钌基催化剂配位环境对聚乙烯氢解性能的影响

doi:10.11949/0438-1157.20240634

化工学报 ›› 2024, Vol. 75 ›› Issue (10): 3588-3599.DOI: 10.11949/0438-1157.20240634

• 催化、动力学与反应器 • 上一篇下一篇

钌基催化剂配位环境对聚乙烯氢解性能的影响

颜诗宇¹(), 高姣姣¹, 杨太顺¹, 谢尚志¹, 杨艳娟¹, 徐晶¹^,²()

^1.广西大学化学化工学院，广西石化资源加工与过程强化技术重点实验室，广西南宁 530004
^2.华东理工大学化工学院，绿色化工与工业催化全国重点实验室，上海 200237

收稿日期:2024-06-07 修回日期:2024-07-08 出版日期:2024-10-25 发布日期:2024-11-04
通讯作者: 徐晶
作者简介:颜诗宇（1998—），女，硕士研究生，1090336837@qq.com
基金资助:
广西科技基地和人才专项(桂科AD23026311);广西科技重大专项(桂科 AA23062018)

Effect of coordination environment of ruthenium-based catalysts on their performance for polyethylene hydrogenolysis

Shiyu YAN¹(), Jiaojiao GAO¹, Taishun YANG¹, Shangzhi XIE¹, Yanjuan YANG¹, Jing XU¹^,²()

^1.Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2024-06-07 Revised:2024-07-08 Online:2024-10-25 Published:2024-11-04
Contact: Jing XU

摘要/Abstract

摘要：

聚乙烯氢解可以产生多种碳氢化合物，产品分布非常宽，产物选择性调控具有一定挑战性。通过调控钌负载量制备了不同钌粒径的Ru/CeO₂催化剂，利用TEM、in situ DRIFTS和模型计算等多种技术，发现聚乙烯催化氢解的产物分布与钌金属配位环境密切相关。表征和模型计算表明，不同尺寸的钌纳米颗粒具有不同的几何结构和配位环境。钌平均粒径为0.85 nm时，低配位的边/角位点占主导，其C₂~C₄₀选择性达到92%。钌平均粒径达到2.75 nm时，高配位的平台位点占主导，C₂~C₄₀选择性仅为8%，甲烷选择性高达92%。结合截断六角双锥模型和CO-DRIFTS实验，推断Ru/CeO₂催化剂上产物的选择性可能与聚乙烯氢解中间体和钌纳米颗粒表面的相互作用有关，提出了Ru/CeO₂催化剂上聚乙烯氢解两种反应路径与配位环境的关系。

关键词: 废塑料降解, 催化剂, 加氢, 碳氢化合物, 钌纳米颗粒

Abstract:

Polyethylene hydrogenolysis can produce a variety of hydrogen hydride compounds, the product distribution is very wide, and the product selective regulation is challenging. A series of Ru/CeO₂ catalysts with different Ru particle sizes were prepared by regulating Ru loading. It was observed that the product distribution of polyethylene hydrogenolysis closely correlated with the coordination environments of metal Ru as determined by multiple techniques including TEM, in situ DRIFTS and model calculations. Characterizations and model calculations revealed that Ru nanoparticles with different particle sizes exhibited different metal dispersion, geometric structures and coordination environments. The C₂—C₄₀ alkanes selectivity of 92% was achieved by using Ru particle sizes with mean diameter of 0.85 nm where the edge/corner sites with low-coordination are dominant. The C₂—C₄₀ alkanes selectivity of 8% and the methane selectivity of 92% was obtained by using the Ru particle sizes with mean diameter of 2.75 nm where the terrace sites with highly coordinated platform sites are dominate. Combined with truncated hexagonal bipyramid model and CO-DRIFTS experiment, the selectivity of products over Ru/CeO₂ catalysts was correlated with the interaction between intermediates of polyethylene hydrogenolysis and the surface of Ru nanoparticles. Furthermore, the relation between reaction pathways in polyethylene hydrogenolysis and coordination environments of metal Ru was proposed.

Key words: degradation of waste plastic, catalyst, hydrogenation, hydrocarbons, ruthenium nanoparticles

中图分类号:

TQ 426

颜诗宇, 高姣姣, 杨太顺, 谢尚志, 杨艳娟, 徐晶. 钌基催化剂配位环境对聚乙烯氢解性能的影响[J]. 化工学报, 2024, 75(10): 3588-3599.

Shiyu YAN, Jiaojiao GAO, Taishun YANG, Shangzhi XIE, Yanjuan YANG, Jing XU. Effect of coordination environment of ruthenium-based catalysts on their performance for polyethylene hydrogenolysis[J]. CIESC Journal, 2024, 75(10): 3588-3599.

图/表 13

图1 不同钌负载量的Ru/CeO2催化剂的性能评价（反应条件：1 g PE，50 mg Ru/CeO2，3.5 MPa H2，500 r/min，4 h）

Fig.1 Performance evaluation of Ru/CeO2 catalysts with different Ru loadings(reaction conditions: 1 g PE, 50 mg Ru/CeO2, 3.5 MPa H2, 500 r/min, 4 h)

表1 纯CeO2载体的性能评价

Table 1 Performance evaluation of CeO2 support

催化剂	产率/%			转化率/%
催化剂	CH₄	C₂~C₆	C₇~C₄₀	转化率/%
CeO₂	0.1	0.2	1.1	1.4

图2 相同钌投入量的Ru/CeO2催化剂的性能评价[反应条件：1 g PE，Ru/CeO2 (1 mg Ru)，3.5 MPa H2，500 r/min，4 h]

Fig.2 Performance evaluation of Ru/CeO2 catalysts with the same Ru amount[reaction conditions: 1 g PE, Ru/CeO2 (1 mg Ru), 3.5 MPa H2, 500 r/min, 4 h]

表2 催化剂的结构参数

Table 2 Physicochemical properties of the catalysts

催化剂	钌含量^① /%	比表面积^②/(m²/g)	孔容^③ /(cm³/g)	平均孔径^④/nm	钌平均粒径^⑤/nm	钌金属分散度^⑥/%
CeO₂	—	16.4	0.045	6.66	—	—
0.5% Ru/CeO₂	0.38	17.9	0.051	7.25	0.85	100
2% Ru/CeO₂	1.83	18.8	0.049	7.12	1.55	85
9% Ru/CeO₂	8.58	13.0	0.028	8.41	2.75	48

图3 CeO2和还原后的Ru/CeO2催化剂的氮气脱附曲线(a)和孔径分布(b)

Fig.3 Nitrogen desorption curves (a) and pore size distribution (b) of CeO2 and Ru/CeO2 catalysts after reduction

图4 CeO2和还原后的Ru/CeO2催化剂的XRD谱图

Fig.4 XRD patterns of CeO2 and Ru/CeO2 catalysts after reduction

图5 CeO2和Ru/CeO2催化剂的H2-TPR图

Fig.5 H2-TPR profiles of CeO2 and Ru/CeO2 catalysts

图6 Ru/CeO2催化剂的表征（所有样品均为还原后催化剂）

Fig.6 Characterization of Ru/CeO2 catalysts (all samples are reduced catalysts)

图7 钌纳米颗粒的几何结构理论模型示意图和三种切面的各位点的原子配位数

Fig.7 Geometric structure model and the atomic coordination number of Ru nanoparticle

图8 不同类型的活性位点的比例和数量

Fig.8 The fraction and number of different types of active site

图9 Ru/CeO2催化剂的CO-DRIFT谱图

Fig.9 CO-DRIFT spectra of Ru/CeO2 catalysts

图10 产物选择性与氢气压力的关系

Fig.10 The relationship between product selectivity and H2 pressure

图11 Ru/CeO2催化PE氢解的两种可能反应机制（参考文献[45]）

Fig.11 Two possible mechanisms with which hydrogenolysis on the surface of Ru/CeO2 could proceed (based on the works of Ref.[45])

参考文献 45

1	van Fan Y, Jiang P, Tan R R, et al. Forecasting plastic waste generation and interventions for environmental hazard mitigation[J]. Journal of Hazardous Materials, 2022, 424: 127330.
2	Ali W, Ali H, Souissi S, et al. Are bioplastics an ecofriendly alternative to fossil fuel plastics?[J]. Environmental Chemistry Letters, 2023, 21(4): 1991-2002.
3	Kunwar B, Cheng H N, Chandrashekaran S R, et al. Plastics to fuel: a review[J]. Renewable and Sustainable Energy Reviews, 2016, 54: 421-428.
4	Bunescu A, Lee S, Li Q, et al. Catalytic hydroxylation of polyethylenes[J]. ACS Central Science, 2017, 3(8): 895-903.
5	Schwab S T, Baur M, Nelson T F, et al. Synthesis and deconstruction of polyethylene-type materials[J]. Chemical Reviews, 2024, 124(5): 2327-2351.
6	Faraca G, Astrup T. Plastic waste from recycling centres: characterisation and evaluation of plastic recyclability[J]. Waste Management, 2019, 95: 388-398.
7	Zhang F, Zeng M H, Yappert R D, et al. Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization[J]. Science, 2020, 370(6515): 437-441.
8	Celik G, Kennedy R M, Hackler R A, et al. Upcycling single-use polyethylene into high-quality liquid products[J]. ACS Central Science, 2019, 5(11): 1795-1803.
9	Yuan X Z, Cho M K, Lee J G, et al. Upcycling of waste polyethylene terephthalate plastic bottles into porous carbon for CF₄ adsorption[J]. Environmental Pollution, 2020, 265: 114868.
10	Lee W T, van Muyden A, Bobbink F D, et al. Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts[J]. Nature Communications, 2022, 13(1): 4850.
11	Rorrer J E, Troyano-Valls C, Beckham G T, et al. Hydrogenolysis of polypropylene and mixed polyolefin plastic waste over Ru/C to produce liquid alkanes[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(35): 11661-11666.
12	Rorrer J E, Beckham G T, Román-Leshkov Y. Conversion of polyolefin waste to liquid alkanes with Ru-based catalysts under mild conditions[J]. JACS Au, 2020, 1(1): 8-12.
13	Fihri A, Bouhrara M, Patil U, et al. Fibrous nano-silica supported ruthenium (KCC-1/Ru): a sustainable catalyst for the hydrogenolysis of alkanes with good catalytic activity and lifetime[J]. ACS Catalysis, 2012, 2(7): 1425-1431.
14	Lee W T, Bobbink F D, van Muyden A P, et al. Catalytic hydrocracking of synthetic polymers into grid-compatible gas streams[J]. Cell Reports Physical Science, 2021, 2(2): 100332.
15	Chen L X, Zhu Y F, Meyer L C, et al. Effect of reaction conditions on the hydrogenolysis of polypropylene and polyethylene into gas and liquid alkanes[J]. Reaction Chemistry & Engineering, 2022, 7(4): 844-854.
16	Nakaji Y, Tamura M, Miyaoka S, et al. Low-temperature catalytic upgrading of waste polyolefinic plastics into liquid fuels and waxes[J]. Applied Catalysis B: Environmental, 2021, 285: 119805.
17	Wang C, Xie T J, Kots P A, et al. Polyethylene hydrogenolysis at mild conditions over ruthenium on tungstated zirconia[J]. JACS Au, 2021, 1(9): 1422-1434.
18	Kim T, Nguyen-Phu H, Kwon T, et al. Investigating the impact of TiO₂ crystalline phases on catalytic properties of Ru/TiO₂ for hydrogenolysis of polyethylene plastic waste[J]. Environmental Pollution, 2023, 331: 121876.
19	Jaydev S D, Martín A J, Pérez-Ramírez J. Direct conversion of polypropylene into liquid hydrocarbons on carbon-supported platinum catalysts[J]. ChemSusChem, 2021, 14(23): 5179-5185.
20	Pinzón M, Romero A, de Lucas Consuegra A, et al. Hydrogen production by ammonia decomposition over ruthenium supported on SiC catalyst[J]. Journal of Industrial and Engineering Chemistry, 2021, 94: 326-335.
21	Sakpal T, Lefferts L. Structure-dependent activity of CeO₂ supported Ru catalysts for CO₂ methanation[J]. Journal of Catalysis, 2018, 367: 171-180.
22	Guo Y, Mei S, Yuan K, et al. Low-temperature CO₂ methanation over CeO₂-supported Ru single atoms, nanoclusters, and nanoparticles competitively tuned by strong metal–support interactions and H-spillover effect[J]. ACS Catalysis, 2018, 8(7): 6203-6215.
23	Mi R L, Li D, Hu Z, et al. Morphology effects of CeO₂ nanomaterials on the catalytic combustion of toluene: a combined kinetics and diffuse reflectance infrared Fourier transform spectroscopy study[J]. ACS Catalysis, 2021, 11(13): 7876-7889.
24	Wang C F, Sun H M, Liu X Q, et al. Low-temperature CO₂ methanation over Ru/CeO₂: investigation into Ru loadings[J]. Fuel, 2023, 345: 128238.
25	Bezkrovnyi O, Vorokhta M, Pawlyta M, et al. In situ observation of highly oxidized Ru species in Ru/CeO₂ catalyst under propane oxidation[J]. Journal of Materials Chemistry A, 2022, 10(31): 16675-16684.
26	Liao W Q, Yue M N, Chen J Y, et al. Decoupling the interfacial catalysis of CeO₂-supported Rh catalysts tuned by CeO₂ morphology and Rh particle size in CO₂ hydrogenation[J]. ACS Catalysis, 2023, 13(8): 5767-5779.
27	Wang J, Wei Z Z, Mao S J, et al. Highly uniform Ru nanoparticles over N-doped carbon: pH and temperature-universal hydrogen release from water reduction[J]. Energy & Environmental Science, 2018, 11(4): 800-806.
28	Zhang Q, Kusada K, Wu D S, et al. Selective control of FCC and hcp crystal structures in Au-Ru solid-solution alloy nanoparticles[J]. Nature Communications, 2018, 9(1): 510.
29	Ye M X, Li Y R, Yang Z R, et al. Ruthenium/TiO₂-catalyzed hydrogenolysis of polyethylene terephthalate: reaction pathways dominated by coordination environment[J]. Angewandte Chemie International Edition, 2023, 62(19): e202301024.
30	Mahmood J, Li F, Jung S M, et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction[J]. Nature Nanotechnology, 2017, 12(5): 441-446.
31	Van Hardeveld R, Hartog F. The statistics of surface atoms and surface sites on metal crystals[J]. Surface Science, 1969, 15(2): 189-230.
32	Kim T W, Kim D, Jo Y, et al. Potassium as the best alkali metal promoter in boosting the hydrogenation activity of Ru/MgO for aromatic LOHC molecules by facilitated heterolytic H₂ adsorption[J]. Journal of Catalysis, 2023, 419: 112-124.
33	Kim T W, Chun H J, Jo Y, et al. Electronic vs. geometric effects of Al₂O₃-supported Ru species on the adsorption of H₂ and substrate for aromatic LOHC hydrogenation[J]. Journal of Catalysis, 2023, 428: 115178.
34	Matsubu J C, Yang V N, Christopher P. Isolated metal active site concentration and stability control catalytic CO₂ reduction selectivity[J]. Journal of the American Chemical Society, 2015, 137(8): 3076-3084.
35	Lyu S S, Cheng Q P, Liu Y H, et al. Dopamine sacrificial coating strategy driving formation of highly active surface-exposed Ru sites on Ru/TiO₂ catalysts in Fischer-Tropsch synthesis[J]. Applied Catalysis B: Environmental, 2020, 278: 119261.
36	Kellner C S, Bell A T. Effects of dispersion on the activity and selectivity of alumina-supported ruthenium catalysts for carbon monoxide hydrogenation[J]. Journal of Catalysis, 1982, 75(2): 251-261.
37	Abdel-Mageed A M, Widmann D, Olesen S E, et al. Selective CO methanation on Ru/TiO₂ catalysts: role and influence of metal-support interactions[J]. ACS Catalysis, 2015, 5(11): 6753-6763.
38	Chen S L, Abdel-Mageed A M, Li D, et al. Morphology-engineered highly active and stable Ru/TiO₂ catalysts for selective CO methanation[J]. Angewandte Chemie International Edition, 2019, 58(31): 10732-10736.
39	Yu H L, Wei Y, Lin T J, et al. Identifying the performance descriptor in direct syngas conversion to long-chain α-olefins over ruthenium-based catalysts promoted by alkali metals[J]. ACS Catalysis, 2023, 13(6): 3949-3959.
40	Kale M J, Christopher P. Utilizing quantitative in situ FTIR spectroscopy to identify well-coordinated Pt atoms as the active site for CO oxidation on Al₂O₃-supported Pt catalysts[J]. ACS Catalysis, 2016, 6(8): 5599-5609.
41	Jia C H, Xie S Q, Zhang W L, et al. Deconstruction of high-density polyethylene into liquid hydrocarbon fuels and lubricants by hydrogenolysis over Ru catalyst[J]. Chem Catalysis, 2021, 1(2): 437-455.
42	Flaherty D W, Iglesia E. Transition-state enthalpy and entropy effects on reactivity and selectivity in hydrogenolysis of n-alkanes[J]. Journal of the American Chemical Society, 2013, 135(49): 18586-18599.
43	Flaherty D W, Hibbitts D D, Iglesia E. Metal-catalyzed C—C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability[J]. Journal of the American Chemical Society, 2014, 136(27): 9664-9676.
44	Xie T J, Wittreich G R, Vlachos D G. Multiscale modeling of hydrogenolysis of ethane and propane on Ru(0001): implications for plastics recycling[J]. Applied Catalysis B: Environmental, 2022, 316: 121597.
45	Nakagawa Y, Oya S I, Kanno D, et al. Regioselectivity and reaction mechanism of Ru-catalyzed hydrogenolysis of squalane and model alkanes[J]. ChemSusChem, 2017, 10(1): 189-198.

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钌基催化剂配位环境对聚乙烯氢解性能的影响

Effect of coordination environment of ruthenium-based catalysts on their performance for polyethylene hydrogenolysis

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