Chinese Journal of Magnetic Resonance >

2019 , Vol. 36 >Issue 3: 298 - 308

DOI: https://doi.org/10.11938/cjmr20182680

Articles

In Operando Nuclear Magnetic Resonance Spectroscopy Study on Photocatalytic Methanol Reforming

  • LIU Wen-qing ,
  • SONG Yan-hong ,
  • WANG Xue-lu ,
  • YAO Ye-feng
Expand
  • Shanghai Key Laboratory of Magnetic Resonance, College of Physics and Materials Science, East China Normal University, Shanghai 200062, China

Received date: 2018-01-06

  Online published: 2018-11-26

Fold

Abstract

The reaction of photocatalytic methanol reforming in a real solid-liquid reaction environment was studied by in operando nuclear magnetic resonance (NMR) spectroscopy. Four liquid-state intermediate products were detected in the reaction systems investigated, including HOCH2OH, CH3OCH2OH, HCOOH and HCOOCH3. It was also demonstrated that the crystal types of TiO2 catalysts had a strong influence on the production of the four intermediate products. And the contents of the four products increased with the increasing illumination time. Palladium (Pd) loading enhanced the production of CH3OCH2OH and HOCH2OH by 2~3 orders of magnitude, but had little effects on the production of HCOOCH3 and HCOOH.

Key words： in operando NMR; methanol reforming; photocatalytic; liquid-state NMR

Cite this article

LIU Wen-qing , SONG Yan-hong , WANG Xue-lu , YAO Ye-feng . In Operando Nuclear Magnetic Resonance Spectroscopy Study on Photocatalytic Methanol Reforming[J]. Chinese Journal of Magnetic Resonance, 2019 , 36(3) : 298 -308 . DOI: 10.11938/cjmr20182680

References

[1] RODRIGUEZLUGO R E, TRINCADO M, VOGT M, et al. A homogeneous transition metal complex for clean hydrogen production from methanol-water mixtures[J]. Nat Chem, 2013, 5(4):342-347.
[2] NIELSEN M, ALBERICO E, BAUMANN W, et al. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide[J]. Nature, 2013, 495(7439):85-89.
[3] CLARKE H T, GILLESPIE H B, WEISSHAUS S Z. The action of formaldehyde on amines and amino acids[J]. J Am Chem Soc, 1933, 55(11):4571-4587.
[4] HEYDUK A F, NOCERA D G. Hydrogen produced from hydrohalic acid solutions by a two-electron mixed-valence photocatalyst[J]. Science, 2001, 293(5535):1639-1641.
[5] WANG X L, LIU W, YU Y Y, et al. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions[J]. Nat Communi, 2016, 7:11918.
[6] CHEN X B, SHEN S H, GUO L J, et al. Semiconductor-based photocatalytic hydrogen generation[J]. Chem Rev, 2010, 110(11):6503-6570.
[7] ONISHI H, IWASAWA Y. Dynamic visualization of a metal-oxide-surface/gas-phase reaction:Time-resolved observation by scanning tunneling microscopy at 800 K[J]. Phys Rev Lett, 1996, 76(5):791-794.
[8] SCHEIBER P, RISS A, SCHMID M, et al. Observation and destruction of an elusive adsorbate with STM:O2/TiO2(110)[J]. Phys Rev Lett, 2010, 105(21):5332-5337.
[9] ZHANG Z, BONDARCHUK O, WHITE J M, et al. Imaging adsorbate O-H bond cleavage:methanol on TiO2(110)[J]. J Am Chem Soc, 2006, 128(13):4198-4199.
[10] LI B, ZHAO J, ONDA K, et al. Ultrafast interfacial proton-coupled electron transfer[J]. Science, 2010, 110(12):7082-7099.
[11] MCLAREN A D. The beckmann rearrangement of aliphatic ketoximes[J]. Science, 1946, 103(2678):503.
[12] XU C B, YANG W S, GUO Q, et al. Molecular hydrogen formation from photocatalysis of methanol on anatase-TiO2(101)[J]. J Am Chem Soc, 2014, 136(2):602-605.
[13] XU C B, YANG W S, GUO Q, et al. Molecular hydrogen formation from photocatalysis of methanol on TiO2(110)[J]. J Am Chem Soc, 2013, 135(28):10206-10209.
[14] GUO Q, XU C B, REN Z F, et al. Stepwise photocatalytic dissociation of methanol and water on TiO2(110)[J]. J Am Chem Soc, 2012, 134(32):13366.
[15] ZHANG M, DE R M, FREI H. Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst[J]. Nat Chem, 2014, 6(4):362-367.
[16] HIGHFIELD J G, CHEN M. H, NGUYEN P T, et al. Mechanistic investigations of photo-driven processes over TiO2 by in-situ DRIFTS-MS:Part 1. Platinization and methanol reforming[J]. Energy Environ Sci, 2009, 2(9):991-1002.
[17] CHEN T, FENG Z C, WU G P, et al. Mechanistic studies of photocatalytic reaction of methanol for hydrogen production on Pt/TiO2 by in situ fourier transform IR and time-resolved IR spectroscopy[J]. J Phys Chem C, 2007, 111(22):8005-8014.
[18] BLANC F, LESKES M, GREY C P. In situ solid-state NMR spectroscopy of electrochemical cells:batteries, supercapacitors, and fuel cells[J]. Acc Chem Res, 2013, 46(9):1952-1963.
[19] CATTANEO A S, VILLA D C, ANGIONI S, et al. Operando electrochemical NMR microscopy of polymer fuel cells[J]. Energy Environ Sci, 2015, 8(8):2383-2388.
[20] CHAN K W H. Probing adsorbates on Pt electrode surfaces by the Use of 13C spin-echo NMR[J]. J Electrochem Soc, 1990, 137(1):367-368.
[21] TONG Y Y, WIECKOWSKI A, OLDFIELD E. NMR of electrocatalysts[J]. J Phys Chem B, 2002, 106(10):2434-2446.
[22] XU S T, ZHANG W P, LIU X C, et al. Enhanced in situ continuous-flow MAS NMR for reaction kinetics in the nanocages[J]. J Am Chem Soc, 2009, 131(38):13722-13727.
[23] YAMAMOTO M, NAKAMURA R, KASAYA T, et al. Back cover:spontaneous and widespread electricity generation in natural deep-sea hydrothermal fields[J]. Angew Chem, 2017, 56(21):5725.
[24] ZHANG W P, XU S T, HAN X W, et al. ChemInform abstract:in situ solid-state NMR for heterogeneous catalysis:A joint experimental and theoretical approach[J]. Chem Soc Rev, 2011, 43(1):192-210.
[25] SÁNCHEZ V M, COJULUN J A, SCHERLIS D A. Dissociation free energy profiles for water and methanol on TiO2 surfaces[J]. J Phys Chem C, 2010, 114(26):11522-11526.
[26] SETVÃN M, ASCHAUER U, SCHEIBER P, et al. Reaction of O2 with subsurface oxygen vacancies on TiO2 anatase (101)[J]. Science, 2013, 341(6149):988-991.
[27] SULEIMANOV N M, KHANTIMEROV S M, SCHEUERMANN R, et al. In situ muSR and NMR investigation of methanol dissociation on carbon-supported nanoscaled Pt-Ru catalyst[J]. J Solid State Electr, 2013, 17(8):2115-2121.
[28] SCHRAUBEN J N, HAYOUN R, VALDEZ C N, et al. Titanium and zinc oxide nanoparticles are proton-coupled electron transfer agents[J]. Science, 2012, 336(6086):1298-1301.
[29] PILLENTON S, RAFTERY D. Solid-state NMR studies of the adsorption and photooxidation of ethanol on mixed TiO2-SnO2 photocatalysts[J]. Solid State Nuclear Magnetic Resonance, 2003, 24(4):236-253.
[30] BALDOVINO-MEDRANO V G, POLLEFEYT G, BLIZNUK V, et al. Synergetic behavior of TiO2-supported Pd(z)Pt(1-z) catalysts in the green synthesis of methyl formate[J]. Chemcatchem, 2016, 8(6):1157-1166.
Options
Outlines

/

〈 〉

Copyright © 2017 Editorial Board of Chinese Journal of Magnetic Resonance
Powered by Beijing Magtech Co. Ltd