Catalytic activity of transition metal doped Cu(111) surfaces for ethanol synthesis from acetic acid hydrogenation: a DFT study

نویسندگان

  • Minhua Zhang
  • Rui Yao
  • Haoxi Jiang
  • Guiming Li
  • Yifei Chen
چکیده

Transition metal (Co, Ni, Ru, Rh, Pd and Pt) doped Cu(111) models are selected to examine the effects of transition metals on Cu surface for ethanol synthesis from acetic acid hydrogenation using density functional theory (DFT) calculations. On these surfaces, the adsorption of the main intermediates and reaction barriers of key elementary steps are investigated. The calculation results indicate that oxophilic metals are projected to be more active in acetic acid adsorption and acetaldehyde adsorption compared to less-oxophilic metals. Those metals with larger C adsorption energies generally have better C–OH bond cracking activity. Additionally, a good linear Brønsted–Evans–Polanyi (BEP) correlation is established for predicting the preferences of C–OH bond scission of acetic acid on other metals. Finally, O–H bond formation in C2-oxygenates (CH3CO, CH3CHO, CH3CH2O) hydrogenation is examined on all these surfaces. The reactions are more likely to occur on less-oxophilic metal-doped Cu surfaces. Therefore, it appears to involve an intricate balance between C–OH cracking and O–H bond formation reactions. That means those metal-doped Cu-based catalysts that are capable of preferentially activating C–OH bond without considerably inhibiting O–H bond formation of C2-oxygenates are predicted to achieve optimum catalytic activity for ethanol synthesis from acetic acid hydrogenation. The results can provide theoretical guidance for related experiments as well as the designing of Cu-based catalysts for ethanol synthesis.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

First-principles study of chemical reactions at metal surfaces

We have studied the adsorption state and the hydrogenation process of formate on clean and Zn-deposited Cu(111) surfaces by using DFT-GGA-pseudopotential calculations. After the deposition of Zn on the Cu(111) surface, the Zn atom is substitutionally adsorbed in the first layer of the Cu surface and Cu-Zn surface alloys are formed which is in agreement with experimental results. However, our ca...

متن کامل

Tailoring the Energy Band Gap of Transition Metal Doped TiO2 Thin Film

Water splitting for hydrogen production under sunlight using TiO2 as photo catalyst provides a better route for solar energy and attracts the attention of many researchers. The photo catalytic activity of TiO2 under sunlight irradiation depends on the band gap energy. The transition metal doped TiO2 shows an edge over TiO2 in optical absorbance and photo catalytic activity. Thin film of Cr dope...

متن کامل

Synthesis and characterization of transition metal doped ZnSe/ZnS nanocrystals by a rapid photochemical method

In the present work, a one pot, rapid and room temperature photochemical Synthesis of transition metal (TM; Cu, Mn, Cr)-doped ZnSe/ZnS core/shell nanocrystals (NCs) was reported. FT-IR spectrum confirmed the capping of ZnSe by thioglycolic acid. XRD and TEM analysis demonstrated zinc blende phase NCs with an average size of around 3 and 5 nm for TM:ZnSe and TM:ZnSe/ZnS NCs, respectively. PL spe...

متن کامل

Experimental and DFT studies of the conversion of ethanol and acetic acid on PtSn-based catalysts.

Reaction kinetics studies were conducted for the conversions of ethanol and acetic acid over silica-supported Pt and Pt/Sn catalysts at temperatures from 500 to 600 K. Addition of Sn to Pt catalysts inhibits the decomposition of ethanol to CO, CH4, and C2H6, such that PtSn-based catalysts are active for dehydrogenation of ethanol to acetaldehyde. Furthermore, PtSn-based catalysts are selective ...

متن کامل

A density functional theory analysis of trends in glycerol decomposition on close-packed transition metal surfaces.

We describe an accelerated density functional theory (DFT)-based computational strategy to determine trends in the decomposition of glycerol via elementary dehydrogenation, C-C, and C-O bond scission reactions on close-packed transition metal surfaces. Beginning with periodic DFT calculations on Pt(111), the thermochemistry of glycerol dehydrogenation on Pd(111), Rh(111), Cu(111) and Ni(111) is...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2016