Synergistic Doping and Intercalation: Realizing Deep Phase Modulation on MoS2 Arrays for High-Efficiency Hydrogen Evolution Reaction

Deng, Shengjue; Luo, Mi; Ai, Changzhi; Zhang, Yan; Liu, Bo; Huang, Lei; Jiang, Zheng; Zhang, Qinghua; Gu, Lin; Lin, Shiwei; Wang, Xiuli; Yu, Lei; Wen, Jianguo; Wang, Jiaao; Pan, Guoxiang; Xia, Xinhui; Tu, Jiangping

doi:10.1002/anie.201909698

Synergistic Doping and Intercalation: Realizing Deep Phase Modulation on MoS₂ Arrays for High-Efficiency Hydrogen Evolution Reaction

Journal Article · Thu Sep 05 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201909698· OSTI ID:1756165

Deng, Shengjue ^[1]; Luo, Mi ^[2]; Ai, Changzhi ^[3]; Zhang, Yan ^[1]; Liu, Bo ^[1]; Huang, Lei ^[1]; Jiang, Zheng ^[2]; Zhang, Qinghua ^[4]; Gu, Lin ^[4]; Lin, Shiwei ^[3]; Wang, Xiuli ^[1]; Yu, Lei ^[5]; Wen, Jianguo ^[5]; Wang, Jiaao ^[6]; Pan, Guoxiang ^[7]; ^[1]; Tu, Jiangping ^[1]

Zhejiang Univ., Hangzhou (China)
Chinese Academy of Sciences (CAS), Shanghai (China)
South China Sea Hainan Univ., Haikou (China)
Chinese Academy of Sciences (CAS), Beijing (China)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Jinan, Jinan (China)
Huzhou Univ. (China)

A synergistic N doping plus PO₄^3- intercalation strategy is used to induce high conversion (ca. 41%) of 2H-MoS₂ into 1T-MoS, which is much higher than single N doping (ca. 28 %) or single PO₄^3- intercalation ca. 10%). A scattering mechanism is proposed to illustrate the synergistic phase transformation from the 2H to the 1T phase, which was confirmed by synchrotron radiation and.spherical aberration TEM. To further enhance reaction kindies, the designed (N, PO₄^3-)-MoS₂ nanosheds are combined with conductive vertical graphene (VG) skeleton forming binder-free arrays fir high efficiencyhydrogen evolution reaction (HER). Owing 10 the decreased band gap, lower d-band censer, and smaller hydrogen adsorption/desorption energy, the designed (NPO₄^3-)-MoSJVG electrode shows excellent HER perfor mance with a lower Tafel slope and overpotential than N-MoS₂/VG, PO₄^3--MoS₂/VG counterparts, and other Mo-base catalysts in the literature.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1756165

Alternate ID(s):: OSTI ID: 22861020

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 45 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

Synthesis of Large-Area MoS₂ Atomic Layers with Chemical Vapor Deposition Lee, Yi-Hsien; Zhang, Xin-Quan; Zhang, Wenjing Advanced Materials, Vol. 24, Issue 17, p. 2320-2325 https://doi.org/10.1002/adma.201104798	journal	March 2012
Wafer Scale Phase-Engineered 1T- and 2H-MoSe ₂ /Mo Core-Shell 3D-Hierarchical Nanostructures toward Efficient Electrocatalytic Hydrogen Evolution Reaction Qu, Yindong; Medina, Henry; Wang, Sheng-Wen Advanced Materials, Vol. 28, Issue 44 https://doi.org/10.1002/adma.201602697	journal	September 2016
Directional Construction of Vertical Nitrogen-Doped 1T-2H MoSe ₂ /Graphene Shell/Core Nanoflake Arrays for Efficient Hydrogen Evolution Reaction Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang Advanced Materials, Vol. 29, Issue 21 https://doi.org/10.1002/adma.201700748	journal	April 2017
Phase Modulation of (1T-2H)-MoSe2/TiC-C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction Deng, Shengjue; Yang, Fan; Zhang, Qinghua Advanced Materials, Vol. 30, Issue 34 https://doi.org/10.1002/adma.201802223	journal	July 2018
Directional Construction of Vertical Nitrogen‐Doped 1T‐2H MoSe ₂ /Graphene Shell/Core Nanoflake Arrays for Efficient Hydrogen Evolution Reaction Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang Advanced Materials, Vol. 33, Issue 4 https://doi.org/10.1002/adma.202006055	journal	January 2021
Phase Modulation of (1T‐2H)‐MoSe ₂ /TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction Deng, Shengjue; Yang, Fan; Zhang, Qinghua Advanced Materials, Vol. 33, Issue 4 https://doi.org/10.1002/adma.202006056	journal	January 2021
Hollow TiO ₂ @Co ₉ S ₈ Core-Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang Advanced Science, Vol. 5, Issue 3 https://doi.org/10.1002/advs.201700772	journal	December 2017
Hollow TiO ₂ @Co ₉ S ₈ Core–Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang Advanced Science, Vol. 8, Issue 8 https://doi.org/10.1002/advs.202003294	journal	April 2021
3D Porous Hierarchical Nickel-Molybdenum Nitrides Synthesized by RF Plasma as Highly Active and Stable Hydrogen-Evolution-Reaction Electrocatalysts Zhang, Yongqi; Ouyang, Bo; Xu, Jing Advanced Energy Materials, Vol. 6, Issue 11 https://doi.org/10.1002/aenm.201600221	journal	April 2016
Dual-Functional N Dopants in Edges and Basal Plane of MoS ₂ Nanosheets Toward Efficient and Durable Hydrogen Evolution Xiao, Wen; Liu, Peitao; Zhang, Jingyan Advanced Energy Materials, Vol. 7, Issue 7 https://doi.org/10.1002/aenm.201602086	journal	December 2016
Ultrastable In-Plane 1T-2H MoS ₂ Heterostructures for Enhanced Hydrogen Evolution Reaction Wang, Shuai; Zhang, Di; Li, Bin Advanced Energy Materials, Vol. 8, Issue 25 https://doi.org/10.1002/aenm.201801345	journal	July 2018
Multiscale Graphene-Based Materials for Applications in Sodium Ion Batteries Zhang, Yan; Xia, Xinhui; Liu, Bo Advanced Energy Materials, Vol. 9, Issue 8 https://doi.org/10.1002/aenm.201803342	journal	January 2019
Single-Layer Semiconducting Nanosheets: High-Yield Preparation and Device Fabrication Zeng, Zhiyuan; Yin, Zongyou; Huang, Xiao Angewandte Chemie, Vol. 123, Issue 47 https://doi.org/10.1002/ange.201106004	journal	October 2011
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction Kibsgaard, Jakob; Jaramillo, Thomas F. Angewandte Chemie, Vol. 126, Issue 52 https://doi.org/10.1002/ange.201408222	journal	October 2014
Rapid Synthesis of Cobalt Nitride Nanowires: Highly Efficient and Low-Cost Catalysts for Oxygen Evolution Zhang, Yongqi; Ouyang, Bo; Xu, Jing Angewandte Chemie, Vol. 128, Issue 30 https://doi.org/10.1002/ange.201604372	journal	June 2016
Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries Li, Xiaona; Liang, Jianwen; Lu, Yue Angewandte Chemie, Vol. 129, Issue 11 https://doi.org/10.1002/ange.201611691	journal	February 2017
Self-Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution Wang, Longlu; Liu, Xia; Luo, Jinming Angewandte Chemie, Vol. 129, Issue 26 https://doi.org/10.1002/ange.201703066	journal	May 2017
Structure Re-determination and Superconductivity Observation of Bulk 1T MoS ₂ Fang, Yuqiang; Pan, Jie; He, Jianqiao Angewandte Chemie, Vol. 130, Issue 5 https://doi.org/10.1002/ange.201710512	journal	January 2018
Tailoring the d-Band Centers Enables Co ₄ N Nanosheets To Be Highly Active for Hydrogen Evolution Catalysis Chen, Zhiyan; Song, Yao; Cai, Jinyan Angewandte Chemie, Vol. 130, Issue 18 https://doi.org/10.1002/ange.201801834	journal	March 2018
Single-Layer Semiconducting Nanosheets: High-Yield Preparation and Device Fabrication Zeng, Zhiyuan; Yin, Zongyou; Huang, Xiao Angewandte Chemie International Edition, Vol. 50, Issue 47, p. 11093-11097 https://doi.org/10.1002/anie.201106004	journal	October 2011
Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction Kibsgaard, Jakob; Jaramillo, Thomas F. Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201408222	journal	October 2014
Rapid Synthesis of Cobalt Nitride Nanowires: Highly Efficient and Low-Cost Catalysts for Oxygen Evolution Zhang, Yongqi; Ouyang, Bo; Xu, Jing Angewandte Chemie International Edition, Vol. 55, Issue 30 https://doi.org/10.1002/anie.201604372	journal	June 2016
Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries Li, Xiaona; Liang, Jianwen; Lu, Yue Angewandte Chemie International Edition, Vol. 56, Issue 11 https://doi.org/10.1002/anie.201611691	journal	February 2017
Self-Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution Wang, Longlu; Liu, Xia; Luo, Jinming Angewandte Chemie International Edition, Vol. 56, Issue 26 https://doi.org/10.1002/anie.201703066	journal	May 2017
Structure Re-determination and Superconductivity Observation of Bulk 1T MoS ₂ Fang, Yuqiang; Pan, Jie; He, Jianqiao Angewandte Chemie International Edition, Vol. 57, Issue 5 https://doi.org/10.1002/anie.201710512	journal	January 2018
Tailoring the d-Band Centers Enables Co ₄ N Nanosheets To Be Highly Active for Hydrogen Evolution Catalysis Chen, Zhiyan; Song, Yao; Cai, Jinyan Angewandte Chemie International Edition, Vol. 57, Issue 18 https://doi.org/10.1002/anie.201801834	journal	March 2018
Phosphorus-Doped MoS ₂ Nanosheets Supported on Carbon Cloths as Efficient Hydrogen-Generation Electrocatalysts Bian, Luozhen; Gao, Wei; Sun, Jiamin ChemCatChem, Vol. 10, Issue 7 https://doi.org/10.1002/cctc.201701680	journal	February 2018
Prereduction of Metal Oxides via Carbon Plasma Treatment for Efficient and Stable Electrocatalytic Hydrogen Evolution Zhang, Yongqi; Ouyang, Bo; Xu, Kun Small, Vol. 14, Issue 17 https://doi.org/10.1002/smll.201800340	journal	April 2018
Aligned Heterointerface-Induced 1T-MoS ₂ Monolayer with Near-Ideal Gibbs Free for Stable Hydrogen Evolution Reaction Zhang, Kan; Jin, Bingjun; Gao, Yujie Small, Vol. 15, Issue 8 https://doi.org/10.1002/smll.201804903	journal	January 2019
Coupled Biphase (1T‐2H)‐MoSe ₂ on Mold Spore Carbon for Advanced Hydrogen Evolution Reaction Deng, Shengjue; Ai, Changzhi; Luo, Mi Small, Vol. 15, Issue 30 https://doi.org/10.1002/smll.201901796	journal	June 2019
X-ray absorption near-edge spectroscopy (XANES) at the phosphorus K-edge of triorganophosphinechalcogenides Engemann, C.; Franke, R.; Hormes, J. Chemical Physics, Vol. 243, Issue 1-2 https://doi.org/10.1016/S0301-0104(99)00071-3	journal	May 1999
Mn doped MoS 2 /reduced graphene oxide hybrid for enhanced hydrogen evolution Wu, Liqian; Xu, Xiaobing; Zhao, Yuqi Applied Surface Science, Vol. 425 https://doi.org/10.1016/j.apsusc.2017.06.223	journal	December 2017
Vertical graphene/Ti2Nb10O29/hydrogen molybdenum bronze composite arrays for enhanced lithium ion storage Deng, Shengjue; Chao, Dongliang; Zhong, Yu Energy Storage Materials, Vol. 12 https://doi.org/10.1016/j.ensm.2017.11.018	journal	May 2018
Nitrogen doped MoS 2 nanosheets synthesized via a low-temperature process as electrocatalysts with enhanced activity for hydrogen evolution reaction Li, Ruchun; Yang, Linjing; Xiong, Tanli Journal of Power Sources, Vol. 356 https://doi.org/10.1016/j.jpowsour.2017.04.060	journal	July 2017
N-doped MoS2 nanosheets with exposed edges realizing robust electrochemical hydrogen evolution Guo, Jinxue; Liu, Chuan; Sun, Yanfang Journal of Solid State Chemistry, Vol. 263 https://doi.org/10.1016/j.jssc.2018.04.023	journal	July 2018
Oxygen vacancy modulated Ti2Nb10O29-x embedded onto porous bacterial cellulose carbon for highly efficient lithium ion storage Deng, Shengjue; Zhang, Yan; Xie, Dong Nano Energy, Vol. 58 https://doi.org/10.1016/j.nanoen.2019.01.051	journal	April 2019
Recent Advances in Ultrathin Two-Dimensional Nanomaterials Tan, Chaoliang; Cao, Xiehong; Wu, Xue-Jun Chemical Reviews, Vol. 117, Issue 9 https://doi.org/10.1021/acs.chemrev.6b00558	journal	March 2017
Co-Doped MoS ₂ Nanosheets with the Dominant CoMoS Phase Coated on Carbon as an Excellent Electrocatalyst for Hydrogen Evolution Dai, Xiaoping; Du, Kangli; Li, Zhanzhao ACS Applied Materials & Interfaces, Vol. 7, Issue 49 https://doi.org/10.1021/acsami.5b08420	journal	December 2015
Engineering the Electronic Structure of MoS ₂ Nanorods by N and Mn Dopants for Ultra-Efficient Hydrogen Production Sun, Tao; Wang, Jun; Chi, Xiao ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b00783	journal	July 2018
X-ray Photoelectron and Absorption Spectroscopy of Metal-Rich Phosphides M ₂ P and M ₃ P ( M = Cr−Ni) Blanchard, Peter E. R.; Grosvenor, Andrew P.; Cavell, Ronald G. Chemistry of Materials, Vol. 20, Issue 22 https://doi.org/10.1021/cm802123a	journal	November 2008
Vacancy-Induced Ferromagnetism of MoS ₂ Nanosheets Cai, Liang; He, Jingfu; Liu, Qinghua Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja5120908	journal	February 2015
Coherent Atomic and Electronic Heterostructures of Single-Layer MoS₂ Eda, Goki; Fujita, Takeshi; Yamaguchi, Hisato ACS Nano, Vol. 6, Issue 8, p. 7311-7317 https://doi.org/10.1021/nn302422x	journal	July 2012
Structural phase transitions in two-dimensional Mo- and W-dichalcogenide monolayers Duerloo, Karel-Alexander N.; Li, Yao; Reed, Evan J. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5214	journal	July 2014
Phase-engineered low-resistance contacts for ultrathin MoS₂ transistors Kappera, Rajesh; Voiry, Damien; Yalcin, Sibel Ebru Nature Materials, Vol. 13, Issue 12, p. 1128-1134 https://doi.org/10.1038/nmat4080	journal	August 2014
Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2 Lin, Yung-Chang; Dumcenco, Dumitru O.; Huang, Ying-Sheng Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.64	journal	April 2014
Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials Acerce, Muharrem; Voiry, Damien; Chhowalla, Manish Nature Nanotechnology, Vol. 10, Issue 4 https://doi.org/10.1038/nnano.2015.40	journal	March 2015
Electron density modulation of NiCo2S4 nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis Wu, Yishang; Liu, Xiaojing; Han, Dongdong Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03858-w	journal	April 2018
Chemically activating MoS2 via spontaneous atomic palladium interfacial doping towards efficient hydrogen evolution Luo, Zhaoyan; Ouyang, Yixin; Zhang, Hao Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04501-4	journal	May 2018
Tuning orbital orientation endows molybdenum disulfide with exceptional alkaline hydrogen evolution capability Zang, Yipeng; Niu, Shuwen; Wu, Yishang Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09210-0	journal	March 2019
High phase-purity 1T′-MoS2- and 1T′-MoSe2-layered crystals Yu, Yifu; Nam, Gwang-Hyeon; He, Qiyuan Nature Chemistry, Vol. 10, Issue 6 https://doi.org/10.1038/s41557-018-0035-6	journal	April 2018
Synthesis of few-layered MoS ₂ nanosheet-coated electrospun SnO ₂ nanotube heterostructures for enhanced hydrogen evolution reaction Huang, Yunpeng; Miao, Yue-E; Zhang, Longsheng Nanoscale, Vol. 6, Issue 18 https://doi.org/10.1039/C4NR02014F	journal	January 2014
2H → 1T phase transition and hydrogen evolution activity of MoS ₂ , MoSe ₂ , WS ₂ and WSe ₂ strongly depends on the MX ₂ composition Ambrosi, Adriano; Sofer, Zdeněk; Pumera, Martin Chemical Communications, Vol. 51, Issue 40 https://doi.org/10.1039/C5CC00803D	journal	January 2015
A Se-doped MoS ₂ nanosheet for improved hydrogen evolution reaction Ren, Xianpei; Ma, Qiang; Fan, Haibo Chemical Communications, Vol. 51, Issue 88 https://doi.org/10.1039/C5CC06847A	journal	January 2015
Engineering water dissociation sites in MoS ₂ nanosheets for accelerated electrocatalytic hydrogen production Zhang, Jian; Wang, Tao; Liu, Pan Energy & Environmental Science, Vol. 9, Issue 9 https://doi.org/10.1039/C6EE01786J	journal	January 2016
Engineering two-dimensional layered nanomaterials for wearable biomedical sensors and power devices Cao, Xianyi; Halder, Arnab; Tang, Yingying Materials Chemistry Frontiers, Vol. 2, Issue 11 https://doi.org/10.1039/C8QM00356D	journal	January 2018
MoO2 nanobelts@nitrogen self-doped MoS2 nanosheets as effective electrocatalysts for hydrogen evolution reaction Zhou, Weijia; Hou, Dongman; Sang, Yuanhua Journal of Materials Chemistry A, Vol. 2, Issue 29 https://doi.org/10.1039/c4ta01898b	journal	January 2014
Uniquely confining Cu ₂ S nanoparticles in graphitized carbon fibers for enhanced oxygen evolution reaction Zhao, Xiaoqian; Liu, Li; Zhang, Yan Nanotechnology, Vol. 28, Issue 34 https://doi.org/10.1088/1361-6528/aa79d2	journal	July 2017
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

Cited By (6)

Two‐Dimensional MoS ₂ for Li−S Batteries: Structural Design and Electronic Modulation Cao, Yiqi; Lin, Yan; Wu, Jianbo ChemSusChem, Vol. 13, Issue 6 https://doi.org/10.1002/cssc.201902688	journal	March 2020
Introducing Oxygen Defects into Phosphate Ions Intercalated Manganese Dioxide/Vertical Multilayer Graphene Arrays to Boost Flexible Zinc Ion Storage Zhang, Yan; Deng, Shengjue; Pan, Guoxiang Small Methods, Vol. 4, Issue 6 https://doi.org/10.1002/smtd.201900828	journal	February 2020
Amorphous MoS2 confined in nitrogen-doped porous carbon for improved electrocatalytic stability toward hydrogen evolution reaction Lu, Shaojie; Wang, Wenjing; Yang, Shengshuang Nano Research, Vol. 12, Issue 12 https://doi.org/10.1007/s12274-019-2563-9	journal	November 2019
Boosting fast energy storage by synergistic engineering of carbon and deficiency Deng, Shengjue; Zhu, He; Wang, Guizhen Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-13945-1	journal	January 2020
MOF-derived cobalt–nickel phosphide nanoboxes as electrocatalysts for the hydrogen evolution reaction Lu, Yidong; Deng, Yaoyao; Lu, Shuanglong Nanoscale, Vol. 11, Issue 44 https://doi.org/10.1039/c9nr07002h	journal	January 2019
A high-power lithium-ion hybrid capacitor based on a hollow N-doped carbon nanobox anode and its porous analogue cathode Liang, Tian; Wang, Huanwen; Fei, Rixin Nanoscale, Vol. 11, Issue 43 https://doi.org/10.1039/c9nr07091e	journal	January 2019

Similar Records

Effect of Intercalated Metals on the Electrocatalytic Activity of 1T-MoS ₂ for the Hydrogen Evolution Reaction

Journal Article · Wed Nov 08 19:00:00 EST 2017 · ACS Energy Letters · OSTI ID:1470020

Synergistic Phase and Disorder Engineering in 1T‐MoSe ₂ Nanosheets for Enhanced Hydrogen‐Evolution Reaction

Journal Article · Thu May 18 20:00:00 EDT 2017 · Advanced Materials · OSTI ID:1400842

Mechanism of Hydrogen Evolution Reaction on 1T-MoS₂ from First Principles

Journal Article · Sun Jun 19 20:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1485139

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
doping-intercalation
hydrogen evolution reaction
molybdenum sulfide
nitrogen phosphate