skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Rational design of super-alkalis and their role in CO 2 activation

Abstract

Super-alkalis are clusters of atoms. With ionization potentials smaller than those of the alkali atoms, they are playing an increasing role in chemistry as highlighted by recent applications in solar cells as well as in Li-ion batteries. For the past 40 years superalkalis were designed using inorganic elements with the sp orbital character. Here, we show that a large class of superalkalis composed of only simple metal atoms, transition metal complexes as well as organic molecules can be designed by making use of electron counting rules beyond the octet rule. Examples include Al3+, Mn(B3N3H6)2+, B9C3H12+, and C5NH6+ which obey the jellium shell closure rule, the 18-electron rule, the Wade–Mingos rule, and Hückel's aromatic rule, respectively. We further show that the ability of superalkalis to transfer an electron easily can be used to activate a CO2 molecule by transforming it from a linear to a bent structure. These results, based on density functional theory with generalized gradient approximation for exchange–correlation potential, open the door to a new class of catalysts for CO2 activation.

Authors:
 [1]; ORCiD logo [2];  [3]
  1. Peking Univ., Beijing (China). Center for Applied Physics; Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
  2. Peking Univ., Beijing (China). Center for Applied Physic
  3. Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1492961
DOE Contract Number:  
FG02-96ER45579; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 9; Journal Issue: 15; Journal ID: ISSN 2040-3364
Country of Publication:
United States
Language:
English

Citation Formats

Zhao, Tianshan, Wang, Qian, and Jena, Puru. Rational design of super-alkalis and their role in CO 2 activation. United States: N. p., 2017. Web. doi:10.1039/c7nr00227k.
Zhao, Tianshan, Wang, Qian, & Jena, Puru. Rational design of super-alkalis and their role in CO 2 activation. United States. doi:10.1039/c7nr00227k.
Zhao, Tianshan, Wang, Qian, and Jena, Puru. Sun . "Rational design of super-alkalis and their role in CO 2 activation". United States. doi:10.1039/c7nr00227k.
@article{osti_1492961,
title = {Rational design of super-alkalis and their role in CO 2 activation},
author = {Zhao, Tianshan and Wang, Qian and Jena, Puru},
abstractNote = {Super-alkalis are clusters of atoms. With ionization potentials smaller than those of the alkali atoms, they are playing an increasing role in chemistry as highlighted by recent applications in solar cells as well as in Li-ion batteries. For the past 40 years superalkalis were designed using inorganic elements with the sp orbital character. Here, we show that a large class of superalkalis composed of only simple metal atoms, transition metal complexes as well as organic molecules can be designed by making use of electron counting rules beyond the octet rule. Examples include Al3+, Mn(B3N3H6)2+, B9C3H12+, and C5NH6+ which obey the jellium shell closure rule, the 18-electron rule, the Wade–Mingos rule, and Hückel's aromatic rule, respectively. We further show that the ability of superalkalis to transfer an electron easily can be used to activate a CO2 molecule by transforming it from a linear to a bent structure. These results, based on density functional theory with generalized gradient approximation for exchange–correlation potential, open the door to a new class of catalysts for CO2 activation.},
doi = {10.1039/c7nr00227k},
journal = {Nanoscale},
issn = {2040-3364},
number = 15,
volume = 9,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

Theoretical Study on Polynuclear Superalkali Cations with Various Functional Groups as the Central Core
journal, May 2012

  • Tong, Jing; Li, Ying; Wu, Di
  • Inorganic Chemistry, Vol. 51, Issue 11
  • DOI: 10.1021/ic202675j

Polyhedral skeletal electron pair approach
journal, September 1984

  • Mingos, D. Michael P.
  • Accounts of Chemical Research, Vol. 17, Issue 9
  • DOI: 10.1021/ar00105a003

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Superhalogens as building blocks of two-dimensional organic–inorganic hybrid perovskites for optoelectronics applications
journal, January 2016

  • Yao, Qiushi; Fang, Hong; Deng, Kaiming
  • Nanoscale, Vol. 8, Issue 41
  • DOI: 10.1039/C6NR05573G

Do nonmetallic superalkali cations exist?
journal, June 2013


Evolution of the electronic structure and properties of neutral and charged aluminum clusters: A comprehensive analysis
journal, August 1999

  • Rao, B. K.; Jena, P.
  • The Journal of Chemical Physics, Vol. 111, Issue 5
  • DOI: 10.1063/1.479458

Atomic clusters: Building blocks for a class of solids
journal, May 1995


Photoelectron spectroscopic and computational study of (M–CO 2 ) anions, M = Cu, Ag, Au
journal, November 2015

  • Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.
  • The Journal of Chemical Physics, Vol. 143, Issue 17
  • DOI: 10.1063/1.4935061

An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations
journal, December 1988

  • Scuseria, Gustavo E.; Janssen, Curtis L.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 89, Issue 12
  • DOI: 10.1063/1.455269

Assembling crystals from clusters
journal, September 1992


DVM Xα calculations on the electronic structure of “superalkali” cations
journal, October 1982


Projector augmented-wave method
journal, December 1994


Borane Derivatives: A New Class of Super- and Hyperhalogens
journal, July 2011

  • Pathak, Biswarup; Samanta , Devleena; Ahuja, Rajeev
  • ChemPhysChem, Vol. 12, Issue 13
  • DOI: 10.1002/cphc.201100320

A simple measure of electron localization in atomic and molecular systems
journal, May 1990

  • Becke, A. D.; Edgecombe, K. E.
  • The Journal of Chemical Physics, Vol. 92, Issue 9
  • DOI: 10.1063/1.458517

Photoelectron spectroscopy of the molecular anions, Li 3 O and Na 3 O
journal, October 2011

  • Wang, Di; Graham, Jacob D.; Buytendyk, Allyson M.
  • The Journal of Chemical Physics, Vol. 135, Issue 16
  • DOI: 10.1063/1.3657854

STRUCTURE OF B 12 H 12 - 2 ION
journal, August 1960

  • Wunderlich, Jeffrey A.; Lipscomb, William N.
  • Journal of the American Chemical Society, Vol. 82, Issue 16
  • DOI: 10.1021/ja01501a076

MP2 energy evaluation by direct methods
journal, December 1988


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Bonding in molecular clusters and their relationship to bulk metals
journal, January 1986


A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982

  • Purvis, George D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.443164

Origin of the unusual stability of MnO4−
journal, October 1999


Super-ion inspired colorful hybrid perovskite solar cells
journal, January 2016

  • Fang, Hong; Jena, Puru
  • Journal of Materials Chemistry A, Vol. 4, Issue 13
  • DOI: 10.1039/C5TA09646D

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Avoiding the integral storage bottleneck in LCAO calculations of electron correlation
journal, January 1989


Electron affinities of CO2, OCS, and CS2
journal, April 1998

  • Gutsev, Gennady L.; Bartlett, Rodney J.; Compton, Robert N.
  • The Journal of Chemical Physics, Vol. 108, Issue 16
  • DOI: 10.1063/1.476091

Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
journal, April 1984

  • Frisch, Michael J.; Pople, John A.; Binkley, J. Stephen
  • The Journal of Chemical Physics, Vol. 80, Issue 7
  • DOI: 10.1063/1.447079

Electronic Structure and Properties of Transition Metal−Benzene Complexes
journal, April 2001

  • Pandey, Ravindra; Rao, Bijan K.; Jena, Purusottam
  • Journal of the American Chemical Society, Vol. 123, Issue 16
  • DOI: 10.1021/ja0035452

Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries
journal, October 2014

  • Giri, Santanab; Behera, Swayamprabha; Jena, Puru
  • Angewandte Chemie International Edition, Vol. 53, Issue 50
  • DOI: 10.1002/anie.201408648

Atomic Clusters: Opportunities in the Face of Challenges
journal, April 2015


Superalkalis and Superhalogens As Building Blocks of Supersalts
journal, January 2014

  • Giri, Santanab; Behera, Swayamprabha; Jena, Puru
  • The Journal of Physical Chemistry A, Vol. 118, Issue 3
  • DOI: 10.1021/jp4115095

Icosahedral gold cage clusters: M@Au[sub 12][sup −] (M=V, Nb, and Ta)
journal, January 2004

  • Zhai, Hua-Jin; Li, Jun; Wang, Lai-Sheng
  • The Journal of Chemical Physics, Vol. 121, Issue 17
  • DOI: 10.1063/1.1799574

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Experimental Observation and Confirmation of Icosahedral W@Au12 and Mo@Au12 Molecules
journal, December 2002

  • Li, Xi; Kiran, Boggavarapu; Li, Jun
  • Angewandte Chemie International Edition, Vol. 41, Issue 24
  • DOI: 10.1002/anie.200290048

CO 2 Activation and Hydrogenation by PtH n Cluster Anions
journal, July 2016

  • Zhang, Xinxing; Liu, Gaoxiang; Meiwes-Broer, Karl-Heinz
  • Angewandte Chemie International Edition, Vol. 55, Issue 33
  • DOI: 10.1002/anie.201604308

Beyond the Periodic Table of Elements: The Role of Superatoms
journal, April 2013

  • Jena, Puru
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz400156t

Aromatic Superhalogens
journal, March 2014

  • Child, Brandon Z.; Giri, Santanab; Gronert, Scott
  • Chemistry - A European Journal, Vol. 20, Issue 16
  • DOI: 10.1002/chem.201305057