨催化糖分子选择裂解新机理及其对生物质利用的重要意义[J]. 催化学报, 2023, 46(3): 1-3.
[4]	黄志鹏, 杨阳, 穆骏驹, 李根恒, 韩建宇, 任濮宁, 张健, 罗能超, 韩克利, 王峰. 利用金属-自由基相互作用调控自由基的定向转化[J]. 催化学报, 2023, 45(2): 120-131.
[5]	周紫璇, 高鹏. 多相催化CO₂加氢直接合成大宗化学品与液体燃料[J]. 催化学报, 2022, 43(8): 2045-2056.
[6]	林波, 夏梦阳, 许堡荣, 种奔, 陈子浩, 杨贵东. 仿生纳米结构的g-C₃N₄基光催化剂研究进展[J]. 催化学报, 2022, 43(8): 2141-2172.
[7]	王梦茹, 王奕, 牟效玲, 林荣和, 丁云杰. 1,3-丁二烯选择性加氢催化剂的设计策略以及构效关系[J]. 催化学报, 2022, 43(4): 1017-1041.
[8]	吴建祥, 杨雪晶, 龚鸣. 甘油电催化氧化的研究进展：催化剂、机理和应用[J]. 催化学报, 2022, 43(12): 2966-2986.
[9]	苏海胜, 常晓侠, 徐冰君. 表面增强振动光谱在电催化领域的运用: 基本原理、挑战和展望[J]. 催化学报, 2022, 43(11): 2757-2771.
[10]	曾辉炎, 曾衍铨, 漆俊, 顾龙, 洪恩纳, 司锐, 杨纯臻. 析氧反应中催化剂-电解质界面的质子动力学研究[J]. 催化学报, 2022, 43(1): 139-147.
[11]	张学鹏, 王红艳, 郑浩铨, 张伟, 曹睿. 分子催化剂催化水氧化过程及其O-O成键机理[J]. 催化学报, 2021, 42(8): 1253-1268.
[12]	邵方君, 姚子豪, 高怡静, 周强, 包志康, 庄桂林, 钟兴, 伍川, 魏中哲, 王建国. 双功能催化剂Ru₂P在N-杂环加氢和无受体脱氢反应中的几何效应和电子效应[J]. 催化学报, 2021, 42(7): 1185-1194.
[13]	张默, 李慧杰, 张峻豪, 吕红金, 杨国昱. 基于多金属氧酸盐催化剂的光驱动产氢研究进展[J]. 催化学报, 2021, 42(6): 855-871.
[14]	王嘉, 尤瑞, 千坤, 潘洋, 杨玖重, 黄伟新. Cl^-改性对Ag/Al₂O₃催化剂结构及其催化C₃H₆-SCR和H₂/C₃H₆-SCR反应性能的影响[J]. 催化学报, 2021, 42(12): 2242-2253.
[15]	何烨, 李解元, 李康璐, 孙明禄, 袁潮苇, 陈瑞敏, 盛剑平, 冷庚, 董帆. Bi量子点修饰的C掺杂二维BiOCl纳米片:增强的可见光光催化活性和反应路径[J]. 催化学报, 2020, 41(9): 1430-1438.