Pt/HZSM-5 catalyst synthesized by atomic layer deposition for aqueous-phase hydrogenation of levulinic acid to valeric acid
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摘要: 利用原子层沉积（ALD）技术制备出Pt/HZSM-5催化剂，并用于乙酰丙酸（LA）水相加氢制戊酸（VA）。在HZSM-5上沉积五个循环时的5Pt/HZSM-5催化剂，其VA收率高达91.4%，且具有较高的稳定性。研究表明，Pt加氢位点和HZSM-5酸性位点距离越近越有利于VA的选择性生成。通过延长沉积的扩散时间，ALD可将Pt沉积到HZSM-5的微孔通道中，但对HZSM-5的微孔结构和酸性位点影响较小，这体现出ALD在保护HZSM-5结构上的优势。随着ALD沉积Pt循环数的增加，Pt纳米颗粒的平均粒径、表面Pt的电子状态、HZSM-5表面酸位点都没有发生明显的变化，分子筛孔道中的Pt比例则逐渐降低，这导致VA生成的TOF降低。同时，也通过浸渍法制备了负载在HZSM-5上的Pt催化剂作为对比，结果表明，浸渍法导致HZSM-5的孔结构受损，形成了更多的微孔，表面酸性位点数目降低，其催化活性、VA选择性和稳定性都显著低于ALD制备的催化剂。Abstract: A Pt/HZSM-5 catalyst was prepared by atomic layer deposition (ALD) for aqueous-phase hydrogenation of levulinic acid (LA) to valeric acid (VA). 5Pt/HZSM-5 produced with 5 cycles of Pt ALD was identified as a highly active and stable bifunctional catalyst, and a high yield of VA (91.4%) was achieved in aqueous solution. A close interaction between Pt and acid sites of HZSM-5 is favor for the selective generation of VA. The microporous structure and the acid sites of HZSM-5 were not changed after Pt ALD, and some Pt nanoparticles were located in the micropore channel of HZSM-5. This reveals that the Pt ALD has the advantage to protect the structure of zeolite. The average particle size of Pt nanoparticles, electric state of surface Pt, and surface acid sites are nearly not changed with the increase of Pt ALD cycle number. However, the ratio of Pt in the pore channel to that out of the pore decreases with the increase of ALD cycle numbers, resulting in a decrease of TOF of VA yield. For comparison, Pt nanoparticles supported on HZSM-5 were also produced by impregnation. But the pore structure of HZSM-5 was damaged, and more micropore were formed by impregnation method for Pt loading. Moreover, it exhibited very low catalytic activity, selectivity of VA, and stability.
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Key words:
- Pt /
- atomic layer deposition /
- levulinic acid /
- hydrogentation /
- valeric acid
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Figure 4 TEM, HRTEM images, and particle size histograms of different samples
(a), (b): 3Pt/HZSM-5; (c): 5Pt/HZSM-5; (d): 7Pt/HZSM-5; (e): 10Pt/HZSM-5; (f): Pt/HZSM-5-IM
Figure 8 Conversion of LA (a), selectivity of VA (b), TOF of VA formation (c) of the catalysts reaction conditions: 200 ℃, 1 MPa, 50 mg catalyst, 2% LA aqueous solution
■ : 3Pt/HZSM-5; ● : 5Pt/HZSM-5; ▲ : 7Pt/HZSM-5; ▼ : 10Pt/HZSM-5; ◆ : Pt/HZSM-5-IM
Table 1 Catalytic performance of different catalysts in aqueous LA hydrogenationa
Table 2 Physicochemical characteristics of HZSM-5 and HZSM-5 supported Pt catalystsa
Table 3 Summary of XPS results for Pt 4f of the xPt/HZSM-5 catalysts
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