三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态

doi:10.1016/S1872-2067(22)64187-1

催化学报 ›› 2023, Vol. 46: 56-63.DOI: 10.1016/S1872-2067(22)64187-1

三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态

刘玥, 章伟, 刘海超^*()

北京大学化学与分子工程学院院, 北京分子科学国家研究中心, 北京 100871

收稿日期:2022-09-01 接受日期:2022-10-20 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: hcliu@pku.edu.cn (刘海超)
基金资助:
国家重点研发计划(2021YFA1501104);国家自然科学基金(22032001);国家自然科学基金(21832001);国家自然科学基金(21821004);国家自然科学基金(21690081);北京分子科学国家研究中心基金(BNLMS-CXXM-201905)

Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols

Yue Liu, Wei Zhang, Haichao Liu^*()

Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2022-09-01 Accepted:2022-10-20 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: hcliu@pku.edu.cn (H. Liu)
Supported by:
National Key Research and Development Program of China(2021YFA1501104);The Natural Science Foundation of China(22032001);The Natural Science Foundation of China(21832001);The Natural Science Foundation of China(21821004);The Natural Science Foundation of China(21690081);Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201905)

摘要/Abstract

摘要：

纤维素是自然界最丰富的生物质资源, 大量来源于农林废弃物. 近年来, 人们相继发展了以纤维素为原料合成高附加值化学品的多条路径, 它们有望替代目前相应的化石资源路径. 其中, 以碳化钨(W₂C)、三氧化钨(WO₃)和钨酸(H₂WO₄)为代表的钨基催化剂表现出选择性断裂糖分子C−C键的独特催化性质, 结合不同种类的共催化剂, 可以将纤维素直接解聚转化为乙二醇、1,2-丙二醇、乙醇和乳酸等多种重要的C_2,3产物. 然而, 钨基催化剂在纤维素反应中的真实状态和活性相结构尚不确定. W₂C最早被报道可以高效催化纤维素直接转化为乙二醇. 随后, 我们发现晶态WO₃也具有相似的催化性能, W₂C在反应后其表面被WO₃所覆盖. 在纤维素反应中, 氢气可以将H₂WO₄还原为钨青铜(H_xWO₃)物种.

本文以WO₃和H₂WO₄为代表性钨基催化剂, 采用X射线粉末衍射(XRD)和紫外可见光谱(UV-Vis)研究反应前后的结构性质, 结合反应动力学, 对比不同粒径大小的WO₃催化剂的活性, 识别它们在纤维素转化反应中的真实活性相态. 纤维素反应在478 K, 6 MPa H₂条件下的水中进行, Ru/C为加氢催化剂. 纤维素转化率和产物选择性与WO₃的用量密切相关, 随着WO₃的添加并将其用量逐渐增加到1.0 g, 纤维素转化率从12.5%提高到23.5%, 乙二醇选择性从7.5%增至51.5%, 而己糖醇选择性则从64.7%下降到16.9%. XRD结果表明, WO₃反应前呈现单斜相(m-WO₃), 而反应后转变为t-H_0.33WO₃, 后者在空气中暴露1 h后又被氧化为m-WO₃. 进一步通过时间分辨XRD和UV-Vis光谱表征发现, 在纤维素反应条件下的还原气氛中, WO₃经由WO₃→H_0.23WO₃→H_0.33WO₃的路径被还原, 反应后在暴露的空气中又被氧化为起始状态的WO₃.

同样, H₂WO₄也经历了相似的变化过程. 在纤维素反应中被还原为t-H_0.33WO₃, 而暴露到空气中时则被氧化为WO₃, 但并未转变为起始的H₂WO₄. 对于W, WO₂和W₂C, 在反应后它们的表面几乎被WO₃层覆盖, 95%以上的表面物种为WO₃. 显然, 无论钨基催化剂的初始状态如何不同, 在纤维素转化合成乙二醇反应条件下和暴露空气后, 都会经历WO₃→H_xWO₃→WO₃的氧化还原循环.

本文还研究了在纤维素反应中WO₃和H_xWO₃的溶解性质, 即它们呈现多相催化剂还是均相催化剂的特征. 尽管常温下WO₃在水中不溶解, 但是在纤维素反应的较高温度条件下, 其在水中的溶解性质尚不清楚. 为此, 采用了两种不同粒径和比表面积的WO₃样品: 一个晶粒尺寸为25 nm, 比表面积为18 m²/g, 而另一个晶粒尺寸为63 nm, 比表面积为1.9 m²/g. 它们在催化纤维素反应中, 前者表现出较高的转化率和乙二醇选择性. 该催化活性与粒径和比表面积密切相关的特性反映出WO₃/H_xWO₃是以多相催化剂形式参加反应. 进一步通过测量水的电导, 发现从室温到453 K, WO₃和H_xWO₃的存在不能改变水的电导, 证明它们在纤维素反应条件下的高温水中也不发生溶解.

综上所述, 在纤维素反应的还原性气氛中, 钨基催化剂经历WO₃→H_0.23WO₃→H_0.33WO₃的还原过程, 而反应后H_0.33WO₃物种暴露在空气中则被氧化为WO₃. 在纤维素反应过程中, WO₃和H_xWO₃不发生溶解, 而是以多相形态催化纤维素转化为二元醇, 揭示了钨基催化剂在还原反应条件下的真实状态.

关键词: 纤维素, 三氧化钨, 钨青铜, 乙二醇, 加氢

Abstract:

Tungsten-based catalysts, including crystalline WO₃ and H₂WO₄, have been reported to be efficient for the selective cleavage of C−C bonds of sugar intermediates involved in the conversion of cellulose to ethylene glycol and propylene glycol in combination with hydrogenation catalysts under H₂ atmosphere. However, there is still not a consensus on the actual states of these catalysts during the reaction. Herein, we demonstrate that both WO₃ and H₂WO₄ tended to undergo reduction to hydrogen tungsten bronze (H_xWO₃) species in the cellulose reaction, consisting of H_0.23WO₃ and H_0.33WO₃, which were then re-oxidized to WO₃ upon exposure to ambient air after the reaction. Both WO₃ and H_xWO₃ were insoluble in water and acted as the heterogeneous catalysts in the cellulose reaction, as further validated by the strong dependence of the catalytic activity of WO₃ on its crystallite size and surface area. Such identification of the heterogeneous H_xWO₃ species, albeit exemplified here only from the in situ reduction of WO₃ and H₂WO₄ in the cellulose reaction, unravels the active state of the tungsten-based catalysts under reductive reaction conditions.

Key words: Cellulose, Tungsten trioxide, Hydrogen tungsten bronze, Ethylene glycol, Hydrogenation

刘玥, 章伟, 刘海超. 三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态[J]. 催化学报, 2023, 46: 56-63.

Yue Liu, Wei Zhang, Haichao Liu. Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols[J]. Chinese Journal of Catalysis, 2023, 46: 56-63.

×
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(22)64187-1

https://www.cjcatal.com/CN/Y2023/V46/I3/56

图/表 11

Table 1 Cellulose conversion and product selectivity under catalysis of WO3 and Ru/C a

Entry	WO₃ loading (g)	Conversion (%)	Product selectivity (carbon%)
Entry	WO₃ loading (g)	Conversion (%)	Ethylene glycol	Triols ^b	Tetritols ^c	Pentitols ^d	Hexitols ^e
1	0	12.5	7.5	6.3	3.2	10.3	64.7
2	0.1	16.2	16.8	9.4	3.8	6.7	56.1
3	0.2	18.1	24.9	12.0	9.8	3.5	42.9
4	0.5	20.4	48.3	9.2	9.3	1.5	21.8
5	1.0	23.4	51.5	9.5	3.8	1.1	16.9

Fig. 1. XRD patterns of WO3 before and after cellulose reaction. Reaction conditions: 1.0 g WO3, 0.02 g Ru/C, 6 MPa H2, 40 mL water, 1.0 g cellulose, 478 K, 30 min.

Fig. 2. XRD patterns of WO3 before and after treatment under sugar reaction conditions in the 2θ range of 10°?60° (a) and of 22°?25° for clarity (b). Experimental conditions: 453 K, 6 MPa H2, 20 mL water, 0.02 g Ru/C, 1.0 g WO3. In order to minimize the exposure of WO3 samples to ambient air, XRD measurement was carried out immediately after their treatment by transferring them from autoclave reactor to XRD sample holder in slurry with the reaction solution.

Scheme 1. Changes of WO3 in the catalytic reaction of cellulose.

Fig. 3. (a) UV-Vis spectra of WO3 mixed with Ru/C as a function of exposure time to 1 bar H2 and 3 kPa H2O at 453 K, and (b) the evolution of reflectance at 700 nm with exposure time to H2 and water vapor at 453 K and after switching to dry air at 298 K. Experiment conditions: 1.0 g WO3, 0.01 g 3%Ru/C, 50 mL/min H2 carrying 3 kPa H2O vapor at 453 K or 50 mL/min dry air at 298 K.

Table 2 Surface W6+ fractions on fresh and used W2C, W and WO2 catalysts.a

Catalyst	W⁶⁺ fraction
Catalyst	On fresh catalyst	On used catalyst
W₂C	46%	95%
W	54%	98%
WO₂	68%	99%

Fig. 5. Comparison of WO3 and WO3(s). (a) XRD patterns of WO3 and WO3(s). (b) Conversions and product selectivities of cellulose reactions catalyzed by WO3 and WO3(s). Reaction condition: 1.0 g cellulose, 0.05 g WO3 or WO3(s), [0.5 g for WO3(s) × 10], 0.05 g Ru/C, 40 mL H2O, 6 MPa H2, 478 K, 30 min.

Fig. 4. XRD patterns of H2WO4 before and after cellulose reaction. Reaction conditions: 1.0 g H2WO4, 0.02 g Ru/C, 6 MPa H2, 40 mL water, 1.0 g cellulose, 478 K, 30 min.

Scheme 2. Changes of tungsten species during catalytic reactions of cellulose under H2 atmosphere in the presence of Ru/C.

Fig. 6. Electrical conductance of water as a function of temperature in the presence and absence of WO3 and HxWO3. For clearly discerning the data points, in the inset graph the temperature of the result from WO3 and HxWO3 were purposely shifted by ?5 K and +5 K, respectively. Experimental conditions: 10 mL water, 0.25 g WO3 or HxWO3.

Fig. 7. Comparison of cellulose reactions catalyzed by WO3 and HxWO3. (a) Cellulose conversion and yields of ethylene glycol and sorbitol as a function of reaction time. (b) Selectivity of ethylene glycol and sorbitol at different conversions of cellulose. Reaction conditions: 1.0 g cellulose, 1.0 g WO3 or HxWO3, 0.03 g Ru/C, 40 mL H2O, 6 MPa H2, 478 K.

参考文献

[1]	Y. H. Liao, S. F. Koelewijn, G. Van den Bossche, J. Van Aelst, S. Van den Bosch, T. Renders, K. Navare, T. Nicolai, K. Van Aelst, M. Maesen, H. Matsushima, J. M. Thevelein, K. Van Acker, B. Lagrain, D. Verboekend, B. F. Sels, Science, 2020, 367, 1385-1390.
[2]	R. L. Shahab, S. Brethauer, M. P. Davey, A. G. Smith, S. Vignolini, J. S. Luterbacher, M. H. Studer, Science, 2020, 369, eabb1214.
[3]	T. Deng, H. Liu, Green Chem., 2013, 15, 116-124.
[4]	W. Liu, Y. Chen, H. Qi, L. Zhang, W. Yan, X. Liu, X. Yang, S. Miao, W. Wang, C. Liu, A. Wang, J. Li, T. Zhang, Angew. Chem. Int. Ed., 2018, 57, 7071-7075.
[5]	L. T. Mika, E. Csefalvay, A. Nemeth, Chem. Rev., 2018, 118, 505-613.
[6]	T. Deng, X. He, H. Liu, Chem. Res. Chin. Uni., 2022, 38, 257-264.
[7]	Y. Liu, L. Chen, W. Zhang, H. Liu, CCS Chem., 2022, 4, 3162-3169.
[8]	F. Gu, H. Liu, Chin. J. Catal., 2020, 41, 1073-1080.
[9]	X. C. Li, Y. Y. Zhang, Q. N. Xia, X. H. Liu, K. H. Peng, S. H. Yang, Y. Q. Wang, Ind. Eng. Chem. Res., 2018, 57, 3545-3553.
[10]	A. Fukuoka, P. L. Dhepe, Angew. Chem. Int. Ed., 2006, 45, 5161-5163.
[11]	N. Li, X. Liu, J. Zhou, Q. Ma, M. Liu, W. Chen, ACS Sustainable Chem. Eng., 2020, 8, 9650-9659.
[12]	N. X. Li, Y. Zheng, L. F. Wei, H. C. Tenga, J. C. Zhou, Green Chem., 2017, 19, 682-691.
[13]	N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H. Wang, X. D. Wang, J. G. G. Chen, Angew. Chem. Int. Ed., 2008, 47, 8510-8513.
[14]	J. C. Chai, S. H. Zhu, Y. L. Cen, J. Guo, J. G. Wang, W. B. Fan, RSC Adv., 2017, 7, 8567-8574.
[15]	Z. J. Tai, J. Y. Zhang, A. Q. Wang, M. Y. Zheng, T. Zhang, Chem. Commun., 2012, 48, 7052-7054.
[16]	C. Li, G. Xu, X. Zhang, Y. Fu, Chin. J. Chem., 2020, 38, 453-457.
[17]	C. W. Liu, C. H. Zhang, S. K. Sun, K. K. Liu, S. L. Hao, J. Xu, Y. L. Zhu, Y. W. Li, ACS Catal., 2015, 5, 4612-4623.
[18]	Y. Liu, C. Luo, H. Liu, Angew. Chem. Int. Ed., 2012, 51, 3249-3253.
[19]	Y. Liu, H. Liu, Catal. Today, 2016, 269, 74-81.
[20]	M. Yang, H. Qi, F. Liu, Y. Ren, X. Pan, L. Zhang, X. Liu, H. Wang, J. Pang, M. Zheng, A. Wang, T. Zhang, Joule, 2019, 3, 1937-1948.
[21]	H. Song, P. Wang, S. Li, W. Deng, Y. Li, Q. Zhang, Y. Wang, Chem. Commun., 2019, 55, 4303-4306.
[22]	C. Li, G. Xu, C. Wang, L. Ma, Y. Qiao, Y. Zhang, Y. Fu, Green Chem., 2019, 21, 2234-2239.
[23]	D. W. Chu, Y. Y. Xin, C. Zhao, Chin. J. Catal., 2021, 42, 844-854.
[24]	N. Shi, Q. Liu, X. He, H. Cen, R. Ju, Y. Zhang, L. Ma, Bioresour. Technol. Rep., 2019, 5, 66-73.
[25]	Y. Liu, W. Zhang, C. Hao, S. Wang, H. Liu, Proc. Natl. Acad. Sci. USA, 2022, 119, e2206399119.
[26]	G. H. Zhao, M. Y. Zheng, R. Y. Sun, Z. J. Tai, J. F. Pang, A. Q. Wang, X. D. Wang, T. Zhang, AIChE J., 2017, 63, 2072-2080.
[27]	N. Li, Z. Ji, L. Wei, Y. Zheng, Q. Shen, Q. Ma, M. Tan, M. Zhan, J. Zhou, Bioresour. Technol., 2018, 264, 58-65.
[28]	J. J. Wiesfeld, P. Peršolja, F. A. Rollier, A. M. Elemans-Mehring, E. J. M. Hensen, Mol. Catal., 2019, 473, 110400.
[29]	L. S. Ribeiro, J. Orfao, J. J. D. Orfao, M. F. R. Pereira, Cellulose, 2018, 25, 2259-2272.
[30]	S. P. Wang, J. Z. Chen, L. M. Chen, Catal. Lett., 2014, 144, 1728-1734.
[31]	J. E. Benson, H. W. Kohn, M. Boudart, J. Catal., 1966, 5, 307-313.
[32]	Y. Xi, Q. Zhang, H. Cheng, J. Phys. Chem. C, 2014, 118, 494-501.
[33]	B. Ma, E. W. Huang, G. J. Wu, W. L. Dai, N. J. Guan, L. D. Li, RSC Adv., 2017, 7, 2606-2614.
[34]	D. R. Lide, CRC Handbook of Chemistry and Physics, 84th ed., 2003-2004.
[35]	P. G. Dickens, R. J. Hurditch, Nature, 1967, 215, 1266-1267.
[36]	L. Jin, Q. Zhang, R. J. Cava, J. Solid State Chem., 2021, 297, 122059.

三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态

Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

[1]	陈智冰, 陈鑫泰, 吕雅丽, 牟效玲, 范佳辉, 李经伟, 严丽, 林荣和, 丁云杰. 用于丁二烯选择性加氢Ni₃ZnC_0.7@Ni@C催化剂的设计[J]. 催化学报, 2024, 60(5): 304-315.
[2]	陈欢, 虞周楠, 杨冰, 张亚峰, 车春霞, 刘晓艳, 张峰, 韩伟, 温翯, 王爱琴, 张涛. 乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用[J]. 催化学报, 2024, 60(5): 190-200.
[3]	王杰, 陈怡和, 王宇达, 赵浩, 叶进裕, 程庆庆, 杨辉. 调控Ru的电子态以促进乙烯在酸中高选择性电氧化合成乙二醇[J]. 催化学报, 2024, 60(5): 376-385.
[4]	Nikolay Nesterov, Alexey Philippov, Vera Pakharukova, Evgeny Gerasimov, Stanislav Yakushkin, Oleg Martyanov. 伯醇对镍基催化剂在转移氢化反应中的抑制作用研究[J]. 催化学报, 2024, 58(3): 168-179.
[5]	Yaejun Baik, Kyeongjin Lee, Minkee Choi. 甘油三酯催化转化为柴油、喷气燃料和润滑油基础油[J]. 催化学报, 2024, 58(3): 15-24.
[6]	鲍文静, 冯超, 马书妍, 闫登伟, 张聪, 岳长乐, 王崇泽, 郭海玲, 王继乾, 孙道峰, 柳云骐, 卢玉坤. 可控构建Co₃S₄@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫[J]. 催化学报, 2024, 57(2): 154-170.
[7]	韩策, 梅丙宝, 张庆华, 张慧敏, 姚鹏飞, 宋平, 宫雪, 崔培昕, 姜政, 谷林, 徐维林. 钒掺杂钨青铜内通道氨配位的钌单原子用于高效析氢反应[J]. 催化学报, 2023, 51(8): 80-89.
[8]	刘诗瑶, 巩玉同, 杨晓, 张楠楠, 刘会斌, 梁长海, 陈霄. 具有富电子镍位点的耐酸金属间化合物CaNi₂Si₂催化剂用于不饱和有机酸酐/酸的水相加氢[J]. 催化学报, 2023, 50(7): 260-272.
[9]	孟帅奇, 李忠玉, 张鹏, Francisca Contreras, 季宇, Ulrich Schwaneberg. 深度学习指导的热裂褐藻角质酶工程用于促进PET解聚[J]. 催化学报, 2023, 50(7): 229-238.
[10]	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(6): 180-187.
[11]	张锋伟, 郭河芳, 刘萌萌, 赵阳, 洪峰, 李静静, 董正平, 乔波涛. 表面应力介导的碳基Pt纳米催化剂用于硝基芳烃的高选择性加氢[J]. 催化学报, 2023, 48(5): 195-204.
[12]	Eun Hyup Kim, Min Hee Lee, Jeehye Kim, Eun Cheol Ra, Ju Hyeong Lee, Jae Sung Lee. 无碱CO₂加氢高效制甲酸Pd/g-C₃N₄催化剂的单原子和纳米簇的协同作用[J]. 催化学报, 2023, 47(4): 214-221.
[13]	曾严, 王慧, 杨惠茹, 隽超, 李丹, 温晓东, 张帆, 邹吉军, 彭冲, 胡常伟. 镍纳米粒子耦合氧空位高效催化转化棕榈酸制备烷烃[J]. 催化学报, 2023, 47(4): 229-242.
[14]	杨成功, 王冬娥, 黄蓉, 韩健强, 塔娜, 马怀军, 曲炜, 潘振栋, 王从新, 田志坚. 高效稳定的MoS₂-TiO₂纳米复合催化剂用于浆态床菲催化加氢[J]. 催化学报, 2023, 46(3): 125-136.
[15]	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.

三氧化钨基催化剂在纤维素选择性转化合成二元醇反应中的活性相态

Unraveling the active states of WO3-based catalysts in the selective conversion of cellulose to glycols

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

Unraveling the active states of WO₃-based catalysts in the selective conversion of cellulose to glycols