Transition metal modification and carbon vacancy promoted Cr2CO2 (MXenes): a new opportunity for a highly active catalyst for the hydrogen evolution reaction

Electrocatalysis has the potential to become a more sustainable approach to generate hydrogen as a clean energy carrier. Developing alternatives to precious metals (Pt, Pd and Ir) for hydrogen production from water splitting is central to the area of renewable energy. Two-dimensional metal carbide and nitride (MXenes) materials have shown characteristics of promising catalysts for the hydrogen evolution reaction (HER). Herein, we performed density functional calculations to predict the stability and electrocatalytic performance of 2D Cr2CO2 with transition metal modification and carbon vacancy engineering. Our results indicated that pure Cr2C and Cr2CO2 MXenes are conductive, which was favorable to the charge transfer during the HER. The Cr2C MXenes tend to be fully terminated by O* under standard conditions [pH = 0, p(H2) = 1 bar, and U = 0 V vs. standard conditions]. The modification by transition metals could tune the Gibbs free energy of reaction for the adsorption of atomic hydrogen (ΔGH*) on Cr2CO2 to close to 0 eV (ideal value) at suitable TM coverage. Charge transfer analysis suggested that surface O atoms gain more electrons by the transition metal doping, and therefore weaken the bonding interaction with H atoms to compare with that of pure Cr2CO2. The HER performance of Cr2CO2 can also be improved via carbon vacancy engineering. These results indicated that transition metal surface modification and carbon vacancy engineering are effective ways for achieving promising HER electrocatalysts for water splitting.

[1]  Wu Li,et al.  Screening Surface Structure of MXenes by High-Throughput Computation and Vibrational Spectroscopic Confirmation , 2018, The Journal of Physical Chemistry C.

[2]  Xiaofeng Wang,et al.  g-C3N4/Ti3C2Tx (MXenes) composite with oxidized surface groups for efficient photocatalytic hydrogen evolution , 2018 .

[3]  Hongda Du,et al.  Universal Descriptor for Large-Scale Screening of High-Performance MXene-Based Materials for Energy Storage and Conversion , 2018 .

[4]  Haotian Wang,et al.  High-throughput theoretical optimization of the hydrogen evolution reaction on MXenes by transition metal modification , 2018 .

[5]  Ning Zhang,et al.  Superior structural, elastic and electronic properties of 2D titanium nitride MXenes over carbide MXenes: a comprehensive first principles study , 2018, 2D Materials.

[6]  S. Joo,et al.  Correction: MXene: an emerging two-dimensional material for future energy conversion and storage applications , 2018 .

[7]  Jinxing Yang,et al.  Carbon vacancies in Ti2CT2 MXenes: defects or a new opportunity? , 2017, Physical chemistry chemical physics : PCCP.

[8]  Zhaojin Li,et al.  Chemical Origin of Termination-Functionalized MXenes: Ti3C2T2 as a Case Study , 2017 .

[9]  P. Ajayan,et al.  Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution , 2017, Nature Energy.

[10]  Zihe Zhang,et al.  Ti2CO2 MXene: a highly active and selective photocatalyst for CO2 reduction , 2017 .

[11]  K. Thygesen,et al.  Two-Dimensional MXenes as Catalysts for Electrochemical Hydrogen Evolution: A Computational Screening Study , 2017 .

[12]  Hui‐Ming Cheng,et al.  Phase transition and in situ construction of lateral heterostructure of 2D superconducting α/β Mo2C with sharp interface by electron beam irradiation. , 2017, Nanoscale.

[13]  Yury Gogotsi,et al.  2D metal carbides and nitrides (MXenes) for energy storage , 2017 .

[14]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[15]  X. Tao,et al.  Pillared Structure Design of MXene with Ultralarge Interlayer Spacing for High-Performance Lithium-Ion Capacitors. , 2017, ACS nano.

[16]  A. Du,et al.  2D MXenes: A New Family of Promising Catalysts for the Hydrogen Evolution Reaction , 2017 .

[17]  Kai Xiao,et al.  Atomic Defects in Monolayer Titanium Carbide (Ti3C2Tx) MXene. , 2016, ACS nano.

[18]  A. Vojvodić,et al.  Two-Dimensional Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution , 2016 .

[19]  Jinlan Wang,et al.  Transition Metal‐Promoted V2CO2 (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution Reaction , 2016, Advanced science.

[20]  Charlie Tsai,et al.  Designing an improved transition metal phosphide catalyst for hydrogen evolution using experimental and theoretical trends , 2015 .

[21]  M. Weeda,et al.  The hydrogen economy – Vision or reality? , 2015 .

[22]  Henny W. Zandbergen,et al.  Controlling Defects in Graphene for Optimizing the Electrical Properties of Graphene Nanodevices , 2015, ACS nano.

[23]  Yao Zheng,et al.  Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. , 2015, Chemical Society reviews.

[24]  Bryan T. Yonemoto,et al.  Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution , 2015, Nature Communications.

[25]  Dehui Deng,et al.  Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. , 2015, Angewandte Chemie.

[26]  Jakob Kibsgaard,et al.  Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction. , 2014, Angewandte Chemie.

[27]  Yury Gogotsi,et al.  Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance , 2014, Nature.

[28]  Thomas F. Jaramillo,et al.  Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials , 2014 .

[29]  Quan Xu,et al.  N-doped graphene as catalysts for oxygen reduction and oxygen evolution reactions: Theoretical considerations , 2014 .

[30]  Charlie Tsai,et al.  Tuning the MoS₂ edge-site activity for hydrogen evolution via support interactions. , 2014, Nano letters.

[31]  Yury Gogotsi,et al.  25th Anniversary Article: MXenes: A New Family of Two‐Dimensional Materials , 2014, Advanced materials.

[32]  Jens K Nørskov,et al.  Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. , 2013, Journal of the American Chemical Society.

[33]  Y. Najjar.  Hydrogen safety: The road toward green technology , 2013 .

[34]  Jing Kong,et al.  Intrinsic structural defects in monolayer molybdenum disulfide. , 2013, Nano letters.

[35]  Desheng Kong,et al.  Synthesis of MoS2 and MoSe2 films with vertically aligned layers. , 2013, Nano letters.

[36]  Yury Gogotsi,et al.  Two-dimensional transition metal carbides. , 2012, ACS nano.

[37]  V. Presser,et al.  Two‐Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2 , 2011, Advanced materials.

[38]  J. Nørskov,et al.  Cover Picture: Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces (ChemCatChem 7/2011) , 2011 .

[39]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[40]  Xiaobo Du,et al.  Stability of Ferromagnetism in Fe, Co, and Ni Metals under High Pressure with GGA and GGA+U , 2010 .

[41]  Jens K Nørskov,et al.  Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT. , 2008, Physical chemistry chemical physics : PCCP.

[42]  J. Nørskov,et al.  Computational high-throughput screening of electrocatalytic materials for hydrogen evolution , 2006, Nature materials.

[43]  Thomas Bligaard,et al.  Trends in the exchange current for hydrogen evolution , 2005 .

[44]  John A. Turner,et al.  Sustainable Hydrogen Production , 2004, Science.

[45]  G. Guo,et al.  First-principles investigations of the orbital magnetic moments in CrO2 , 2002 .

[46]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[47]  C. Humphreys,et al.  Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study , 1998 .

[48]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[49]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[50]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[51]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[52]  Y. Jiao,et al.  Holey Reduced Graphene Oxide Coupled with an Mo2N–Mo2C Heterojunction for Efficient Hydrogen Evolution , 2018, Advanced materials.

[53]  Charlie Tsai,et al.  Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. , 2016, Nature materials.

[54]  Wei-Bing Zhang,et al.  Water Adsorption on a NiO(100) Surface: A GGA+U Study , 2008 .