Electronic state, abundance and microenvironment modulation of Ru nanoclusters within hierarchically porous UiO-66(Ce) for efficient hydrogenation of dicyclopentadiene

doi:10.1016/S1872-2067(23)64562-0

Abstract

Abstract:

Developing catalysts for dicyclopentadiene (DCPD) hydrogenation to tetrahydrodicyclopentadiene (THDCPD) at low temperature is crucial and challenging for the green and energy-saving production of high energy density aviation fuel. Herein, hierarchically porous UiO-66(Ce) encapsulate Ru nanoclusters (NCs) was successfully customized by soft template method and in-situ reduction. The mesoporous UiO-66(Ce) promoted the high dispersion of Ru NCs, and the transfer of substrate molecules. By controlling the synthesis conditions, the electronic state, abundance, and microenvironment of Ru NCs were precisely regulated. Theory calculation and experimental results revealed that metallic Ru as the main active sites greatly promoted the adsorption and activation of substrate molecules. Therefore, mesoporous UiO-66(Ce) encapsulated Ru NCs showed remarkable catalytic DCPD hydrogenation performance with DCPD conversion of 100% and THDCPD selectivity of ~100% (60 °C, only 35 min). This study has brought new inspiration and guidance to the rational design of function materials for various catalytic applications.

Key words: Hierarchically porous, UiO-66(Ce), Ru nanoclusters, Dicyclopentadiene, Microenvironment modulation

Rushuo Li, Linmeng Wang, Peiyun Zhou, Jing Lin, Zhiyuan Liu, Juan Chen, Danfeng Zhao, Xiubing Huang, Zhiping Tao, Ge Wang. Electronic state, abundance and microenvironment modulation of Ru nanoclusters within hierarchically porous UiO-66(Ce) for efficient hydrogenation of dicyclopentadiene[J]. Chinese Journal of Catalysis, 2024, 56: 150-165.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64562-0

https://www.cjcatal.com/EN/Y2024/V56/I1/150

Figures/Tables 11

Scheme 1. Schematic illustration of the HP-UiO-66(Ce) encapsulated Ru NCs.

Fig. 1. High-magnification SEM images of Micro-UiO-66 (a), Meso-UiO-66 (b) and Macro-UiO-66 (d). (c) TEM image of Meso-UiO-66. Nitrogen sorption isotherms (e) and corresponding pore size distributions (f) (calculated by DFT-analysis) for the Micro-UiO-66 and Meso-UiO-66.

Fig. 2. High-magnification SEM images of Ru@Meso-UiO-25-200 (a), Ru@Micro-UiO-25-200 (b), and Ru@Macro-UiO-25-200 (c). The low-magnification (d) and high-magnification (e,f) TEM images, and HAADF-STEM image (g) with elemental mapping images of Ru@Meso- UiO-25-200.

Fig. 3. XPS full survey (a), Ru 3p (b), Ce 3d (c), O 1s (d) spectra, and structure schematic illustration (e) of Ru3+-Meso-UiO-25, Ru@Meso-UiO-25-150, Ru@Meso-UiO-25-180, and Ru@Meso-UiO-25-200.

Fig. 4. Powder XRD patterns of HP-UiO-66(Ce) with different pore sizes encapsulated Ru NCs (a), Meso-UiO-66 reduced at different temperatures (b), Meso-UiO-66 encapsulated Ru NCs reduced at different temperatures (c), Meso-UiO-66 encapsulated Ru NCs with different Ru loadings (d), Meso-UiO-66 with different Ru3+ adsorption temperatures (e), and Meso-UiO-66 encapsulated Ru NCs with different Ru3+ adsorption temperatures (f).

Fig. 5. TEM, HRTEM, and Ru NCs size distribution images of Ru@Meso-UiO-25-200 (a-c), Ru@Meso-UiO-30-200 (d-f), Ru@Meso- UiO-35-200 (g-i), Ru@Meso-UiO-40-200 (j-l), and Ru@Meso-UiO- 60-200 (m-o).

Table 1 Catalytic performances towards the hydrogenation of DCPD over different catalysts for comparison a.

Entry	Sample	T (°C)	t (h)	Con. ^b(%)	Sel. ^c (%)
Entry	Sample	T (°C)	t (h)	DCPD	DHDCPD	THDCPD
1	Micro-UiO-66	100	10	5	100	—
2	Macro-UiO-66	100	5	6.7	100	—
3	Meso-UiO-66	100	5	13.2	100	—
3	Meso-UiO-66	—	2	0	—	—
4	Meso-UiO-200	100	2	6.4	100	—
5	Ru@Micro-UiO-25-200	60	1	5.4	77.3	22.7
6	Ru@Macro-UiO-25-200	60	0.5	38.8	9.3	90.7
7	Ru@Meso-UiO-25-200	60	0.5	99.7	9.1	90.9
8	Ru@Meso-UiO-25-180	60	1	0	—	—
9	Ru@Meso-UiO-25-150	60	1	0	—	—
10	1.5Ru@Meso-UiO-25-200	60	0.5	7	42.7	57.3
11	1Ru@Meso-UiO-25-200	60	0.5	0	—	—
12	0.5Ru@Meso-UiO-25-200	60	0.5	0	—	—
13	Ru@Meso-UiO-30-200	60	0.5	78.7	27.8	72.1
14	Ru@Meso-UiO-35-200	60	0.5	3.8	69.2	30.8
15	Ru@Meso-UiO-40-200	60	0.5	0.8	56	44
16	Ru@Meso-UiO-60-200	60	0.5	0	—	—

Fig. 6. Conversion of DCPD (a) and selectivity of DHDCPD and THDCPD (b) over Ru@Meso-UiO-25-200 at different reaction times. (c,d) Reusability of Ru@Meso-UiO-25-200-AF-H2/Ar in the hydrogenation reaction of DCPD (t = 35 min). Reaction conditions: mDCPD = 200 mg, mcatalyst = 20 mg, Vsolvent = 5 mL, PH2 = 2 MPa, T = 60 °C.

Fig. 7. The optimized simplified structures of Meso-UiO-66 (a), and Ru@Meso-UiO-25-200 (b). (c) The adsorption energy of H2 and DCPD chemisorbed and physiosorbed on Meso-UiO-66 and Ru@Meso- UiO-25-200, ** and * represent physisorbed and chemisorbed species respectively. The structures of catalysts, H2 and DCPD are displayed as ball-and-stick models in which yellow, green, gray, white, and red balls represent Ce, Ru, C, H and O, respectively.

Fig. 8. PDOS of DCPD and H2 adsorbed on Ru@Meso-UiO-25-200 (a,b) and Meso-UiO-66 (c,d), respectively. The Fermi level is set to zero as shown as dashed line. The optimized models of chemisorbed H2 (e) and physisorbed DCPD (f) on Ce-O sites of Meso-UiO-66, chemisorbed H2 (g) and chemisorbed DCPD (h) on Ru active sites of Ru@Meso-UiO-25-200. Charge density difference for DCPD and H2 adsorbed on Ru@Meso-UiO-25-200 (i,j) and Meso-UiO-66 (k,l), respectively. Red and blue represent electron accumulation and depletion, and the isosurface value is set as 0.005 a.u. Charge transfer (ΔQ, e) are calculated from the population analysis in Hirshfeld method.

Fig. 9. Possible reaction pathways of DCPD hydrogenation over the Ru@Meso-UiO-25-200.

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