In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal–Organic Frameworks to Design Atomic Co1–P1N3 Interfacial Structure for Promoting Catalytic Performance

Wan, Jiawei; Zhao, Zhenghang; Shang, Huishan; Peng, Bo; Chen, Wenxing; Pei, Jiajing; Zheng, Lirong; Dong, Juncai; Cao, Rui; Sarangi, Ritimukta; Jiang, Zhuoli; Zhou, Danni; Zhuang, Zhongbin; Zhang, Jiatao; Wang, Dingsheng; Li, Yadong

doi:10.1021/jacs.0c02229

In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal–Organic Frameworks to Design Atomic Co₁–P₁N₃ Interfacial Structure for Promoting Catalytic Performance

Journal Article · Fri Apr 17 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c02229· OSTI ID:1638159

^[1]; ^[2]; Shang, Huishan ^[3]; Peng, Bo ^[4]; ^[3]; Pei, Jiajing ^[4]; Zheng, Lirong ^[5]; ^[5]; Cao, Rui ^[6]; ^[6]; Jiang, Zhuoli ^[3]; Zhou, Danni ^[3]; ^[4]; ^[3]; ^[1]; ^[1]

Tsinghua Univ., Beijing (China)
Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis
Beijing Inst. of Technology (China). Beijing Key Lab. of Construction Tailorable Advanced Functional Materials and Green Applications
Beijing Univ. of Chemical Technology (China)
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics (IHEP). Beijing Synchrotron Radiation Facility
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

The engineering coordination environment offers great opportunity in performance tunability of isolated metal single-atom catalysts. For the most popular metal–N_x(MN_x) structure, the replacement of N atoms by some other atoms with relatively weak electronegativity has been regarded as a promising strategy for optimizing the coordination environment of an active metal center and promoting its catalytic performance, which is still a challenge. Herein, we proposed a new synthetic strategy of an in situ phosphatizing of triphenylphosphine encapsulated within metal–organic frameworks for designing atomic Co₁–P₁N₃ interfacial structure, where a cobalt single atom is costabilized by one P atom and three N atoms (denoted as Co-SA/P-in situ). In the acidic media, the Co-SA/P-in situ catalyst with Co₁–P₁N₃ interfacial structure exhibits excellent activity and durability for the hydrogen evolution reaction (HER) with a low overpotential of 98 mV at 10 mA cm^–2 and a small Tafel slope of 47 mV dec^–1, which are greatly superior to those of catalyst with Co₁–N₄ interfacial structure. We discover that the bond-length-extended high-valence Co₁–P₁N₃ atomic interface structure plays a crucial role in boosting the HER performance, which is supported by in situ X-ray absorption fine structure (XAFS) measurements and density functional theory (DFT) calculation. With this work, we hope to promote the development of high performance metal single-atom catalysts.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; National Key R&D Program of China; National Natural Science Foundation of China; Beijing Institute of Technology

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1638159

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 18 Vol. 142; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Design Principles for Heteroatom-Doped Carbon Nanomaterials as Highly Efficient Catalysts for Fuel Cells and Metal-Air Batteries Zhao, Zhenghang; Li, Mingtao; Zhang, Lipeng Advanced Materials, Vol. 27, Issue 43 https://doi.org/10.1002/adma.201503211	journal	September 2015
Non-Noble Metal-based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications Wang, Jing; Xu, Fan; Jin, Haiyan Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201605838	journal	February 2017
Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries Kim, Sung-Wook; Seo, Dong-Hwa; Ma, Xiaohua Advanced Energy Materials, Vol. 2, Issue 7, p. 710-721 https://doi.org/10.1002/aenm.201200026	journal	May 2012
High Catalytic Activity of Nitrogen and Sulfur Co-Doped Nanoporous Graphene in the Hydrogen Evolution Reaction Ito, Yoshikazu; Cong, Weitao; Fujita, Takeshi Angewandte Chemie International Edition, Vol. 54, Issue 7 https://doi.org/10.1002/anie.201410050	journal	December 2014
Single-Atom Electrocatalysts Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong Angewandte Chemie International Edition, Vol. 56, Issue 45 https://doi.org/10.1002/anie.201703864	journal	October 2017
Single-Site Active Cobalt-Based Photocatalyst with a Long Carrier Lifetime for Spontaneous Overall Water Splitting Liu, Wei; Cao, Linlin; Cheng, Weiren Angewandte Chemie International Edition, Vol. 56, Issue 32 https://doi.org/10.1002/anie.201704358	journal	June 2017
Atomic-Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co ₁ -N ₄ Single-Site Photocatalyst Cao, Yuanjie; Chen, Si; Luo, Qiquan Angewandte Chemie International Edition, Vol. 56, Issue 40 https://doi.org/10.1002/anie.201706467	journal	August 2017
Synergistic Effects between Atomically Dispersed Fe−N−C and C−S−C for the Oxygen Reduction Reaction in Acidic Media Shen, Hangjia; Gracia-Espino, Eduardo; Ma, Jingyuan Angewandte Chemie International Edition, Vol. 56, Issue 44 https://doi.org/10.1002/anie.201706602	journal	September 2017
Relative Efficacy of Co−X ₄ Embedded Graphene (X=N, S, B, and P) Electrocatalysts towards Hydrogen Evolution Reaction: Is Nitrogen Really the Best Choice? Ren, Chunjin; Wen, Lu; Magagula, Saneliswa ChemCatChem, Vol. 12, Issue 2 https://doi.org/10.1002/cctc.201901293	journal	November 2019
A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction Gong, Ming; Wang, Di-Yan; Chen, Chia-Chun Nano Research, Vol. 9, Issue 1 https://doi.org/10.1007/s12274-015-0965-x	journal	December 2015
Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion Sun, Tingting; Xu, Lianbin; Wang, Dingsheng Nano Research, Vol. 12, Issue 9 https://doi.org/10.1007/s12274-019-2345-4	journal	March 2019
Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance Li, Xinyuan; Rong, Hongpan; Zhang, Jiatao Nano Research, Vol. 13, Issue 7 https://doi.org/10.1007/s12274-020-2755-3	journal	March 2020
Electrocatalysts for hydrogen oxidation and evolution reactions Lu, Siqi; Zhuang, Zhongbin Science China Materials, Vol. 59, Issue 3 https://doi.org/10.1007/s40843-016-0127-9	journal	March 2016
Coordination structure dominated performance of single-atomic Pt catalyst for anti-Markovnikov hydroboration of alkenes Xu, Qi; Guo, ChenXi; Tian, Shubo Science China Materials, Vol. 63, Issue 6 https://doi.org/10.1007/s40843-020-1334-6	journal	May 2020
Surface and Interface Engineering of Noble-Metal-Free Electrocatalysts for Efficient Energy Conversion Processes Zhu, Yun Pei; Guo, Chunxian; Zheng, Yao Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00635	journal	February 2017
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles Liu, Lichen; Corma, Avelino Chemical Reviews, Vol. 118, Issue 10 https://doi.org/10.1021/acs.chemrev.7b00776	journal	April 2018
Electron Transfer and Catalytic Mechanism of Organic Molecule-Adsorbed Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction and Evolution Reactions Zhao, Zhenghang; Zhang, Lipeng; Xia, Zhenhai The Journal of Physical Chemistry C, Vol. 120, Issue 4 https://doi.org/10.1021/acs.jpcc.5b09611	journal	January 2016
Hydrothermal Synthesis of a Metal-Organic Framework Containing Large Rectangular Channels Yaghi, O. M.; Li, Hailian Journal of the American Chemical Society, Vol. 117, Issue 41, p. 10401-10402 https://doi.org/10.1021/ja00146a033	journal	October 1995
From Metal–Organic Framework to Nanoporous Carbon: Toward a Very High Surface Area and Hydrogen Uptake Jiang, Hai-Long; Liu, Bo; Lan, Ya-Qian Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja203184k	journal	August 2011
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b06514	journal	September 2017
Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal–Organic Framework Abdel-Mageed, Ali M.; Rungtaweevoranit, Bunyarat; Parlinska-Wojtan, Magdalena Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.8b11386	journal	March 2019
Versatile Strategy for Tuning ORR Activity of a Single Fe-N ₄ Site by Controlling Electron-Withdrawing/Donating Properties of a Carbon Plane Mun, Yeongdong; Lee, Seonggyu; Kim, Kyeounghak Journal of the American Chemical Society, Vol. 141, Issue 15 https://doi.org/10.1021/jacs.8b13543	journal	March 2019
Stereodefined Codoping of sp-N and S Atoms in Few-Layer Graphdiyne for Oxygen Evolution Reaction Zhao, Yasong; Yang, Nailiang; Yao, Huiying Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.8b13695	journal	April 2019
Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells Zhang, Lipeng; Xia, Zhenhai The Journal of Physical Chemistry C, Vol. 115, Issue 22 https://doi.org/10.1021/jp201991j	journal	May 2011
Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution Zheng, Yao; Jiao, Yan; Li, Lu Hua ACS Nano, Vol. 8, Issue 5 https://doi.org/10.1021/nn501434a	journal	April 2014
Selective binding and removal of guests in a microporous metal–organic framework Yaghi, O. M.; Li, Guangming; Li, Hailian Nature, Vol. 378, Issue 6558, p. 703-706 https://doi.org/10.1038/378703a0	journal	December 1995
Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis Fan, Lili; Liu, Peng Fei; Yan, Xuecheng Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10667	journal	February 2016
Hydrogen evolution by a metal-free electrocatalyst Zheng, Yao; Jiao, Yan; Zhu, Yihan Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4783	journal	April 2014
Atomic cobalt on nitrogen-doped graphene for hydrogen generation Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9668	journal	October 2015
Computational high-throughput screening of electrocatalytic materials for hydrogen evolution Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob Nature Materials, Vol. 5, Issue 11, p. 909-913 https://doi.org/10.1038/nmat1752	journal	October 2006
Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01100-7	journal	October 2017
Atomic engineering of high-density isolated Co atoms on graphene with proximal-atom controlled reaction selectivity Yan, Huan; Zhao, Xiaoxu; Guo, Na Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05754-9	journal	August 2018
In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation Hülsey, Max J.; Zhang, Bin; Ma, Zhirui Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09188-9	journal	March 2019
Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction Yang, Hong Bin; Hung, Sung-Fu; Liu, Song Nature Energy, Vol. 3, Issue 2 https://doi.org/10.1038/s41560-017-0078-8	journal	February 2018
Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting Roger, Isolda; Shipman, Michael A.; Symes, Mark D. Nature Reviews Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/s41570-016-0003	journal	January 2017
Heterogeneous single-atom catalysis Wang, Aiqin; Li, Jun; Zhang, Tao Nature Reviews Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/s41570-018-0010-1	journal	May 2018
General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities Fei, Huilong; Dong, Juncai; Feng, Yexin Nature Catalysis, Vol. 1, Issue 1 https://doi.org/10.1038/s41929-017-0008-y	journal	January 2018
A universal principle for a rational design of single-atom electrocatalysts Xu, Haoxiang; Cheng, Daojian; Cao, Dapeng Nature Catalysis, Vol. 1, Issue 5 https://doi.org/10.1038/s41929-018-0063-z	journal	April 2018
Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts Cui, Xinjiang; Li, Wu; Ryabchuk, Pavel Nature Catalysis, Vol. 1, Issue 6 https://doi.org/10.1038/s41929-018-0090-9	journal	June 2018
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells Li, Jiazhan; Chen, Mengjie; Cullen, David A. Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0164-8	journal	October 2018
Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution Cao, Linlin; Luo, Qiquan; Liu, Wei Nature Catalysis, Vol. 2, Issue 2 https://doi.org/10.1038/s41929-018-0203-5	journal	December 2018
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells Wan, Xin; Liu, Xiaofang; Li, Yongcheng Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0237-3	journal	March 2019
Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions Jiao, Yan; Zheng, Yao; Jaroniec, Mietek Chemical Society Reviews, Vol. 44, Issue 8 https://doi.org/10.1039/C4CS00470A	journal	January 2015
Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction Shi, Yanmei; Zhang, Bin Chemical Society Reviews, Vol. 45, Issue 6, p. 1529-1541 https://doi.org/10.1039/C5CS00434A	journal	January 2016
Pt-Based electrocatalysts with high atom utilization efficiency: from nanostructures to single atoms Zhang, Lei; Doyle-Davis, Kieran; Sun, Xueliang Energy & Environmental Science, Vol. 12, Issue 2 https://doi.org/10.1039/C8EE02939C	journal	January 2019
The pervasive chemistry of metal–organic frameworks Long, Jeffrey R.; Yaghi, Omar M. Chemical Society Reviews, Vol. 38, Issue 5, p. 1213-1214 https://doi.org/10.1039/b903811f	journal	January 2009
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Interfacial engineering of cobalt sulfide/graphene hybrids for highly efficient ammonia electrosynthesis Chen, Pengzuo; Zhang, Nan; Wang, Sibo Proceedings of the National Academy of Sciences, Vol. 116, Issue 14 https://doi.org/10.1073/pnas.1817881116	journal	March 2019
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Wavelet analysis of extended x-ray absorption fine structure data Funke, H.; Scheinost, A. C.; Chukalina, M. Physical Review B, Vol. 71, Issue 9 https://doi.org/10.1103/PhysRevB.71.094110	journal	March 2005
Formation enthalpies by mixing GGA and GGA + U calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Calibrating transition-metal energy levels and oxygen bands in first-principles calculations: Accurate prediction of redox potentials and charge transfer in lithium transition-metal oxides Seo, Dong-Hwa; Urban, Alexander; Ceder, Gerbrand Physical Review B, Vol. 92, Issue 11 https://doi.org/10.1103/PhysRevB.92.115118	journal	September 2015
Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst Yang, Hong Bin; Miao, Jianwei; Hung, Sung-Fu Science Advances, Vol. 2, Issue 4 https://doi.org/10.1126/sciadv.1501122	journal	April 2016
Atomically dispersed Fe ³⁺ sites catalyze efficient CO ₂ electroreduction to CO Gu, Jun; Hsu, Chia-Shuo; Bai, Lichen Science, Vol. 364, Issue 6445 https://doi.org/10.1126/science.aaw7515	journal	June 2019
Trends in the Exchange Current for Hydrogen Evolution Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1856988	journal	January 2005

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metals
catalysts
electrodes
evolution reactions
extended x-ray absorption fine structure

In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal–Organic Frameworks to Design Atomic Co1–P1N3 Interfacial Structure for Promoting Catalytic Performance

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In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal–Organic Frameworks to Design Atomic Co₁–P₁N₃ Interfacial Structure for Promoting Catalytic Performance