Computational screening of transition metal-doped phthalocyanine monolayers for oxygen evolution and reduction
Abstract
Rationally designing efficient, low-cost and stable catalysts toward the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) is of significant importance to the development of renewable energy technologies. In this work, we have systematically investigated a series of potentially efficient and stable single late transition metal atom doped phthalocyanines (TM@Pcs, TM = Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir and Pt) as single-atom catalysts (SACs) for applications toward the OER and ORR through a computational screening approach. Our calculations indicate that TM atoms can tightly bind with Pc monolayers with high diffusion energy barriers to prevent the isolated atoms from clustering. The interaction strength between intermediates and TM@Pc governs the catalytic activities for the OER and ORR. Among all the considered TM@Pc catalysts, Ir@Pc and Rh@Pc were found to be efficient OER electrocatalysts with overpotentials ηOER of 0.41 and 0.44 V, respectively, and for the ORR, Rh@Pc exhibits the lowest overpotential ηORR of 0.44 V followed by Ir@Pc (0.55 V), suggesting that Rh@Pc is an efficient bifunctional catalyst for both the OER and ORR. Moreover, it is worth noting that the Rh@Pc catalyst can remain stable against dissolution under the pH = 0 condition. Ab initiomore »
- Authors:
-
- School of Chemical Engineering, Sichuan University, Chengdu, China, Materials Science Division
- Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, USA
- School of Chemical Engineering, Sichuan University, Chengdu, China
- Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, USA, Joint Center for Artificial Photosynthesis
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1581012
- Alternate Identifier(s):
- OSTI ID: 1760217
- Grant/Contract Number:
- SC0004993; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Nanoscale Advances
- Additional Journal Information:
- Journal Name: Nanoscale Advances Journal Volume: 2 Journal Issue: 2; Journal ID: ISSN 2516-0230
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhou, Yanan, Gao, Guoping, Chu, Wei, and Wang, Lin-Wang. Computational screening of transition metal-doped phthalocyanine monolayers for oxygen evolution and reduction. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9NA00648F.
Zhou, Yanan, Gao, Guoping, Chu, Wei, & Wang, Lin-Wang. Computational screening of transition metal-doped phthalocyanine monolayers for oxygen evolution and reduction. United Kingdom. doi:10.1039/C9NA00648F.
Zhou, Yanan, Gao, Guoping, Chu, Wei, and Wang, Lin-Wang. Tue .
"Computational screening of transition metal-doped phthalocyanine monolayers for oxygen evolution and reduction". United Kingdom. doi:10.1039/C9NA00648F.
@article{osti_1581012,
title = {Computational screening of transition metal-doped phthalocyanine monolayers for oxygen evolution and reduction},
author = {Zhou, Yanan and Gao, Guoping and Chu, Wei and Wang, Lin-Wang},
abstractNote = {Rationally designing efficient, low-cost and stable catalysts toward the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) is of significant importance to the development of renewable energy technologies. In this work, we have systematically investigated a series of potentially efficient and stable single late transition metal atom doped phthalocyanines (TM@Pcs, TM = Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir and Pt) as single-atom catalysts (SACs) for applications toward the OER and ORR through a computational screening approach. Our calculations indicate that TM atoms can tightly bind with Pc monolayers with high diffusion energy barriers to prevent the isolated atoms from clustering. The interaction strength between intermediates and TM@Pc governs the catalytic activities for the OER and ORR. Among all the considered TM@Pc catalysts, Ir@Pc and Rh@Pc were found to be efficient OER electrocatalysts with overpotentials ηOER of 0.41 and 0.44 V, respectively, and for the ORR, Rh@Pc exhibits the lowest overpotential ηORR of 0.44 V followed by Ir@Pc (0.55 V), suggesting that Rh@Pc is an efficient bifunctional catalyst for both the OER and ORR. Moreover, it is worth noting that the Rh@Pc catalyst can remain stable against dissolution under the pH = 0 condition. Ab initio molecular dynamic calculations suggest that Rh@Pc could remain stable at 300 K. Our findings highlight a novel family of two-dimensional (2D) materials as efficient and stable SACs and offer a new strategy for catalyst design.},
doi = {10.1039/C9NA00648F},
journal = {Nanoscale Advances},
number = 2,
volume = 2,
place = {United Kingdom},
year = {2020},
month = {2}
}
DOI: 10.1039/C9NA00648F
Works referenced in this record:
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
Transition-metal single atoms in nitrogen-doped graphenes as efficient active centers for water splitting: a theoretical study
journal, January 2019
- Zhou, Yanan; Gao, Guoping; Li, Yan
- Physical Chemistry Chemical Physics, Vol. 21, Issue 6
The synthesis and synergistic catalysis of iron phthalocyanine and its graphene-based axial complex for enhanced oxygen reduction
journal, April 2018
- Guo, Jia; Yan, Xiaomei; Liu, Qin
- Nano Energy, Vol. 46
Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT
journal, January 2016
- Zhang, Zhengping; Yang, Shaoxuan; Dou, Meiling
- RSC Advances, Vol. 6, Issue 71
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure
journal, April 2006
- Stamenkovic, Vojislav; Mun, Bongjin Simon; Mayrhofer, Karl J. J.
- Angewandte Chemie International Edition, Vol. 45, Issue 18
Single-Atom Catalysts for Electrochemical Water Splitting
journal, June 2018
- Zhu, Chengzhou; Shi, Qiurong; Feng, Shuo
- ACS Energy Letters, Vol. 3, Issue 7
Spin Tuning of Electron-Doped Metal–Phthalocyanine Layers
journal, February 2014
- Stepanow, Sebastian; Lodi Rizzini, Alberto; Krull, Cornelius
- Journal of the American Chemical Society, Vol. 136, Issue 14
The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC
journal, February 2007
- Lu, Yuhao; Reddy, Ramana G.
- Electrochimica Acta, Vol. 52, Issue 7
Oxygen reduction and evolution at single-metal active sites: Comparison between functionalized graphitic materials and protoporphyrins
journal, January 2013
- Calle-Vallejo, F.; Martínez, J. I.; García-Lastra, J. M.
- Surface Science, Vol. 607
Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting
journal, July 2017
- Ling, Chongyi; Shi, Li; Ouyang, Yixin
- Nano Letters, Vol. 17, Issue 8
Transition metal anchored C 2 N monolayers as efficient bifunctional electrocatalysts for hydrogen and oxygen evolution reactions
journal, January 2018
- Zhang, Xu; Chen, An; Zhang, Zihe
- Journal of Materials Chemistry A, Vol. 6, Issue 24
Single Layer of Polymeric Cobalt Phthalocyanine: Promising Low-Cost and High-Activity Nanocatalysts for CO Oxidation
journal, April 2013
- Deng, Qingming; Zhao, Lina; Gao, Xingfa
- Small, Vol. 9, Issue 20
Oxygen evolution on well-characterized mass-selected Ru and RuO 2 nanoparticles
journal, January 2015
- Paoli, Elisa A.; Masini, Federico; Frydendal, Rasmus
- Chemical Science, Vol. 6, Issue 1
Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis
journal, September 2011
- Koper, Marc T. M.
- Journal of Electroanalytical Chemistry, Vol. 660, Issue 2
Space-Confinement-Induced Synthesis of Pyridinic- and Pyrrolic-Nitrogen-Doped Graphene for the Catalysis of Oxygen Reduction
journal, September 2013
- Ding, Wei; Wei, Zidong; Chen, Siguo
- Angewandte Chemie International Edition, Vol. 52, Issue 45
Manganese Phthalocyanine Derivatives Synthesized by On-Surface Cyclotetramerization
journal, July 2014
- Piantek, Marten; Serrate, David; Moro-Lagares, Maria
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013
- Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
- Accounts of Chemical Research, Vol. 46, Issue 8
Tailoring molecular architectures of Fe phthalocyanine on nanocarbon supports for high oxygen reduction performance
journal, January 2015
- Zhang, Shiming; Zhang, Heyou; Hua, Xing
- Journal of Materials Chemistry A, Vol. 3, Issue 18
Alternative energy technologies
journal, November 2001
- Dresselhaus, M. S.; Thomas, I. L.
- Nature, Vol. 414, Issue 6861
Computational screening of transition-metal single atom doped C 9 N 4 monolayers as efficient electrocatalysts for water splitting
journal, January 2019
- Zhou, Yanan; Gao, Guoping; Kang, Jun
- Nanoscale, Vol. 11, Issue 39
Absorption induced modulation of magnetism in two-dimensional metal-phthalocyanine porous sheets
journal, May 2013
- Zhou, Jian; Sun, Qiang
- The Journal of Chemical Physics, Vol. 138, Issue 20
Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005
- Nørskov, J. K.; Bligaard, T.; Logadottir, A.
- Journal of The Electrochemical Society, Vol. 152, Issue 3
Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review
journal, July 2001
- Marković, N. M.; Schmidt, T. J.; Stamenković, V.
- Fuel Cells, Vol. 1, Issue 2
Stable and Efficient Nitrogen-Containing Carbon-Based Electrocatalysts for Reactions in Energy-Conversion Systems
journal, June 2018
- Wang, Sicong; Teng, Zhengyuan; Wang, Chengyin
- ChemSusChem, Vol. 11, Issue 14
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Unraveling Oxygen Reduction Reaction Mechanisms on Carbon-Supported Fe-Phthalocyanine and Co-Phthalocyanine Catalysts in Alkaline Solutions
journal, November 2009
- Chen, Rongrong; Li, Haixia; Chu, Deryn
- The Journal of Physical Chemistry C, Vol. 113, Issue 48
Innentitelbild: Fein-Tuning der Porengröße in versteiften ZIF-8_Cm-Gerüsten durch eine Mixed-Linker-Strategie für verbesserte permeative CO 2 /CH 4 -Trennung (Angew. Chem. 1/2019)
journal, December 2018
- Hou, Qianqian; Wu, Ying; Zhou, Sheng
- Angewandte Chemie, Vol. 131, Issue 1
Mo isolated single atoms on S, N-codoped carbon as efficient catalyst for hydrogen evolution reaction: A theoretical evaluation
journal, April 2019
- Gao, Xiaoping; Zhou, Yanan; Tan, Yujia
- Applied Surface Science, Vol. 473
Electrolysis of water on (oxidized) metal surfaces
journal, December 2005
- Rossmeisl, J.; Logadottir, A.; Nørskov, J. K.
- Chemical Physics, Vol. 319, Issue 1-3, p. 178-184
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Single-Atom Catalysts: Emerging Multifunctional Materials in Heterogeneous Catalysis
journal, September 2017
- Zhang, Huabin; Liu, Guigao; Shi, Li
- Advanced Energy Materials, Vol. 8, Issue 1
Effect of Strain on the Reactivity of Metal Surfaces
journal, September 1998
- Mavrikakis, M.; Hammer, B.; Nørskov, J. K.
- Physical Review Letters, Vol. 81, Issue 13
An ethynyl-linked Fe/Co heterometallic phthalocyanine conjugated polymer for the oxygen reduction reaction
journal, January 2018
- Liu, Wenping; Hou, Yuxia; Pan, Houhe
- Journal of Materials Chemistry A, Vol. 6, Issue 18
Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters
journal, March 2010
- Lopez-Acevedo, Olga; Kacprzak, Katarzyna A.; Akola, Jaakko
- Nature Chemistry, Vol. 2, Issue 4
How covalence breaks adsorption-energy scaling relations and solvation restores them
journal, January 2017
- Calle-Vallejo, Federico; Krabbe, Alexander; García-Lastra, Juan M.
- Chemical Science, Vol. 8, Issue 1
Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide
journal, May 2016
- Gao, Guoping; Jiao, Yan; Waclawik, Eric R.
- Journal of the American Chemical Society, Vol. 138, Issue 19
Electronic structure modification of platinum on titanium nitride resulting in enhanced catalytic activity and durability for oxygen reduction and formic acid oxidation
journal, September 2015
- Yang, Sungeun; Chung, Dong Young; Tak, Young-Joo
- Applied Catalysis B: Environmental, Vol. 174-175
Carrier induced magnetic coupling transitions in phthalocyanine-based organometallic sheet
journal, January 2014
- Zhou, Jian; Sun, Qiang
- Nanoscale, Vol. 6, Issue 1
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014
- Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- The Journal of Chemical Physics, Vol. 140, Issue 8
Theoretical insight into highly durable iron phthalocyanine derived non-precious catalysts for oxygen reduction reactions
journal, January 2014
- Seo, Min Ho; Higgins, Drew; Jiang, Gaopeng
- J. Mater. Chem. A, Vol. 2, Issue 46
Nosé–Hoover chains: The canonical ensemble via continuous dynamics
journal, August 1992
- Martyna, Glenn J.; Klein, Michael L.; Tuckerman, Mark
- The Journal of Chemical Physics, Vol. 97, Issue 4
In Situ Photochemical Activation of Sulfate for Enhanced Degradation of Organic Pollutants in Water
journal, February 2017
- Liu, Guoshuai; You, Shijie; Tan, Yang
- Environmental Science & Technology, Vol. 51, Issue 4
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011
- Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
- ChemCatChem, Vol. 3, Issue 7
Assessing Carbon-Based Anodes for Lithium-Ion Batteries: A Universal Description of Charge-Transfer Binding
journal, July 2014
- Liu, Yuanyue; Wang, Y. Morris; Yakobson, Boris I.
- Physical Review Letters, Vol. 113, Issue 2
Electrolysis of water on oxide surfaces
journal, September 2007
- Rossmeisl, J.; Qu, Z. -W.; Zhu, H.
- Journal of Electroanalytical Chemistry, Vol. 607, Issue 1-2
Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions
journal, January 2015
- Jiao, Yan; Zheng, Yao; Jaroniec, Mietek
- Chemical Society Reviews, Vol. 44, Issue 8
Hierarchy of Chemical Bonding in the Synthesis of Fe-Phthalocyanine on Metal Surfaces: A Local Spectroscopy Approach
journal, September 2014
- Kezilebieke, Shawulienu; Amokrane, Anis; Abel, Mathieu
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 18
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
Transition‐Metal Single Atoms Anchored on Graphdiyne as High‐Efficiency Electrocatalysts for Water Splitting and Oxygen Reduction
journal, January 2019
- He, Tianwei; Matta, Sri Kasi; Will, Geoffrey
- Small Methods, Vol. 3, Issue 9
Redox transitions of chromium, manganese, iron, cobalt and nickel protoporphyrins in aqueous solution
journal, January 2008
- de Groot, Matheus T.; Koper, Marc T. M.
- Phys. Chem. Chem. Phys., Vol. 10, Issue 7
High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction
journal, June 2015
- Huang, X.; Zhao, Z.; Cao, L.
- Science, Vol. 348, Issue 6240
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Single Layer of Polymeric Fe-Phthalocyanine: An Organometallic Sheet on Metal and Thin Insulating Film
journal, February 2011
- Abel, Mathieu; Clair, Sylvain; Ourdjini, Oualid
- Journal of the American Chemical Society, Vol. 133, Issue 5
Gold catalysis at the gas–solid interface: role of the support in determining activity and selectivity in the hydrogenation of m-dinitrobenzene
journal, January 2011
- Cárdenas-Lizana, Fernando; Gómez-Quero, Santiago; Perret, Noémie
- Catalysis Science & Technology, Vol. 1, Issue 4
Demetalation of a Single Organometallic Complex
journal, July 2011
- Sperl, Alexander; Kröger, Jörg; Berndt, Richard
- Journal of the American Chemical Society, Vol. 133, Issue 29
Role of renewable energy sources in environmental protection: A review
journal, April 2011
- Panwar, N. L.; Kaushik, S. C.; Kothari, Surendra
- Renewable and Sustainable Energy Reviews, Vol. 15, Issue 3
Strain-Induced Spin Crossover in Phthalocyanine-Based Organometallic Sheets
journal, October 2012
- Zhou, Jian; Wang, Qian; Sun, Qiang
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 21
Two-dimensional iron-phthalocyanine (Fe-Pc) monolayer as a promising single-atom-catalyst for oxygen reduction reaction: a computational study
journal, January 2015
- Wang, Yu; Yuan, Hao; Li, Yafei
- Nanoscale, Vol. 7, Issue 27
Role of Strain and Ligand Effects in the Modification of the Electronic and Chemical Properties of Bimetallic Surfaces
journal, October 2004
- Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.
- Physical Review Letters, Vol. 93, Issue 15
Magnetism of Phthalocyanine-Based Organometallic Single Porous Sheet
journal, September 2011
- Zhou, Jian; Sun, Qiang
- Journal of the American Chemical Society, Vol. 133, Issue 38
A New Fuel Cell Cathode Catalyst
journal, March 1964
- Jasinski, Raymond
- Nature, Vol. 201, Issue 4925, p. 1212-1213
Pre-combustion CO 2 capture by transition metal ions embedded in phthalocyanine sheets
journal, June 2012
- Lü, Kun; Zhou, Jian; Zhou, Le
- The Journal of Chemical Physics, Vol. 136, Issue 23
Probing the Influence of the Conjugated Structure and Halogen Atoms of Poly-Iron-Phthalocyanine on the Oxygen Reduction Reaction by X-ray Absorption Spectroscopy and Density Functional Theory
journal, February 2015
- Peng, Yingxiang; Cui, Lufang; Yang, Shifeng
- Electrochimica Acta, Vol. 154
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution
journal, January 2014
- Morales-Guio, Carlos G.; Stern, Lucas-Alexandre; Hu, Xile
- Chemical Society Reviews, Vol. 43, Issue 18
Remarkable Performance of Ir 1 /FeO x Single-Atom Catalyst in Water Gas Shift Reaction
journal, October 2013
- Lin, Jian; Wang, Aiqin; Qiao, Botao
- Journal of the American Chemical Society, Vol. 135, Issue 41
Bifunctional CoNx embedded graphene electrocatalysts for OER and ORR: A theoretical evaluation
journal, April 2018
- Zhang, Xilin; Yang, Zongxian; Lu, Zhansheng
- Carbon, Vol. 130
Towards the computational design of solid catalysts
journal, April 2009
- Nørskov, J.; Bligaard, T.; Rossmeisl, J.
- Nature Chemistry, Vol. 1, Issue 1, p. 37-46
Computational screening of two-dimensional coordination polymers as efficient catalysts for oxygen evolution and reduction reaction
journal, August 2017
- Gao, Guoping; Waclawik, Eric R.; Du, Aijun
- Journal of Catalysis, Vol. 352
Rationale for mixing exact exchange with density functional approximations
journal, December 1996
- Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
- The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
Iron polyphthalocyanine sheathed multiwalled carbon nanotubes: A high-performance electrocatalyst for oxygen reduction reaction
journal, May 2016
- Wang, Xinxia; Wang, Bin; Zhong, Jun
- Nano Research, Vol. 9, Issue 5
Transition metal-embedded two-dimensional C 3 N as a highly active electrocatalyst for oxygen evolution and reduction reactions
journal, January 2019
- Zhou, Yanan; Gao, Guoping; Kang, Jun
- Journal of Materials Chemistry A, Vol. 7, Issue 19
Density Functional Theory Study of Iron Phthalocyanine Porous Layer Deposited on Graphene Substrate: A Pt-Free Electrocatalyst for Hydrogen Fuel Cells
journal, January 2016
- Mussell, Sean; Choudhury, Pabitra
- The Journal of Physical Chemistry C, Vol. 120, Issue 10
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009
- Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.
- Nature Chemistry, Vol. 1, Issue 7, p. 552-556
Space-Confinement-Induced Synthesis of Pyridinic- and Pyrrolic-Nitrogen-Doped Graphene for the Catalysis of Oxygen Reduction
journal, September 2013
- Ding, Wei; Wei, Zidong; Chen, Siguo
- Angewandte Chemie, Vol. 125, Issue 45