Introduction of Ag(i) ions into a sulfonic acid functionalized MOF ((Cr)-MIL-101-SO3H) significantly enhances its interactions with olefin double bonds, leading to its much higher selectivities for the separation of C2H4-C2H6 and C3H6-C3H8 at room temperature over the original (Cr)-MIL-101-SO3H and other adsorbents at room temperature.

Glucose conversion to 5‐hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Brönsted acid. In this work, a sulfonic acid functionalized metal‐organic framework MIL‐101(Cr)‐SO3H containing both Lewis acid and Brönsted acid sites, was examined as the catalyst for γ‐valerolactone‐mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second‐order kinetics with an apparent activation energy of 100.9 kJ mol−1. Continuous reaction in the fixed‐bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass‐derived carbohydrate to HMF with a bifunctional metal‐organic framework. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4403–4417, 2016

A metal-organic framework immobilized with Ag(i) sites, namely, (Cr)-MIL-101-SO3Ag, was successfully developed as a highly efficient desulfurization adsorbent because of the strong binding of these Ag(i) sites for thiophene derivatives.