Mg-vacancy-induced Ni-vacancy clusters: highly efficient hydrogen production from cellulose

H2 production from aqueous phase reforming (APR) is of great importance, but an enhancement in the H2 production efficiency is required. Our previous work reported the catalytic production of H2 over metal oxide (MMO)-supported Ni derived from Ni-containing layered double hydroxides (Ni-MgAl-LDHs). Herein, we report the catalytic production of H2 from APR of cellulose over MMO-supported defect-rich Ni derived from Ni-MgAl-LDHs with abundant Mg(II) vacancies (VMg). The well-retained VMg during calcination under an H2 atmosphere induced the formation of Ni vacancies not only at the Ni–MMO interface, but also on the surface of the Ni particles. An H2 yield of up to 70.4% was achieved via the APR of cellulose over the defect-rich Ni–MMO, which is almost 2.5 times that from the APR of cellulose reported to date (∼30%). A combined investigation via quasi in situ XPS, EPR, PAS, and in situ FT-IR verified that the Mg vacancies on the support surface facilitate the cleavage of the C–H bond, while the Ni vacancies on the Ni particles boost the breakage of the C–C bond.

[1]  R. Deka,et al.  Controlling and Stabilization of Ru Nanoparticles by Tuning the Nitrogen Content of the Support for Enhanced H2 Production through Aqueous-Phase Reforming of Glycerol , 2020 .

[2]  Guanyi Chen,et al.  Hydrogen Production via Aqueous-Phase Reforming of Ethylene Glycol over a Nickel–Iron Alloy Catalyst: Effect of Cobalt Addition , 2020, Energy & Fuels.

[3]  Wenlong Wang,et al.  Ni0/Niδ+ Synergistic Catalysis on a Nanosized Ni Surface for Simultaneous Formation of C–C and C–N Bonds , 2019, ACS Catalysis.

[4]  Wenqing Zhang,et al.  Stabilizing Low-coordinated O-ions to Operate Cationic and Anionic Redox Chemistry of Li-ion Battery Materials. , 2019, ACS applied materials & interfaces.

[5]  Xiao-hui Liu,et al.  NiAl2O4 Spinel Supported Pt Catalyst: High Performance and Origin in Aqueous-Phase Reforming of Methanol , 2019, ACS Catalysis.

[6]  B. Jackson,et al.  Methane dissociation on stepped Ni surfaces resolved by impact site, collision energy, vibrational state, and lattice distortion. , 2019, The Journal of chemical physics.

[7]  B. Jackson,et al.  Quantum dynamics studies of the dissociative chemisorption of CH4 on the steps and terraces of Ni(211). , 2018, The Journal of chemical physics.

[8]  Wenjun Yan,et al.  Interface–Promoted Dehydrogenation and Water–Gas Shift toward High-Efficient H2 Production from Aqueous Phase Reforming of Cellulose , 2018 .

[9]  Zhi Yu,et al.  Ultrathin and vacancy-rich CoAl-layered double hydroxide/graphite oxide catalysts: promotional effect of cobalt vacancies and oxygen vacancies in alcohol oxidation , 2018 .

[10]  Carsten Sievers,et al.  Peculiar hydrogenation reactivity of Ni–Niδ+ clusters stabilized by ceria in reducing nitrobenzene to azoxybenzene , 2017 .

[11]  Yong Wang,et al.  Investigation of the promoting effect of Mn on a Pt/C catalyst for the steam and aqueous phase reforming of glycerol , 2017 .

[12]  David G. Evans,et al.  Promoted Synergic Catalysis between Metal Ni and Acid–Base Sites toward Oxidant-Free Dehydrogenation of Alcohols , 2017 .

[13]  D. Su,et al.  Ru-Cluster-Modified Ni Surface Defects toward Selective Bond Breaking between C−O and C−C , 2016 .

[14]  N. Kazantzis,et al.  Sankey-Diagram-based insights into the hydrogen economy of today , 2016 .

[15]  F. B. Passos,et al.  Alumina supported bimetallic Pt–Fe catalysts applied to glycerol hydrogenolysis and aqueous phase reforming , 2016 .

[16]  A. Karim,et al.  Elucidation of the Roles of Re in Aqueous-Phase Reforming of Glycerol over Pt–Re/C Catalysts , 2015 .

[17]  B. Liu,et al.  First-Principles Study of Structure Sensitivity of Ethylene Glycol Conversion on Platinum , 2015 .

[18]  Sib Krishna Ghoshal,et al.  Hydrogen the future transportation fuel: From production to applications , 2015 .

[19]  K. P. Jong,et al.  Toward stable nickel catalysts for aqueous phase reforming of biomass-derived feedstock under reducing and alkaline conditions , 2014 .

[20]  Chong Xiao,et al.  Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. , 2014, Journal of the American Chemical Society.

[21]  H. Friedrich,et al.  Pt-Re synergy in aqueous-phase reforming of glycerol and the water–gas shift reaction , 2014 .

[22]  E. Hensen,et al.  Aqueous phase reforming of glycerol over Re-promoted Pt and Rh catalysts , 2014 .

[23]  F. Ribeiro,et al.  Effect of Co Loading on the Activity and Selectivity of PtCo Aqueous Phase Reforming Catalysts , 2014 .

[24]  F. Cavani,et al.  In Situ DRIFTS-MS Study of the Anaerobic Oxidation of Ethanol over Spinel Mixed Oxides , 2013 .

[25]  G. Pacchioni,et al.  Electron transfer at oxide surfaces. The MgO paradigm: from defects to ultrathin films. , 2013, Chemical reviews.

[26]  A. Harris,et al.  Effect of CeO₂ addition to Al₂O₃ supports for Pt catalysts on the aqueous-phase reforming of glycerol. , 2013, ChemSusChem.

[27]  D. Su,et al.  A Surface Defect-Promoted Ni Nanocatalyst with Simultaneously Enhanced Activity and Stability , 2013 .

[28]  K. Seshan,et al.  Aqueous phase reforming of ethylene glycol - Role of intermediates in catalyst performance , 2012 .

[29]  L. Pfefferle,et al.  High-Yield Hydrogen Production from Aqueous Phase Reforming over Single-Walled Carbon Nanotube Supported Catalysts , 2012 .

[30]  D. Tichit,et al.  Acido-basic and catalytic properties of transition-metal containing Mg–Al hydrotalcites and their corresponding mixed oxides , 2012 .

[31]  Qianhe Liu,et al.  Preparation of Ce-modified Raney Ni Catalysts and Their Application in Aqueous-Phase Reforming of Cellulose , 2011 .

[32]  Xiujian Zhao,et al.  Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency. , 2011, Journal of the American Chemical Society.

[33]  Xiujian Zhao,et al.  Formation of AgI/TiO2 nanocomposite leads to excellent thermochromic reversibility and photostability , 2011 .

[34]  W. Gac.  Acid–base properties of Ni–MgO–Al2O3 materials , 2011 .

[35]  Zhijian Tian,et al.  Direct conversion of cellulose into hydrogen by aqueous-phase reforming process , 2010 .

[36]  Qiang Wang,et al.  High-index faceted platinum nanocrystals supported on carbon black as highly efficient catalysts for ethanol electrooxidation. , 2010, Angewandte Chemie.

[37]  R. A. Santen,et al.  Complementary structure sensitive and insensitive catalytic relationships. , 2009, Accounts of chemical research.

[38]  Thomas Bligaard,et al.  The nature of the active site in heterogeneous metal catalysis. , 2008, Chemical Society reviews.

[39]  M. Balat.  Potential importance of hydrogen as a future solution to environmental and transportation problems , 2008 .

[40]  A. Shluger,et al.  Chemistry at corners and edges: generation and adsorption of H atoms on the surface of MgO nanocubes. , 2005, The Journal of chemical physics.

[41]  J. Nørskov,et al.  Controlling the catalytic bond-breaking selectivity of Ni surfaces by step blocking , 2005, Nature materials.

[42]  P. Nambissan,et al.  Positron annihilation studies of some anomalous features of Ni Fe 2 O 4 nanocrystals grown in Si O 2 , 2005 .

[43]  G. Huber,et al.  Raney Ni-Sn Catalyst for H2 Production from Biomass-Derived Hydrocarbons , 2003, Science.

[44]  Zhipan Liu,et al.  General rules for predicting where a catalytic reaction should occur on metal surfaces: a density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces. , 2003, Journal of the American Chemical Society.

[45]  David G. Evans,et al.  Preparation of Layered Double-Hydroxide Nanomaterials with a Uniform Crystallite Size Using a New Method Involving Separate Nucleation and Aging Steps , 2002 .

[46]  J. Dumesic,et al.  Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water , 2002, Nature.

[47]  M. Paganini,et al.  O− radical ions on MgO as a tool to unravel structure and location of ionic vacancies at the surface of oxides: a coupled experimental and theoretical investigation , 2001 .

[48]  M. Dresselhaus,et al.  Alternative energy technologies , 2001, Nature.

[49]  E. Riedo,et al.  Identification of defect sites on MgO(100) thin films by decoration with Pd atoms and studying CO adsorption properties. , 2001, Journal of the American Chemical Society.

[50]  C. Mirodatos,et al.  CO Hydrogenation on a Nickel Catalyst: II. A Mechanistic Study by Transient Kinetics and Infrared Spectroscopy , 1998 .

[51]  S. Ardizzone,et al.  Magnesium salts and oxide: an XPS overview , 1997 .

[52]  F. Illas,et al.  Ab Initio Cluster Model Calculations on the Chemisorption of CO2 and SO2 Probe Molecules on MgO and CaO (100) Surfaces. A Theoretical Measure of Oxide Basicity , 1994 .

[53]  C. Mirodatos,et al.  CO hydrogenation on a nickel catalyst. I: Kinetics and modeling of a low temperature sintering process , 1994 .

[54]  D. Goodman,et al.  XPS characterization of ultra-thin MgO films on a Mo(100) surface , 1994 .

[55]  Andreas Poullikkas,et al.  A comparative overview of hydrogen production processes , 2017 .

[56]  Jing-Yuan Wang,et al.  Sorption enhanced aqueous phase reforming of glycerol for hydrogen production over Pt-Ni supported on multi-walled carbon nanotubes , 2015 .

[57]  R. V. van Santen,et al.  Complementary Structure Sensitive and Insensitive Catalytic Relationships , 2009 .

[58]  Dg Evans,et al.  Structural aspects of layered double hydroxides , 2006 .