Reaction Mechanism of One-Step Conversion of Ethanol to 1,3-Butadiene over Zn-Y/BEA and Superior Catalysts Screening

The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated,and no catalyst screening effort has been done based on central metal atoms.In this work,density functional theory(DFT)calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over ZnY/BEA catalyst.The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step,and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step.Based on the mechanism revealed,six elements were selected to replace Y for screening superior combination of Zn-M/BEA(M=Sn,Nb,Ta,Hf,Zr,Ti;BEA:beta polymorph A)for this reaction.As a result,Zn-Y/BEA(0.69 eV)is proven to be the most preferring catalyst compared with the other six ones,and Zn-Zr/BEA(0.85 eV),Zn-Ti/BEA(0.87 eV),and Zn-Sn/BEA(0.93 eV)can be potential candidates for the conversion of ethanol to butadiene.This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction.

Ultrafast Decay Dynamics of 2-Hydroxypyridine Excited to S_(1) Electronic State

The S_(1) state decay dynamics of 2-hydroxypyridine following UV excitation at a wavelength range of 276.9-250.0 nm is investigated using femtosecond time-resolved photoelectron imaging technique.Based on pump wavelength dependence of the decay dynamics,a refined decay picture is proposed.At pump wavelength of 276.9 nm,the S_(1) state is depopulated through intersystem crossing to lower triplet state(s).At 264.0 nm,both intersystem crossing to lower triplet state(s)and internal conversion to the ground state are in operation.At 250.0 nm,internal conversion to the ground state becomes dominated.

Ultrafast Decay Dynamics of N-Ethylpyrrole Excited to the S_(1)Electronic State:A Femtosecond Time-Resolved Photoelectron Imaging Study

N-ethylpyrrole is one of ethylsubstituted derivatives of pyrrole and its excited-state decay dynamics has never been explored.In this work,we investigate ultrafast decay dynamics of N-ethylpyrrole excited to the S_(1)electronic state using a femtosecond time-resolved photoelectron imaging method.Two pump wavelengths of 241.9 and 237.7 nm are employed.At 241.9 nm,three time constants,5.0±0.7 ps,66.4±15.6 ps and 1.3±0.1 ns,are derived.For 237.7 nm,two time constants of 2.1±0.1 ps and 13.1±1.2 ps are derived.We assign all these time constants to be associated with different vibrational states in the S_(1)state.The possible decay mechanisms of different S_(1)vibrational states are briefly discussed.

Ultrafast Dynamics of Water Molecules Excited to Electronic ■ States:A Time-Resolved Photoelectron Spectroscopy Study

The ultrafast dynamics of water molecules excited to the two F states is studied by combining two-photon excitation and time-resolved photoelectron imaging techniques. The lifetimes of the F1A1 and F1B1 states of H2O (D2O) were derived to be 1.0±0.3 (1.9±0.4) and 10±3 (30±10) ps, respectively. We propose that the F1A1 state mainly decays through the D state, due to the nonadiabatic coupling between them, while the F1B1 state decays through the F1A1 state via Coriolis interaction.