Control and Impact of Metal Loading Heterogeneities at the Nanoscale on the Performance of Pt/Zeolite Y Catalysts for Alkane Hydroconversion

Lars I van der Wal; Jogchum Oenema; Luc C J Smulders; Nonne J Samplonius; Karan R Nandpersad; Jovana Zečević; Krijn P de Jong

doi:10.1021/acscatal.1c00211

Control and Impact of Metal Loading Heterogeneities at the Nanoscale on the Performance of Pt/Zeolite Y Catalysts for Alkane Hydroconversion

ACS Catal. 2021 Apr 2;11(7):3842-3855. doi: 10.1021/acscatal.1c00211. Epub 2021 Mar 12.

Authors

Lars I van der Wal¹, Jogchum Oenema¹, Luc C J Smulders¹, Nonne J Samplonius¹, Karan R Nandpersad¹, Jovana Zečević¹, Krijn P de Jong¹

Affiliation

¹ Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.

Abstract

The preparation of zeolite-based bifunctional catalysts with low noble metal loadings while maintaining optimal performance has been studied. We have deposited 0.03 to 1.0 wt % Pt on zeolite H-USY (Si/Al ∼ 30 at./at.) using either platinum(II) tetraammine nitrate (PTA, Pt(NH₃)₄(NO₃)₂) or hexachloroplatinic(IV) acid (CPA, H₂PtCl₆·6H₂O) and studied the nanoscale Pt loading heterogeneities and global hydroconversion performance of the resulting Pt/Y catalysts. Pt/Y samples prepared with PTA and a global Pt loading as low as 0.3 wt % Pt (n _Pt/n _A = 0.08 mol/mol, where n_Pt is the number of Pt surface sites and n _A is the number of acid sites) maintained catalytic performance during n-heptane (T = 210-350 °C, P = 10 bar) as well as n-hexadecane (T = 170-280 °C, P = 5 bar) hydroisomerization similar to a 1.0 wt % Pt sample. For Pt/Y catalysts prepared with CPA, a loading of 0.3 wt % Pt (n _Pt/n _A = 0.08 mol/mol) sufficed for n-heptane hydroisomerization, whereas a detrimental effect on n-hexadecane hydroisomerization was observed, in particular undesired secondary cracking occurred to a significant extent. The differences between PTA and CPA are explained by differences in Pt loading per zeolite Y crystal (size ∼ 500 nm), shown from extensive transmission electron microscopy energy-dispersive X-ray spectroscopy experiments, whereby crystal-based n _Pt/n _A ratios could be determined. From earlier studies, it is known that the Al content per crystal of USY varied tremendously and that PTA preferentially is deposited on crystals with higher Al content due to ion-exchange with zeolite protons. Here, we show that this preferential deposition of PTA on Al-rich crystals led to a more constant value of n _Pt/n _A ratio from one zeolite crystal to another, which was beneficial for catalytic performance. Use of CPA led to a large variation of Pt loading independent of Al content, giving rise to larger variations of n _Pt/n _A ratio from crystal to crystal that negatively affected the catalytic performance. This study thus shows the impact of local metal loading variations at the zeolite crystal scale (nanoscale) caused by different interactions of metal precursors with the zeolite, which are essential to design and synthesize optimal catalysts, in particular at low noble metal loadings.