Hydrogenation of Covalent Organic Framework Induces Conjugated π Bonds and Electronic Topological Transition to Enhance Hydrogen Evolution Catalysis

Zhang, Tan; Jiang, Zhen; Rappe, Andrew M.

doi:10.1021/jacs.4c03973

Title: Hydrogenation of Covalent Organic Framework Induces Conjugated π Bonds and Electronic Topological Transition to Enhance Hydrogen Evolution Catalysis

Journal Article · Wed May 22 00:00:00 UTC 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c03973 · OSTI ID:2476637

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University of Pennsylvania, Philadelphia, PA (United States); Univ. of Pennsylvania
University of Pennsylvania, Philadelphia, PA (United States)

Recently, many topological materials have been discovered as promising electrocatalysts in chemical conversion processes and energy storage. However, it remains unclear how the topological electronic states specifically modulate the catalytic reaction. Here, the two-dimensional metal phthalocyanine-based covalent organic framework (MP_c-COF) is studied by ab initio thermodynamic calculations to clearly reveal the promotional effect on the electrochemical hydrogen evolution reaction (HER) induced by topological gapless bands (TGBs). We find that the prehydrogenated (and fluorinated) H₄CdPc-COF(F) shows the best HER performance, with 0.016 V (near zero) overpotential. By tracking changes to the electronic structure and free energy as the prehydrogenation and HER processes occur, we are able to separately attribute the high HER efficiency in part due to the increase of the electron bath by donating electrons to the conjugated π bonds and also to the existence of TGBs. Specifically, the significant catalytic promotion by TGBs is proven to decrease the free energy by 0.218 eV to near zero. When the TGBs are destroyed, e.g., by replacing N with P and opening a band gap, the HER efficiency is reduced. As a result, this study opens avenues for deterministically harnessing topological band features to improve electrocatalysis.

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Research Organization:: University of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; FG02-07ER46431; SC0019281

OSTI ID:: 2476637

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Topological Engineering of Pt‐Group‐Metal‐Based Chiral Crystals toward High‐Efficiency Hydrogen Evolution Catalysts Yang, Qun; Li, Guowei; Manna, Kaustuv Advanced Materials, Vol. 32, Issue 14 https://doi.org/10.1002/adma.201908518	journal	April 2020
Facet Engineering to Regulate Surface States of Topological Crystalline Insulator Bismuth Rhombic Dodecahedrons for Highly Energy Efficient Electrochemical CO₂ Reduction Xie, Huan; Zhang, Tan; Xie, Ruikuan Advanced Materials, Vol. 33, Issue 31 https://doi.org/10.1002/adma.202008373	journal	June 2021
A Bimetallic Zn/Fe Polyphthalocyanine-Derived Single-Atom Fe-N ₄ Catalytic Site:A Superior Trifunctional Catalyst for Overall Water Splitting and Zn-Air Batteries Pan, Yuan; Liu, Shoujie; Sun, Kaian Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201804349	journal	May 2018
A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction Zhong, Haixia; Ly, Khoa Hoang; Wang, Mingchao Angewandte Chemie International Edition, Vol. 58, Issue 31 https://doi.org/10.1002/anie.201907002	journal	July 2019
Two‐Dimensional Conjugated Aromatic Networks as High‐Site‐Density and Single‐Atom Electrocatalysts for the Oxygen Reduction Reaction Yang, Shaoxuan; Yu, Yihuan; Dou, Meiling Angewandte Chemie International Edition, Vol. 58, Issue 41 https://doi.org/10.1002/anie.201908023	journal	September 2019
Enhancing CO ₂ Electroreduction to Methane with a Cobalt Phthalocyanine and Zinc–Nitrogen–Carbon Tandem Catalyst Lin, Long; Liu, Tianfu; Xiao, Jianping Angewandte Chemie International Edition, Vol. 59, Issue 50 https://doi.org/10.1002/anie.202009191	journal	October 2020
Tunablee_gOrbital Occupancy in Heusler Compounds for Oxygen Evolution Reaction** Yu, Mingquan; Li, Guowei; Fu, Chenguang Angewandte Chemie International Edition, Vol. 60, Issue 11 https://doi.org/10.1002/anie.202013610	journal	February 2021
Progress, Advantages, and Challenges of Topological Material Catalysts Xie, Ruikuan; Zhang, Tan; Weng, Hongming Small Science, Vol. 2, Issue 4 https://doi.org/10.1002/smsc.202100106	journal	February 2022
Cobalt phthalocyanine coordinated to pyridine-functionalized carbon nanotubes with enhanced CO2 electroreduction Zhu, Minghui; Chen, Jiacheng; Guo, Rong Applied Catalysis B: Environmental, Vol. 251 https://doi.org/10.1016/j.apcatb.2019.03.047	journal	August 2019
Conjugated nickel phthalocyanine polymer selectively catalyzes CO2-to-CO conversion in a wide operating potential window Wei, Shuting; Zou, Haiyuan; Rong, Weifeng Applied Catalysis B: Environmental, Vol. 284 https://doi.org/10.1016/j.apcatb.2020.119739	journal	May 2021
Supported Cobalt Polyphthalocyanine for High-Performance Electrocatalytic CO2 Reduction Han, Na; Wang, Yu; Ma, Lu Chem, Vol. 3, Issue 4 https://doi.org/10.1016/j.chempr.2017.08.002	journal	October 2017
In-situ cobalt and nitrogen doped mesoporous graphitic carbon electrocatalyst via directly pyrolyzing hyperbranched cobalt phthalocyanine for hydrogen evolution reaction Yang, Jian; Cai, Chao; Li, Yulan Electrochimica Acta, Vol. 262 https://doi.org/10.1016/j.electacta.2018.01.014	journal	February 2018
Spin Chern number and topological phase transition on the Lieb lattice with spin–orbit coupling Chen, Rui; Zhou, Bin Physics Letters A, Vol. 381, Issue 10 https://doi.org/10.1016/j.physleta.2017.01.021	journal	March 2017
Exotic Topological Bands and Quantum States in Metal–Organic and Covalent–Organic Frameworks Jiang, Wei; Ni, Xiaojuan; Liu, Feng Accounts of Chemical Research, Vol. 54, Issue 2 https://doi.org/10.1021/acs.accounts.0c00652	journal	January 2021
Topological Insulating Phase in Single-Layer Pentagonal Covalent Organic Frameworks: A Reticular Design Using Metal Phthalocyanine Pham, Hung Q.; Pham-Tran, Nguyen-Nguyen Chemistry of Materials, Vol. 33, Issue 12 https://doi.org/10.1021/acs.chemmater.1c00671	journal	June 2021
Emergence of a Two-Dimensional Topological Dirac Semimetal Phase in a Phthalocyanine-Based Covalent Organic Framework Ni, Xiaojuan; Huang, Huaqing; Brédas, Jean-Luc Chemistry of Materials, Vol. 34, Issue 7 https://doi.org/10.1021/acs.chemmater.1c04317	journal	March 2022
Iron Phthalocyanine/Two-Dimensional Metal–Organic Framework Composite Nanosheets for Enhanced Alkaline Hydrogen Evolution Zhang, Xiaoyin; Lin, Rijia; Meng, Xiangmin Inorganic Chemistry, Vol. 60, Issue 13 https://doi.org/10.1021/acs.inorgchem.1c01259	journal	June 2021
Enhancing Oxygen Electroreduction Activity of Single-Site Fe–N–C Catalysts by a Metal Support Jiang, Zhen; Alexandrov, Vitaly The Journal of Physical Chemistry C, Vol. 123, Issue 50 https://doi.org/10.1021/acs.jpcc.9b07860	journal	November 2019
Topological Band Engineering of Lieb Lattice in Phthalocyanine-Based Metal–Organic Frameworks Jiang, Wei; Zhang, Shunhong; Wang, Zhengfei Nano Letters, Vol. 20, Issue 3 https://doi.org/10.1021/acs.nanolett.9b05242	journal	February 2020
An Insight into Anchoring of Cobalt Phthalocyanines onto Carbon: Efficiency of the CO₂ Reduction Reaction Ma, Jing-Jing; Zhu, Hong-Lin; Zheng, Yue-Qing ACS Applied Energy Materials, Vol. 4, Issue 2 https://doi.org/10.1021/acsaem.0c02645	journal	February 2021
Iron Phthalocyanine-Knitted Polymers as Electrocatalysts for the Oxygen Reduction Reaction Valverde-González, Antonio; Guan, Li Zhi; Ferrer, M. Luisa ACS Applied Materials & Interfaces, Vol. 12, Issue 29 https://doi.org/10.1021/acsami.0c07412	journal	June 2020
Intrinsic Defect-Rich Graphene Coupled Cobalt Phthalocyanine for Robust Electrochemical Reduction of Carbon Dioxide Liang, Fengxia; Zhang, Jun; Hu, Zewei ACS Applied Materials & Interfaces, Vol. 13, Issue 21 https://doi.org/10.1021/acsami.1c04344	journal	May 2021
Expediting Hydrogen Evolution through Topological Surface States on Bi₂Te₃ Qu, Qing; Liu, Bin; Liang, Jing ACS Catalysis, Vol. 10, Issue 4 https://doi.org/10.1021/acscatal.9b04318	journal	January 2020
Magnetism of Phthalocyanine-Based Organometallic Single Porous Sheet Zhou, Jian; Sun, Qiang Journal of the American Chemical Society, Vol. 133, Issue 38 https://doi.org/10.1021/ja204990j	journal	September 2011
Edge-Functionalized Polyphthalocyanine Networks with High Oxygen Reduction Reaction Activity Yang, Shaoxuan; Yu, Yihuan; Dou, Meiling Journal of the American Chemical Society, Vol. 142, Issue 41 https://doi.org/10.1021/jacs.0c07249	journal	September 2020
Graphdiyne/Graphene Heterostructure: A Universal 2D Scaffold Anchoring Monodispersed Transition-Metal Phthalocyanines for Selective and Durable CO₂ Electroreduction Gu, Huoliang; Zhong, Lixiang; Shi, Guoshuai Journal of the American Chemical Society, Vol. 143, Issue 23 https://doi.org/10.1021/jacs.1c02326	journal	June 2021
Strain-Induced Spin Crossover in Phthalocyanine-Based Organometallic Sheets Zhou, Jian; Wang, Qian; Sun, Qiang The Journal of Physical Chemistry Letters, Vol. 3, Issue 21 https://doi.org/10.1021/jz301303t	journal	October 2012
Alternative energy technologies Dresselhaus, M. S.; Thomas, I. L. Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104599	journal	November 2001
Topological insulators in Bi₂Se₃, Bi₂Te₃ and Sb₂Te₃ with a single Dirac cone on the surface Zhang, Haijun; Liu, Chao-Xing; Qi, Xiao-Liang Nature Physics, Vol. 5, Issue 6, p. 438-442 https://doi.org/10.1038/nphys1270	journal	May 2009
Experimental realization and characterization of an electronic Lieb lattice Slot, Marlou R.; Gardenier, Thomas S.; Jacobse, Peter H. Nature Physics, Vol. 13, Issue 7 https://doi.org/10.1038/nphys4105	journal	April 2017
Transition metal on topological chiral semimetal PdGa with tailored hydrogen adsorption and reduction Yang, Qun; Li, Guowei; Zhang, Yudi npj Computational Materials, Vol. 7, Issue 1 https://doi.org/10.1038/s41524-021-00684-5	journal	December 2021
Topological quantum materials for energy conversion and storage Luo, Huixia; Yu, Peifeng; Li, Guowei Nature Reviews Physics, Vol. 4, Issue 9 https://doi.org/10.1038/s42254-022-00477-9	journal	July 2022
Recent advances in electrocatalysis with phthalocyanines Yang, Shaoxuan; Yu, Yihuan; Gao, Xinjin Chemical Society Reviews, Vol. 50, Issue 23 https://doi.org/10.1039/D0CS01605E	journal	January 2021
Engineering of flat bands and Dirac bands in two-dimensional covalent organic frameworks (COFs): relationships among molecular orbital symmetry, lattice symmetry, and electronic-structure characteristics Ni, Xiaojuan; Li, Hong; Liu, Feng Materials Horizons, Vol. 9, Issue 1 https://doi.org/10.1039/D1MH00935D	journal	January 2022
Tunable electron property induced by B-doping in g-C₃N₄ Yang, Bo; Bu, Hongxia; Liu, Xiaobiao RSC Advances, Vol. 11, Issue 26 https://doi.org/10.1039/D1RA00149C	journal	January 2021
Topology on a new facet of bismuth Hsu, Chuang-Han; Zhou, Xiaoting; Chang, Tay-Rong Proceedings of the National Academy of Sciences, Vol. 116, Issue 27 https://doi.org/10.1073/pnas.1900527116	journal	June 2019
Topological semimetals predicted from first-principles calculations Weng, Hongming; Dai, Xi; Fang, Zhong Journal of Physics: Condensed Matter, Vol. 28, Issue 30 https://doi.org/10.1088/0953-8984/28/30/303001	journal	June 2016
Interaction-driven topological and nematic phases on the Lieb lattice Tsai, Wei-Feng; Fang, Chen; Yao, Hong New Journal of Physics, Vol. 17, Issue 5 https://doi.org/10.1088/1367-2630/17/5/055016	journal	May 2015
Two-dimensional graphitic carbon nitrides: Strain-tunable ferromagnetic ordering Bafekry, A.; Neek-Amal, M.; Peeters, F. M. Physical Review B, Vol. 101, Issue 16 https://doi.org/10.1103/PhysRevB.101.165407	journal	April 2020
Topological band evolution between Lieb and kagome lattices Jiang, Wei; Kang, Meng; Huang, Huaqing Physical Review B, Vol. 99, Issue 12 https://doi.org/10.1103/PhysRevB.99.125131	journal	March 2019
Topological Insulators and Nematic Phases from Spontaneous Symmetry Breaking in 2D Fermi Systems with a Quadratic Band Crossing Sun, Kai; Yao, Hong; Fradkin, Eduardo Physical Review Letters, Vol. 103, Issue 4 https://doi.org/10.1103/PhysRevLett.103.046811	journal	July 2009
Colloquium: Topological insulators Hasan, M. Z.; Kane, C. L. Reviews of Modern Physics, Vol. 82, Issue 4, p. 3045-3067 https://doi.org/10.1103/RevModPhys.82.3045	journal	November 2010
Topological insulators with inversion symmetry Fu, Liang; Kane, C. L. Physical Review B, Vol. 76, Issue 4 https://doi.org/10.1103/physrevb.76.045302	journal	July 2007
A pyrolysis-free path toward superiorly catalytic nitrogen-coordinated single atom Peng, Peng; Shi, Lei; Huo, Feng Science Advances, Vol. 5, Issue 8 https://doi.org/10.1126/sciadv.aaw2322	journal	August 2019
Surface states in bulk single crystal of topological semimetal Co ₃ Sn ₂ S ₂ toward water oxidation Li, Guowei; Xu, Qiunan; Shi, Wujun Science Advances, Vol. 5, Issue 8 https://doi.org/10.1126/sciadv.aaw9867	journal	August 2019
Energy Resources and Global Development Chow, J. Science, Vol. 302, Issue 5650 https://doi.org/10.1126/science.1091939	journal	November 2003
Sustainable Hydrogen Production Turner, J. A. Science, Vol. 305, Issue 5686 https://doi.org/10.1126/science.1103197	journal	August 2004

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Title: Hydrogenation of Covalent Organic Framework Induces Conjugated π Bonds and Electronic Topological Transition to Enhance Hydrogen Evolution Catalysis

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