Design and preparation of highly active hydrodesulfurization (HDS) catalysts is very important for the removal of air pollution. Herein, we report an extraordinarily active HDS catalyst, which is synthesized by loading of Pd on mesoporous zeolite Y (Pd/HY-M). The mesoporous zeolite Y is successfully synthesized using a water glass containing N,N-dimethyl-N-octadecyl-N-(3-triethoxysilylpropyl) ammonium [(C(2)H(5)O)(3)SiC(3)H(6)N(CH(3))(2)C(18)H(37)](+) cation as a mesoscale template. Compared with mesoporous Beta and ZSM-5 supported Pd catalysts (80.0% and 73.4% for Pd/HBeta-M and Pd/HZSM-5-M, respectively) as well as commercial catalyst of γ-Al(2)O(3) supported Pd catalyst (31.4%), Pd/HY-M catalyst exhibited very high activity in HDS of 4,6-dimethyldibenzothiophene (4,6-DM-DBT, 97.3%). The higher activity of Pd/HY-M than that of Pd/HBeta-M and Pd/HZSM-5-M is assigned to the larger micropore size of zeolite Y compared to that of Beta and ZSM-5. Theoretical simulation and adsorption experimental data show that 4,6-DM-DBT has difficulty entering the micropores of ZSM-5 and Beta zeolites, but the micropores of Y zeolite are accessible.

Isoreticular principle has been employed to realize a flexible-robust metal–organic framework (MOF) with extended pore structure for the adsorptive removal of trace acetylene from ethylene under ambient conditions. The substitution from zinc­(II) to copper­(II) of high coordination distortion leads to elongated Cu–F bonds that expand the closed pore cavities in the prototypical MOF from 3.5 × 3.9 × 4.1 to 3.6 × 4.3 × 4.2 Å3. The optimal cavity size together with strong binding sites thus endows the new Cu analogue to possess open pore space accessible for trace C2H2 within a substantial low-pressure range while excluding C2H4 molecules, as validated by gas isotherms and single-crystal structure of its partially C2H2-loading phase. In contrast to the Zn prototype, at 298 K and 1.0 bar, the guest-free Cu analogue shows significant C2H2 uptake increase with a total capacity of 4.57 mmol g–1, and gains an over two orders of magnitude jump in IAST selectivity for C2H2/C2H4 (1/99, v/v). These results are higher than the benchmark MOFs for molecular sieving of C2H2/C2H4, leading a high C2H4 productivity of 14.9 mmol g–1. Crystallography studies, molecular modeling, selectivity evaluation, and breakthrough experiments have comprehensively demonstrated this flexible-robust MOF as an efficient adsorbent for C2H2/C2H4 separation.

The separation of C 2 H 2 /CO 2 is an important process in industry but challenged by the trade-off of capacity and selectivity owning to their similar physical properties and identical kinetic molecular size. We report the first example of symmetrically interpenetrated dodecaborate pillared MOF, ZNU-1, for benchmark selective separation of C 2 H 2 from CO 2 with ahigh C 2 H 2 capacity of 76.3 cm 3 g À1 and recordC 2 H 2 /CO 2 selectivity of 56.6 (298 K, 1bar) among all the robust porous materials without open metal sites.S ingle crystal structure analysis and modeling indicated that the interpenetration shifting from asymmetric to symmetric mode provided optimal pore chemistry with ideal synergistic "2+ +2" dihydrogen bonding sites for tight C 2 H 2 trapping.The exceptional separation performance was further evidenced by simulated and experimental breakthroughs with excellent recyclability and high productivity (2.4 mol kg À1 )o f9 9.5 %p urity C 2 H 2 during stepped desorption process.

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Separation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB12H12(dpb)2 (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C2H2. The high C2H2 capacity and remarkable C2H2/CO2 selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B−Hδ−⋅⋅⋅Hδ+−C≡C−Hδ+⋅⋅⋅Hδ−−B). This new type of C2H2‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.