Ir-Fe/BN催化剂上Ru物种在1,2-二醇氢解制仲醇反应中的促进作用

doi:10.1016/S1872-2067(24)60110-5

催化学报 ›› 2024, Vol. 65: 89-102.DOI: 10.1016/S1872-2067(24)60110-5

Ir-Fe/BN催化剂上Ru物种在1,2-二醇氢解制仲醇反应中的促进作用

刘奔^a^,^†, 中川善直^a^,^b^,^*(), 藪下瑞帆^a^,^b, 冨重圭一^a^,^b^,^c^,^*()

^a日本东北大学工学部应用化学系, 仙台, 日本
^b日本东北大学稀有金属与绿色创新研究中心, 仙台, 日本
^c日本东北大学材料科学高等研究所, 仙台, 日本

收稿日期:2024-06-25 接受日期:2024-07-29 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: yoshinao@erec.che.tohoku.ac.jp (中川善直), tomishige@tohoku.ac.jp (冨重圭一).
作者简介:
^†目前地址: 复旦大学化学系, 上海200433, 中国.

Promoting role of Ru species on Ir-Fe/BN catalyst in 1,2-diols hydrogenolysis to secondary alcohols

Ben Liu^a^,^†, Yoshinao Nakagawa^a^,^b^,^*(), Mizuho Yabushita^a^,^b, Keiichi Tomishige^a^,^b^,^c^,^*()

^aDepartment of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07 Aoba, Aramaki, Aoba-ku, Sendai, 980-8579, Japan
^bResearch Center for Rare Metal and Green Innovation, Tohoku University, 468-1, Aoba, Aramaki, Aoba-ku, Sendai, 980-0845, Japan
^cAdvanced Institute for Materials Research (WPI-AIMR), Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai, 980-8577, Japan

Received:2024-06-25 Accepted:2024-07-29 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: yoshinao@erec.che.tohoku.ac.jp (Y. Nakagawa), tomishige@tohoku.ac.jp (K. Tomishige).
About author:
^†Present address: Department of Chemistry, Fudan University, Shanghai 200433, China.

摘要/Abstract

摘要：

贵金属基双金属催化剂已被系统研究并广泛应用于区域选择性C‒O键氢解进行生物质转化等领域, 而进一步采用贵金属改性非常有应用前景, 亟待深入研究. 本文发现, 在所筛选的贵金属(Ru, Pt, Rh, Pd, Au和Ag)中, Ru是1,2-丁二醇(1,2-BuD)末端C‒O氢解为2-丁醇(2-BuOH)的Ir-Fe/BN(Ir = 5 wt%, Fe/Ir = 0.25)催化剂的有效改性剂. 微量的Ru(0.5 wt%)改性后, 即可高选择性获得2-BuOH(>60%), 活性提升约1倍, 提升Ru负载量(3 wt%)可继续提高活性, 但2-BuOH选择性较低, 并产生了末端C-C键断裂的副产物. 最优催化剂(Ru(0.5)-Ir-Fe/BN)可重复在1,2-BuD氢解反应中使用至少4次, 2-BuOH收率适中(47%). 结果还表明,添加0.5 wt%的Ru促进了Ir-Fe/BN上各种醇的氢解反应. 结合催化反应和表征结果, 研究了Ru物种在三金属催化剂中的促进机理. Ru(0.5)-Ir-Fe/BN中Ru物种与Ir形成合金, 并在与BN表面的界面上富集, 在Ru-Ir-Fe合金中Ru和Fe之间不需要直接相互作用. Ir-Fe合金表面的Ir-Fe界面可能是1,2-二醇通过直接C‒O氢解制备仲醇的活性位点, 其中Ru改性的Ir活化H₂形成氢化物类物质. 由于与Ir物种的直接相互作用和较少暴露于底物, 大大抑制了Ru物种断裂C-C键的活性. Ru负载量较高时(3 wt%)导致形成富Ru三金属合金, 该合金进一步充当C‒C键断裂的活性位.

关键词: 生物质多元醇, 仲醇, 加氢脱氧, 三金属合金, 氮化硼

Abstract:

Noble metal-based-bimetallic catalysts have been highly investigated and applied in wide applications including biomass transformation via regioselective C−O hydrogenolysis while further modification especially with noble metal is highly promising yet still under investigation. Herein, Ru was found as an effective modifier among the screened noble metals (Ru, Pt, Rh, Pd, Au, and Ag) for Ir-Fe/BN (Ir = 5 wt%, Fe/Ir = 0.25) catalyst in terminal C−O hydrogenolysis of 1,2-butanediol (1,2-BuD) to 2-butanol (2-BuOH). Only trace amount of Ru (up to 0.5 wt%) was effective in terms of high 2-BuOH selectivity (> 60%) and activity (about twice). Larger amount of Ru species (3 wt%) highly enhanced the activity but gave low selectivity to 2-BuOH with by-products of terminal C−C bond scission. Optimized catalyst (Ru(0.5)-Ir-Fe/BN) was reusable at least 4 times and gave moderate 2-BuOH yield (47%) in hydrogenolysis of 1,2-BuD. The promoting effect of Ru addition (0.5 wt%) to Ir-Fe/BN on hydrogenolysis of various alcohols was also confirmed. Combining catalytic tests with various characterizations, the promotion mechanism of Ru species in trimetallic catalysts was clarified. The Ru species in Ru(0.5)-Ir-Fe/BN form alloy with Ir and are enriched at the interface with BN surface, and direct interaction between Ru and Fe was not necessary in Ru-Ir-Fe alloy. The interface of Ir and Fe on the surface of Ir-Fe alloy may work as active sites for 1,2-diols to secondary alcohols via direct C−O hydrogenolysis, in which Ru-modified Ir activates H₂ to form hydride-like species. The activity of Ru species in C−C bond cleavage was highly suppressed due to the direct interaction with Ir species and less exposed to substrate. Larger loading amount of Ru species (3 wt%) led to the formation Ru-rich trimetallic alloy, which further works as active sites for C−C bond scission.

Key words: Biomass-based polyols, Secondary alcohol, Hydrodeoxygenation, Trimetallic alloy, Boron nitride

刘奔, 中川善直, 藪下瑞帆, 冨重圭一. Ir-Fe/BN催化剂上Ru物种在1,2-二醇氢解制仲醇反应中的促进作用[J]. 催化学报, 2024, 65: 89-102.

Ben Liu, Yoshinao Nakagawa, Mizuho Yabushita, Keiichi Tomishige. Promoting role of Ru species on Ir-Fe/BN catalyst in 1,2-diols hydrogenolysis to secondary alcohols[J]. Chinese Journal of Catalysis, 2024, 65: 89-102.

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Entry	Catalyst	Conv. /%	Selectivity/%-C								C.B./%
Entry	Catalyst	Conv. /%	1-BuOH	2-BuOH	Butane	1-PrOH	2-PrOH	Propane	Ethane	Methane	C.B./%
1 ^a	Ir/BN	0.6	—	—	—	—	—	—	—	—	102
2 ^a	0.4 wt% FeO_x/BN	<0.5	—	—	—	—	—	—	—	—	103
3 ^a	Ir-Fe/BN	14.6	6.1	68.8	14.8	6.6	0.0	0.6	0.0	3.0	95
4	Ru(0.5)-Ir-Fe/BN	25.7	5.7	62.3	15.9	10.1	0.0	0.6	0.3	5.1	90
5	Pt(0.5)-Ir-Fe/BN	13.9	5.1	61.9	17.3	9.8	0.0	0.0	0.0	5.8	92
6	Rh(0.5)-Ir-Fe/BN	11.9	4.5	55.5	15.4	15.9	0.0	0.3	0.0	8.5	95
7	Pd(0.5)-Ir-Fe/BN	7.1	6.7	66.4	16.4	6.8	0.0	0.0	0.0	3.7	96
8	Au(0.5)-Ir-Fe/BN	9.7	4.9	70.1	16.3	5.4	0.0	0.0	0.0	3.2	92
9	Ag(0.5)-Ir-Fe/BN	10.8	5.2	68.5	17.9	4.6	0.0	0.8	0.0	3.0	92
10	Ru(0.5)/BN	41.5	3.2	5.3	6.8	32.2	0.0	5.3	15.3	31.8	89
11	Ru(0.5)-Fe/BN	<0.5	—	—	—	—	—	—	—	—	100
12	Ru(0.5)-Ir/BN	3.1	18.2	37.1	16.0	12.9	0.0	3.0	2.8	10.0	100
13 ^b	Physical mixture	35.3	5.9	42.0	15.4	20.6	0.0	2.7	1.9	11.5	92

Entry	Catalyst	Conv. /%	Selectivity/%-C								C.B./%
Entry	Catalyst	Conv. /%	1-BuOH	2-BuOH	Butane	1-PrOH	2-PrOH	Propane	Ethane	Methane	C.B./%
1 ^a	Ir/BN	0.6	—	—	—	—	—	—	—	—	102
2 ^a	0.4 wt% FeO_x/BN	<0.5	—	—	—	—	—	—	—	—	103
3 ^a	Ir-Fe/BN	14.6	6.1	68.8	14.8	6.6	0.0	0.6	0.0	3.0	95
4	Ru(0.5)-Ir-Fe/BN	25.7	5.7	62.3	15.9	10.1	0.0	0.6	0.3	5.1	90
5	Pt(0.5)-Ir-Fe/BN	13.9	5.1	61.9	17.3	9.8	0.0	0.0	0.0	5.8	92
6	Rh(0.5)-Ir-Fe/BN	11.9	4.5	55.5	15.4	15.9	0.0	0.3	0.0	8.5	95
7	Pd(0.5)-Ir-Fe/BN	7.1	6.7	66.4	16.4	6.8	0.0	0.0	0.0	3.7	96
8	Au(0.5)-Ir-Fe/BN	9.7	4.9	70.1	16.3	5.4	0.0	0.0	0.0	3.2	92
9	Ag(0.5)-Ir-Fe/BN	10.8	5.2	68.5	17.9	4.6	0.0	0.8	0.0	3.0	92
10	Ru(0.5)/BN	41.5	3.2	5.3	6.8	32.2	0.0	5.3	15.3	31.8	89
11	Ru(0.5)-Fe/BN	<0.5	—	—	—	—	—	—	—	—	100
12	Ru(0.5)-Ir/BN	3.1	18.2	37.1	16.0	12.9	0.0	3.0	2.8	10.0	100
13 ^b	Physical mixture	35.3	5.9	42.0	15.4	20.6	0.0	2.7	1.9	11.5	92

Entry	Catalyst	Conv./%	Selectivity/%-C								C.B./%
Entry	Catalyst	Conv./%	1-BuOH	2-BuOH	Butane	1-PrOH	2-PrOH	Propane	Ethane	Methane	C.B./%
1 ^a	Ir-Fe/BN	14.6	6.1	68.8	14.8	6.6	0.0	0.6	0.0	3.0	95
2	Ru(0.1)-Ir-Fe/BN	15.7	5.0	66.7	16.5	7.5	0.0	0.3	0.0	3.9	94
3	Ru(0.3)-Ir-Fe/BN	18.9	5.4	66.0	13.2	10.7	0.0	0.5	0.0	4.3	92
4	Ru(0.5)-Ir-Fe/BN	25.7	5.7	62.3	15.9	10.1	0.0	0.6	0.3	5.1	90
5 ^b	Ru(0.5)-Ir-Fe/BN	23.3	5.4	58.5	19.4	10.2	0.0	0.7	0.5	5.2	94
6 ^c	Ru(2)-Ir(20)-Fe(1.4)/BN	30.1	7.3	68.5	10.4	9.7	0.0	0.6	0.3	3.2	91
7	Ru(1)-Ir-Fe/BN	28.3	5.3	55.7	15.6	14.3	0.0	1.2	0.6	7.3	93
8	Ru(1.5)-Ir-Fe/BN	48.2	5.3	50.4	15.5	17.1	0.0	2.0	1.1	8.6	93
9	Ru(2)-Ir-Fe/BN	68.4	4.4	40.5	17.0	18.8	0.0	4.2	2.9	12.2	87
10 ^d	Ru(3)-Ir-Fe/BN	29.8	6.1	36.2	14.1	25.9	0.0	4.1	3.0	10.7	101
11	Ru(3)-Ir-Fe/BN	95.3	2.4	28.2	18.9	13.6	0.0	10.5	8.2	18.4	88

Entry	Catalyst	Conv./%	Selectivity/%-C								C.B./%
Entry	Catalyst	Conv./%	1-BuOH	2-BuOH	Butane	1-PrOH	2-PrOH	Propane	Ethane	Methane	C.B./%
1 ^a	Ir-Fe/BN	14.6	6.1	68.8	14.8	6.6	0.0	0.6	0.0	3.0	95
2	Ru(0.1)-Ir-Fe/BN	15.7	5.0	66.7	16.5	7.5	0.0	0.3	0.0	3.9	94
3	Ru(0.3)-Ir-Fe/BN	18.9	5.4	66.0	13.2	10.7	0.0	0.5	0.0	4.3	92
4	Ru(0.5)-Ir-Fe/BN	25.7	5.7	62.3	15.9	10.1	0.0	0.6	0.3	5.1	90
5 ^b	Ru(0.5)-Ir-Fe/BN	23.3	5.4	58.5	19.4	10.2	0.0	0.7	0.5	5.2	94
6 ^c	Ru(2)-Ir(20)-Fe(1.4)/BN	30.1	7.3	68.5	10.4	9.7	0.0	0.6	0.3	3.2	91
7	Ru(1)-Ir-Fe/BN	28.3	5.3	55.7	15.6	14.3	0.0	1.2	0.6	7.3	93
8	Ru(1.5)-Ir-Fe/BN	48.2	5.3	50.4	15.5	17.1	0.0	2.0	1.1	8.6	93
9	Ru(2)-Ir-Fe/BN	68.4	4.4	40.5	17.0	18.8	0.0	4.2	2.9	12.2	87
10 ^d	Ru(3)-Ir-Fe/BN	29.8	6.1	36.2	14.1	25.9	0.0	4.1	3.0	10.7	101
11	Ru(3)-Ir-Fe/BN	95.3	2.4	28.2	18.9	13.6	0.0	10.5	8.2	18.4	88

Substrate	Catalyst	Conv./%	Product (Selectivity/%-C)				C.B./%
(1,2-PrD)	Ir-Fe/BN	12.6	(60.8)	(15.0)	(11.6)	others (12.6)	101
(1,2-PrD)	Ru(0.5)-Ir-Fe/BN	24.1	(56.9)	(13.4)	(11.0)	others (18.7)	97
(Glycerol)	Ir-Fe/BN	21.1	(88.0)	(0.6)	(1.8)	others (9.6)	100
(Glycerol)	Ru(0.5)-Ir-Fe/BN	29.0	(68.7)	(1.0)	(0.9)	others (29.4)	90
(1,2-BuD)	Ir-Fe/BN	14.6	(68.8)	(6.1)	(14.8)	others (10.3)	95
(1,2-BuD)	Ru(0.5)-Ir-Fe/BN	25.7	(62.3)	(5.7)	(15.9)	others (16.1)	90
(1,3-BuD)	Ir-Fe/BN	43.4	(84.5)	(7.8)	(0.8)	others (6.9)	90
(1,3-BuD)	Ru(0.5)-Ir-Fe/BN	54.0	(80.1)	(6.8)	(0.8)	others (12.3)	90

Ir-Fe/BN催化剂上Ru物种在1,2-二醇氢解制仲醇反应中的促进作用

Promoting role of Ru species on Ir-Fe/BN catalyst in 1,2-diols hydrogenolysis to secondary alcohols

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Entry	Catalyst	XRD d/nm^a	TEM d/nm^b	D_XRD /%^a	D_CO /%^c	Valence of Ru^d (XANES)	Valence of Fe^d (XANES)	Valence of Ir^d (XANES)	Ru⁰:Ir⁰:Fe⁰ (XANES)	Ru:Ir:Fe (nominal)	Ru:Ir:Fe^e (XPS)
1	Ir/BN	3.1	n.d.	24	9	—	—	0.9	—	—	—
2	0.4 wt% FeO_x/BN	—	n.d.	—	0	—	2.9	—	—	—	—
3	Ru(0.5)/BN	—	n.d.	—	2	0.3	—	—	—	—	—
4	Ir-Fe/BN	2.6	1.7	42	6	—	0.7	0.6	0:1:0.2	0:1:0.25	0:1:0.4
5	Ru(0.5)-Ir/BN	2.8	1.8	—	9	0	—	0.6	0.2:1:0	0.19:1:0	0.06:1:0
6	Ru(0.5)-Ir-Fe/BN	2.5 (2.0^f)	2.0	44 (55^f)	5 (8^g)	0	0.7	0.6	0.2:1:0.2	0.19:1:0.25	0.05:1:0.3
7	Ru(1.5)-Ir-Fe/BN	n.d.	n.d.	n.d.	5	n.d.	n.d.	n.d.	n.d.	0.57:1:0.25	n.d.
8	Ru(3)-Ir-Fe/BN	2.9	2.4	38	5	0	0.4	0.7	1.3:1:0.2	1.1:1:0.25	n.d.

Sample (loading in wt%)	Edge	Shells	CN^a	R/10^-1 nm^b	σ/10^-1 nm^c
Ru(0.5)/BN	Ru K	Ru-Ru	9.8	2.68	0.070
Ru(0.5)/BN		Ru-O	2.6	2.04	0.060
Ru(0.5)- Ir(5)/BN	Ru K	Ru-Ir	6.9	2.70	0.073
		Ru-Ru	0.8	2.68	0.067
		Ru-B	2.6	2.23	0.062
	Ir L₃	Ir-Ir	7.3	2.75	0.066
		Ir-Ru	1.3^d	2.70^d	0.072
Ru(0.5)-Ir(5)- Fe(0.4)/BN	Ru K	Ru-Ir	6.8	2.68	0.073
		Ru-Ru	1.6	2.74	0.061
		Ru-B	1.9	2.17	0.060
	Fe K	Fe-O	0.7	1.95	0.090
		Fe-Ir	6.0	2.62	0.089
	Ir L₃	Ir-Fe	1.5^d	2.62^d	0.083
		Ir-Ru	1.3^d	2.68^d	0.076
		Ir-Ir	6.2	2.74	0.067
Ru(3)-Ir(5)- Fe(0.4)/BN	Ru K	Ru-Ru	6.2	2.66	0.074
		Ru-Ir	4.0	2.68	0.076
		Ru-Fe	0.4	2.60	0.068
	Fe K	Fe-Fe	0.8	2.55	0.060
		Fe-Ru	1.9	2.60	0.080
		Fe-Ir	3.5	2.63	0.083
	Ir L₃	Ir-Fe	0.9^d	2.63^d	0.103
		Ir-Ru	4.4	2.68	0.071
		Ir-Ir	4.1	2.74	0.065

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