Zr对Ni/Ti3C2催化剂结构及催化肉桂醛选择加氢的影响

doi:10.16085/j.issn.1000-6613.2023-1741

化工进展 ›› 2024, Vol. 43 ›› Issue (11): 6184-6194.DOI: 10.16085/j.issn.1000-6613.2023-1741

• 工业催化 • 上一篇

Zr对Ni/Ti₃C₂催化剂结构及催化肉桂醛选择加氢的影响

李孟函¹(), 苏通明¹, 秦祖赠¹(), 纪红兵¹^,²()

^1.广西大学化学化工学院，广西石化资源加工及过程强化技术重点实验室，广西南宁 530004
^2.浙江工业大学浙江绿色石化与轻烃转化研究院，浙江杭州 310014

收稿日期:2023-10-07 修回日期:2024-04-07 出版日期:2024-11-15 发布日期:2024-12-07
通讯作者: 秦祖赠,纪红兵
作者简介:李孟函（1998—），女，硕士研究生，研究方向为工业催化。E-mail：lmh799648213@163.com。
基金资助:
国家自然科学基金(21968007);广西自然科学基金(2020GXNSFDA297007);广西石化资源加工及过程强化技术重点实验室开放课题(2023K002)

Effect of Zr on the structure and the hydrogenation properties for cinnamaldehyde of Ni/Ti₃C₂ catalyst

LI Menghan¹(), SU Tongming¹, QIN Zuzeng¹(), JI Hongbing¹^,²()

^1.School of Chemistry and Chemical Engineering, Guangxi Key Laboratory of Petrochemical Resourse Processing and Process Intensification Technology, Guangxi University, Nanning 530004, Guangxi, China
^2.Zhejiang Green Petrochemical and Light Hydrocarbon Transformation Research Institute, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2023-10-07 Revised:2024-04-07 Online:2024-11-15 Published:2024-12-07
Contact: QIN Zuzeng, JI Hongbing

摘要/Abstract

摘要：

采用KBH₄还原法制备了Zr负载量为5%～15%（质量分数）的NiZr/Ti₃C₂（MXene）催化剂，通过结构表征结合催化剂上肉桂醛选择加氢活性测试，研究添加Zr对Ni/Ti₃C₂催化剂结构及其催化肉桂醛选择加氢的影响。结果表明，随着Zr负载量的增加，能减少Ni金属颗粒团聚，载体Ti₃C₂的层状结构清晰，催化剂比表面积先增加后减小，表面酸性位点的种类变化不大，其中，10Ni10Zr/Ti₃C₂催化剂的活性金属Ni的平均粒径最小且具有最大比表面积（132.8m²/g），其Brønsted酸强度和稳定性略微增强，Lewis酸强度和稳定性降低，表现出最佳催化性能；在同一反应条件下，与10Ni/Ti₃C₂催化剂相比，10Ni10Zr/Ti₃C₂催化剂上肉桂醛的转化率从92.57%提高到98.34%，苯丙醛的选择性从91.15%增加到94.81%，苯丙醛收率提高了8.86%，在循环实验中表现出较高的稳定性。

关键词: NiZr/Ti₃C₂, 催化, 肉桂醛, 选择加氢, KBH₄还原

Abstract:

NiZr/Ti₃C₂ (Ni mass fraction 10%) catalysts with a Zr supporting amount of 5%—15% were prepared by a KBH₄ reduction method, and the effect of the Zr addition on the structure of the Ni/Ti₃C₂ catalyst and its catalytic activities for cinnamaldehyde selective hydrogenation were investigated by characterization combined with cinnamaldehyde selective hydrogenation on the catalysts. The results showed that with the increase in the Zr supporting amount, the agglomeration of Ni metal particles decreased, and the Ti₃C₂ support of the catalysts exhibited a well-defined layer structure. The specific surface area of the catalysts increased first and then decreased, while the types of surface acid sites changed little. Among them, the 10Ni10Zr/Ti₃C₂ catalyst exhibited a smallest average Ni active metal particle size and a maximum specific surface area of 132.8m²/g, as well as the Brønsted acid strength and stability was slightly enhanced, and the Lewis acid strength and stability was decreased, showing the optimal catalytic activity. Under the same reaction conditions, on the 10Ni10Zr/Ti₃C₂ catalysts, the cinnamaldehyde conversion was increased from 92.57% to 98.34%, the hydrocinnamaldehyde selectivity was increased from 91.15% to 94.81%, the hydrocinnamaldehyde yield was increased by 8.86% compared with the 10Ni/Ti₃C₂ catalyst. Furthermore, the 10Ni10Zr/Ti₃C₂ exhibited a high stability in cycling experiments.

Key words: NiZr/Ti₃C₂, catalysis, cinnamaldehyde, selective hydrogenation, KBH₄ reduction

中图分类号:

TQ531.7

李孟函, 苏通明, 秦祖赠, 纪红兵. Zr对Ni/Ti₃C₂催化剂结构及催化肉桂醛选择加氢的影响[J]. 化工进展, 2024, 43(11): 6184-6194.

LI Menghan, SU Tongming, QIN Zuzeng, JI Hongbing. Effect of Zr on the structure and the hydrogenation properties for cinnamaldehyde of Ni/Ti₃C₂ catalyst[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6184-6194.

图/表 13

图1 Ti3C2(a)、还原后10Ni/Ti3C2(b)、10Ni5Zr/Ti3C2(c)、10Ni10Zr/Ti3C2(d)和10Ni15Zr/Ti3C2(e)的X射线衍射谱

图2 Ti3C2(a)、还原后10Ni/Ti3C2(b)、10Ni5Zr/Ti3C2(c)、10Ni10Zr/Ti3C2(d)和10Ni15Zr/Ti3C2(e)的红外光谱

图3 样品的SEM照片

图4 催化剂的活性金属粒径分布图谱

表1 Ti3C2和Ni基负载Ti3C2催化剂的结构性质

样品	比表面积/m²·g^-1	孔体积/10^-2cm³·g^-1	平均孔径/nm
Ti₃C₂	4.7	1.83	12.17
10Ni/Ti₃C₂	9.6	3.63	11.84
10Ni5Zr/Ti₃C₂	51.6	10.73	6.64
10Ni10Zr/Ti₃C₂	132.8	15.63	3.48
10Ni15Zr/Ti₃C₂	102.2	9.81	2.69

图5 样品的TEM和HRTEM图谱

图6 样品的N2吸附-脱附等温线和BJH解吸的孔径分布

图7 还原后10Ni/Ti3C2和10Ni10Zr/Ti3C2的XPS图谱

图8 催化剂的吡啶吸附-脱附的红外光谱

图9 Ti3C2(a)、还原后10Ni/Ti3C2(b)、10Ni5Zr/Ti3C2(c)、10Ni10Zr/Ti3C2(d)、10Ni15Zr/Ti3C2(e)的NH3-TPD图谱

图10 催化剂上肉桂醛加氢活性测试（催化剂1.0g；肉桂醛1.0g；H2压力2.0MPa；溶剂为30mL乙醇；反应温度120℃）

表2 Ni/Ti3C2和NiZr/Ti3C2催化剂的肉桂醛加氢最优活性

催化剂	时间/min	C_CAL/%	S_HCAL/%	Y_HCAL/%
10Ni/Ti₃C₂	50	92.57	91.15	84.38
10Ni5Zr/Ti₃C₂	10	100.00	25.31	25.31
10Ni10Zr/Ti₃C₂	50	98.34	94.81	93.24
10Ni15Zr/Ti₃C₂	60	27.41	87.32	23.93

图11 10Ni10Zr/Ti3C2的循环稳定性

参考文献 36

1	LI Rongrong, YAO Wubing, JIN Yanxian, et al. Selective hydrogenation of the C ̿ C bond in cinnamaldehyde over an ultra-small Pd-Ag alloy catalyst[J]. Chemical Engineering Journal, 2018, 351: 995-1005.
2	HAN Shiying, LIU Yunfei, LI Jiang, et al. Improvement effect of Ni to Pd-Ni/SBA-15 catalyst for selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde[J]. Catalysts, 2018, 8(5): 200.
3	YANG Xu, WU Liangpeng, DU Li, et al. High performance Pd catalyst using silica modified titanate nanotubes (STNT) as support and its catalysis toward hydrogenation of cinnamaldehyde at ambient temperature[J]. RSC Advances, 2014, 4(108): 63062-63069.
4	Dipak DAS, Kamalesh PAL, LLORCA Jordi, et al. Chemoselective hydrogenation of cinnamaldehyde at atmospheric pressure over combustion synthesized Pd catalysts[J]. Reaction Kinetics, Mechanisms and Catalysis, 2017, 122(1): 135-153.
5	ZHAO Yuan, LIU Mingming, FAN Binbin, et al. Pd nanoparticles supported on ZIF-8 as an efficient heterogeneous catalyst for the selective hydrogenation of cinnamaldehyde[J]. Catalysis Communications, 2014, 57: 119-123.
6	YU Jianyan, YAN Li, TU Gaomei, et al. Magnetically responsive core-shell Pd/Fe₃O₄@C composite catalysts for the hydrogenation of cinnamaldehyde[J]. Catalysis Letters, 2014, 144(12): 2065-2070.
7	FUJIWARA Seika, TAKANASHI Naoto, NISHIYABU Ryuhei, et al. Boronate microparticle-supported nano-palladium and nano-gold catalysts for chemoselective hydrogenation of cinnamaldehyde in environmentally preferable solvents[J]. Green Chemistry, 2014, 16(6): 3230-3236.
8	XU Hailong, CHEN Miaomiao, JI Min. Solid Lewis acid-base pair catalysts constructed by regulations on defects of UiO-66 for the catalytic hydrogenation of cinnamaldehyde[J]. Catalysis Today, 2022, 402: 52-59.
9	CUI Haishuai, ZHONG Linhao, LV Yang, et al. A facile synthesis of in-situ formed amorphous zirconia catalysts for efficient transfer hydrogenation of unsaturated aldehydes[J]. Fuel, 2022, 317: 123551.
10	王颖杰, 祝新利. 溶胶-凝胶法制备高分散Ni-Cu/SiO₂促进间甲酚直接脱氧制甲苯[J]. 化工进展, 2024, 43（7）：3824-3833.
	WANG Yingjie, ZHU Xinli. Preparation of highly dispersed Ni-Cu/SiO₂ by sol-gel method to promote direct deoxygenation of m-cresol to toluene[J]. Chemical Industry and Engineering Progress, 2024, 43（7）：3824-3833.
11	万成凤, 李志达, 张春月, 等. MXene负载CoP纳米棒高效电催化分解水制氢[J]. 化工进展, 2024, 43（6）：3232-3239.
	WAN Chengfeng, LI Zhida, ZHANG Chunyue, et al. MXene-loaded CoP nanorods for efficient electrocatalytic decomposition of water to produce hydrogen[J]. Chemical Industry and Engineering Progress, 2024, 43（6）：3232-3239.
12	YUAN Zhenluo, ZHANG Dafeng, FAN Guangxin, et al. Synergistic effect of CeF₃ nanoparticles supported on Ti₃C₂ MXene for catalyzing hydrogen storage of NaAlH₄ [J]. ACS Applied Energy Materials, 2021, 4(3): 2820-2827.
13	LIU Anmin, YANG Qiyue, REN Xuefeng, et al. Two-dimensional CuAg/Ti₃C₂ catalyst for electrochemical synthesis of ammonia under ambient conditions: A combined experimental and theoretical study[J]. Sustainable Energy & Fuels, 2020, 4(10): 5061-5071.
14	LI Menghan, LUO Xuan, SU Tongming, et al. NiZr/N-doped TiO₂/Ti₃C₂ catalyst for the selective hydrogenation of cinnamaldehyde: Effect of N-doping of TiO₂ [J]. ChemistrySelect, 2023, 8(48): e202303437.
15	CHEN Liuyun, HUANG Kelin, XIE Qingruo, et al. The enhancement of photocatalytic CO₂ reduction by the in situ growth of TiO₂ on Ti₃C₂ MXene[J]. Catalysis Science & Technology, 2021, 11(4): 1602-1614.
16	GAO Han, ZHAO Binxia, LUO Jinchao, et al. Fe-Ni-Al pillared montmorillonite as a heterogeneous catalyst for the catalytic wet peroxide oxidation degradation of orange acid Ⅱ: Preparation condition and properties study[J]. Microporous and Mesoporous Materials, 2014, 196: 208-215.
17	ZHANG Guangcheng, FAN Guoli, YANG Lan, et al. Tuning surface-interface structures of ZrO₂ supported copper catalysts by in situ introduction of indium to promote CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2020, 605: 117805.
18	KE Tao, SHEN Shuyi, RAJAVEL Krishnamoorthy, et al. In situ growth of TiO₂ nanoparticles on nitrogen-doped Ti₃C₂ with isopropyl amine toward enhanced photocatalytic activity[J]. Journal of Hazardous Materials, 2021, 402: 124066.
19	LI Hui, HAO Yubao, LU Haiqiang, et al. A systematic study on visible-light N-doped TiO₂ photocatalyst obtained from ethylenediamine by sol-gel method[J]. Applied Surface Science, 2015, 344: 112-118.
20	ZHENG Rui, LI Chunhu, HUANG Kelei, et al. TiO₂/Ti₃C₂ intercalated with g-C₃N₄ nanosheets as 3D/2D ternary heterojunctions photocatalyst for the enhanced photocatalytic reduction of nitrate with high N₂ selectivity in aqueous solution[J]. Inorganic Chemistry Frontiers, 2021, 8(10): 2518-2531.
21	SU Tongming, HOOD Zachary D, NAGUIB Michael, et al. Monolayer Ti₃C₂T _x as an effective co-catalyst for enhanced photocatalytic hydrogen production over TiO₂ [J]. ACS Applied Energy Materials, 2019, 2(7): 4640-4651.
22	HE Jun, LIU Xiaoyi, DENG Yonghe, et al. Improved magnetic loss and impedance matching of the FeNi-decorated Ti₃C₂T _x MXene composite toward the broadband microwave absorption performance[J]. Journal of Alloys and Compounds, 2021, 862: 158684.
23	WANG Fei, BI Yanshuai, CHEN Nan, et al. In-situ synthesis of Ni nanoparticles confined within SiO₂ networks with interparticle mesopores with enhanced selectivity for cinnamaldehyde hydrogenation[J]. Chemical Physics Letters, 2018, 711: 152-155.
24	WU Zhaoxuan, YANG Bing, MIAO Shu, et al. Lattice strained Ni-Co alloy as a high-performance catalyst for catalytic dry reforming of methane[J]. ACS Catalysis, 2019, 9(4): 2693-2700.
25	YANG Chao, TAN Qiuyan, LI Qin, et al. 2D/2D Ti₃C₂ MXene/g-C₃N₄ nanosheets heterojunction for high efficient CO₂ reduction photocatalyst: Dual effects of urea[J]. Applied Catalysis B: Environmental, 2020, 268: 118738.
26	HUANG Kelei, LI Chunhu, ZHANG Xiuli, et al. Self-assembly synthesis of phosphorus-doped tubular g-C₃N₄/Ti₃C₂ MXene Schottky junction for boosting photocatalytic hydrogen evolution[J]. Green Energy & Environment, 2023, 8(1): 233-245.
27	HUANG Kelei, LI Chunhu, MENG Xiangchao. In-situ construction of ternary Ti₃C₂ MXene@TiO₂/ZnIn₂S₄ composites for highly efficient photocatalytic hydrogen evolution[J]. Journal of Colloid and Interface Science, 2020, 580: 669-680.
28	ROMERO-SÁEZ M, DONGIL A B, BENITO N, et al. CO₂ methanation over nickel-ZrO₂ catalyst supported on carbon nanotubes: A comparison between two impregnation strategies[J]. Applied Catalysis B: Environmental, 2018, 237: 817-825.
29	GAO Xueying, YU Xin, PENG Lincai, et al. Magnetic Fe₃O₄ nanoparticles and ZrO₂-doped mesoporous MCM-41 as a monolithic multifunctional catalyst for γ-valerolactone production directly from furfural[J]. Fuel, 2021, 300: 120996.
30	Mehmet AKÇAY. The surface acidity and characterization of Fe-montmorillonite probed by in situ FT-IR spectroscopy of adsorbed pyridine[J]. Applied Catalysis A: General, 2005, 294(2): 156-160.
31	WU Jianfeng, SU Tongming, JIANG Yuexiu, et al. In situ DRIFTS study of O₃ adsorption on CaO, γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO at room temperature for the catalytic ozonation of cinnamaldehyde[J]. Applied Surface Science, 2017, 412: 290-305.
32	TRAVERT Arnaud, VIMONT Alexandre, LAVALLEY Jean-Claude. An example of misinterpretation of IR spectra of adsorbed species due to gas phase H₂O: Comment on “The surface acidity and characterization of Fe-montmorillonite probed by in situ FT-IR spectroscopy of adsorbed pyridine” [Appl. Catal. A 294 (2005) 156-160][J]. Applied Catalysis A: General, 2006, 302(2): 333-334.
33	YANG Lan, JIANG Zhongshan, FAN Guoli, et al. The promotional effect of ZnO addition to supported Ni nanocatalysts from layered double hydroxide precursors on selective hydrogenation of citral[J]. Catalysis Science & Technology, 2014, 4(4): 1123-1131.
34	CHMIELARZ Lucjan, Piotr KUŚTROWSKI, ZBROJA Małorzata, et al. SCR of NO by NH₃ on alumina or titania pillared montmorillonite modified with Cu or Co Part II. Temperature programmed studies[J]. Applied Catalysis B: Environmental, 2004, 53(1): 47-61.
35	WANG Xiaofeng, LIANG Xinhua, GENG Peng, et al. Recent advances in selective hydrogenation of cinnamaldehyde over supported metal-based catalysts[J]. ACS Catalysis, 2020, 10(4): 2395-2412.
36	LIU Hongli, LI Zhong, LI Yingwei. Chemoselective hydrogenation of cinnamaldehyde over a pt-lewis acid collaborative catalyst under ambient conditions[J]. Industrial & Engineering Chemistry Research, 2015, 54(5): 1487-1497.

[1]	高聪志, 张雅萱, 林璐, 邓晓婷, 殷霞, 丁一刚, 肖艳华, 杜治平. 新戊二醇的合成工艺[J]. 化工进展, 2024, 43(S1): 469-478.
[2]	万震, 王绍庆, 李志合, 赵天生. HZSM-5分子筛催化木质素热解制芳烃研究进展[J]. 化工进展, 2024, 43(S1): 517-532.
[3]	李琳, 黄国勇, 徐盛明, 郁丰善, 翁雅青, 曹才放, 温嘉玮, 王春霞, 王俊莲, 顾斌涛, 张袁华, 刘斌, 王才平, 潘剑明, 徐泽良, 王翀, 王珂. 铝基废催化剂载体的回收与再生制备[J]. 化工进展, 2024, 43(S1): 640-649.
[4]	李新月, 李振京, 韩沂杭, 郭永强, 闫瑜, 哈力米热·卡热木拉提, 赵会吉, 柴永明, 刘东, 殷长龙. 油脂加氢脱氧生产绿色柴油催化剂的研究进展[J]. 化工进展, 2024, 43(S1): 351-364.
[5]	林梅洁, 米烁东, 包成. 金属-掺杂氧化铈体系H₂/CO电化学反应机理研究进展[J]. 化工进展, 2024, 43(S1): 209-224.
[6]	李帅哲, 聂懿宸, PHIDSAVARD Keomeesay, 顾雯, 张伟, 刘娜, 徐高翔, 刘莹, 李兴勇, 陈玉保. 非贵金属催化生物质加氢脱氧制备烃基生物燃料的研究进展[J]. 化工进展, 2024, 43(S1): 225-242.
[7]	熊磊, 丁飞燕, 李聪, 王群乐, 吕起, 翟晓娜, 刘峰. 金属Pt负载型非均相催化剂研究进展[J]. 化工进展, 2024, 43(S1): 295-304.
[8]	宋财城, 陈晓贞, 刘丽, 杨成敏, 郑步梅, 尹晓莹, 孙进, 姚运海, 段为宇. 碳基载体负载加氢脱硫催化剂的研究进展[J]. 化工进展, 2024, 43(S1): 305-314.
[9]	韩洪晶, 车宇, 田宇轩, 王海英, 张亚男, 陈彦广. 木质素催化氢解催化剂及溶剂的研究进展[J]. 化工进展, 2024, 43(S1): 315-324.
[10]	胡兴, 刘易, 杜泽学. 3-氯丙烯直接合成环氧氯丙烷催化剂研究进展[J]. 化工进展, 2024, 43(S1): 325-334.
[11]	于梦洁, 吴语童, 罗发祥, 豆义波. 低浓度二氧化碳还原光催化剂结构设计的研究进展[J]. 化工进展, 2024, 43(S1): 335-350.
[12]	张浩, 刘世钰, 沈卫华, 方云进. Ca-ZSM-5催化尿素脱水制备单氰胺[J]. 化工进展, 2024, 43(S1): 365-373.
[13]	何世坤, 张荣花, 李昊阳, 潘晖, 冯君锋. 脱铝分子筛固体酸催化葡萄糖制备5-羟甲基糠醛[J]. 化工进展, 2024, 43(S1): 374-381.
[14]	张日东, 吕建华, 刘继东, 郭豹, 李文松. Ru-K-NaY催化草酸二甲酯脱羰基制备碳酸二甲酯[J]. 化工进展, 2024, 43(S1): 382-390.
[15]	廖旭, 周骏, 罗杰, 曾瑞琳, 王泽宇, 李尊华, 林金清. 多孔离子聚合物催化二氧化碳环加成反应的研究进展[J]. 化工进展, 2024, 43(9): 4925-4940.

Zr对Ni/Ti₃C₂催化剂结构及催化肉桂醛选择加氢的影响

Effect of Zr on the structure and the hydrogenation properties for cinnamaldehyde of Ni/Ti₃C₂ catalyst

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价