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Title: Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

Abstract

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

Authors:
 [1];  [2];  [1];  [3];  [4]; ORCiD logo [4];  [5];  [5];  [6];  [2];  [1]
  1. Zhejiang Univ., Hangzhou (China)
  2. Univ. of California, Davis, CA (United States)
  3. Chinese Academy of Sciences (CAS), Dalian (China)
  4. King Abdullah Univ. of Science and Tech., Thuwal (Saudi Arabia)
  5. West Virginia Univ., Morgantown, WV (United States)
  6. Xiamen Univ., Xiamen (China)
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1511705
Grant/Contract Number:  
FG02-04ER15513
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Wang, Liang, Guan, Erjia, Zhang, Jian, Yang, Junhao, Zhu, Yihan, Han, Yu, Yang, Ming, Cen, Cheng, Fu, Gang, Gates, Bruce C., and Xiao, Feng-Shou. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation. United States: N. p., 2018. Web. doi:10.1038/s41467-018-03810-y.
Wang, Liang, Guan, Erjia, Zhang, Jian, Yang, Junhao, Zhu, Yihan, Han, Yu, Yang, Ming, Cen, Cheng, Fu, Gang, Gates, Bruce C., & Xiao, Feng-Shou. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation. United States. https://doi.org/10.1038/s41467-018-03810-y
Wang, Liang, Guan, Erjia, Zhang, Jian, Yang, Junhao, Zhu, Yihan, Han, Yu, Yang, Ming, Cen, Cheng, Fu, Gang, Gates, Bruce C., and Xiao, Feng-Shou. Tue . "Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation". United States. https://doi.org/10.1038/s41467-018-03810-y. https://www.osti.gov/servlets/purl/1511705.
@article{osti_1511705,
title = {Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation},
author = {Wang, Liang and Guan, Erjia and Zhang, Jian and Yang, Junhao and Zhu, Yihan and Han, Yu and Yang, Ming and Cen, Cheng and Fu, Gang and Gates, Bruce C. and Xiao, Feng-Shou},
abstractNote = {Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.},
doi = {10.1038/s41467-018-03810-y},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

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Works referenced in this record:

One-step Synthesis of Core-Gold/Shell-Ceria Nanomaterial and Its Catalysis for Highly Selective Semihydrogenation of Alkynes
journal, October 2015

  • Mitsudome, Takato; Yamamoto, Masaaki; Maeno, Zen
  • Journal of the American Chemical Society, Vol. 137, Issue 42
  • DOI: 10.1021/jacs.5b07521

Enhanced Photoactivity of Oxygen-Deficient Anatase TiO 2 Sheets with Dominant {001} Facets
journal, December 2009

  • Liu, Gang; Yang, Hua Gui; Wang, Xuewen
  • The Journal of Physical Chemistry C, Vol. 113, Issue 52
  • DOI: 10.1021/jp907749r

A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores
journal, May 2017

  • Zhang, Jian; Wang, Liang; Shao, Yi
  • Angewandte Chemie International Edition, Vol. 56, Issue 33
  • DOI: 10.1002/anie.201703938

Activity and Selectivity in Nitroarene Hydrogenation over Au Nanoparticles on the Edge/Corner of Anatase
journal, May 2016


Transforming Nonselective into Chemoselective Metal Catalysts for the Hydrogenation of Substituted Nitroaromatics
journal, July 2008

  • Corma, Avelino; Serna, Pedro; Concepción, Patricia
  • Journal of the American Chemical Society, Vol. 130, Issue 27
  • DOI: 10.1021/ja800959g

Direct vs. indirect pathway for nitrobenzene reduction reaction on a Ni catalyst surface: a density functional study
journal, January 2014

  • Mahata, Arup; Rai, Rohit K.; Choudhuri, Indrani
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 47
  • DOI: 10.1039/C4CP04355C

Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store
journal, October 2012

  • Kitano, Masaaki; Inoue, Yasunori; Yamazaki, Youhei
  • Nature Chemistry, Vol. 4, Issue 11
  • DOI: 10.1038/nchem.1476

Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014

  • Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank
  • Nature Chemistry, Vol. 6, Issue 4
  • DOI: 10.1038/nchem.1873

Tuning the Chemoselective Hydrogenation of Nitrostyrenes Catalyzed by Ionic Liquid-Supported Platinum Nanoparticles
journal, November 2012

  • Beier, Matthias J.; Andanson, Jean-Michel; Baiker, Alfons
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs300529y

Reduction of Nitroaromatic Compounds on Supported Gold Nanoparticles by Visible and Ultraviolet Light
journal, November 2010

  • Zhu, Huaiyong; Ke, Xuebin; Yang, Xuzhuang
  • Angewandte Chemie International Edition, Vol. 49, Issue 50
  • DOI: 10.1002/anie.201003908

A Molecular Mechanism for the Chemoselective Hydrogenation of Substituted Nitroaromatics with Nanoparticles of Gold on TiO 2 Catalysts:  A Cooperative Effect between Gold and the Support
journal, December 2007

  • Boronat, Mercè; Concepción, Patricia; Corma, Avelino
  • Journal of the American Chemical Society, Vol. 129, Issue 51
  • DOI: 10.1021/ja076721g

In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method
journal, September 2012

  • Cantillo, David; Baghbanzadeh, Mostafa; Kappe, C. Oliver
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201205792

Product Selectivity Controlled by Zeolite Crystals in Biomass Hydrogenation over a Palladium Catalyst
journal, June 2016

  • Wang, Chengtao; Wang, Liang; Zhang, Jian
  • Journal of the American Chemical Society, Vol. 138, Issue 25
  • DOI: 10.1021/jacs.6b04951

Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts
journal, July 2006


Interfacial electronic effects control the reaction selectivity of platinum catalysts
journal, January 2016

  • Chen, Guangxu; Xu, Chaofa; Huang, Xiaoqing
  • Nature Materials, Vol. 15, Issue 5
  • DOI: 10.1038/nmat4555

Metal–organic frameworks as selectivity regulators for hydrogenation reactions
journal, October 2016


Highly Efficient and Selective Hydrogenation of Nitroaromatics on Photoactivated Rutile Titanium Dioxide
journal, October 2012

  • Shiraishi, Yasuhiro; Togawa, Yoshiki; Tsukamoto, Daijiro
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs300500p

High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO 2 for Hydrogenation of Nitroarenes
journal, February 2016

  • Zhang, Sai; Chang, Chun-Ran; Huang, Zheng-Qing
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11413

Novel Palladium-on-Carbon/Diphenyl Sulfide Complex for Chemoselective Hydrogenation: Preparation, Characterization, and Application
journal, February 2008

  • Mori, Akinori; Mizusaki, Tomoteru; Kawase, Masami
  • Advanced Synthesis & Catalysis, Vol. 350, Issue 3
  • DOI: 10.1002/adsc.200700571

Effect of potassium promoter on precipitated iron-manganese catalyst for Fischer?Tropsch synthesis
journal, July 2004


Gold-Catalyzed Direct Hydrogenative Coupling of Nitroarenes To Synthesize Aromatic Azo Compounds
journal, June 2014

  • Liu, Xiang; Li, Hai-Qian; Ye, Sen
  • Angewandte Chemie International Edition, Vol. 53, Issue 29
  • DOI: 10.1002/anie.201404543

FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes
journal, December 2014

  • Wei, Haisheng; Liu, Xiaoyan; Wang, Aiqin
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6634

Probing the Low-Temperature Water–Gas Shift Activity of Alkali-Promoted Platinum Catalysts Stabilized on Carbon Supports
journal, February 2014

  • Zugic, Branko; Zhang, Shiran; Bell, David C.
  • Journal of the American Chemical Society, Vol. 136, Issue 8
  • DOI: 10.1021/ja4123889

Pd-Pb Alloy Nanocrystals with Tailored Composition for Semihydrogenation: Taking Advantage of Catalyst Poisoning
journal, May 2015

  • Niu, Wenxin; Gao, Yongjun; Zhang, Weiqing
  • Angewandte Chemie International Edition, Vol. 54, Issue 28
  • DOI: 10.1002/anie.201503148

Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines
journal, November 2013


Temperature Dependence of the Raman Spectrum in Anatase TiO 2
journal, May 1980

  • Ohsaka, Toshiaki
  • Journal of the Physical Society of Japan, Vol. 48, Issue 5
  • DOI: 10.1143/JPSJ.48.1661

Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes
journal, May 2013

  • Westerhaus, Felix A.; Jagadeesh, Rajenahally V.; Wienhöfer, Gerrit
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1645

The new breed of cutting-edge catalysts
journal, September 2016


The Nitro Group in Organic Synthesis
journal, December 2001


Reduction of Nitroaromatic Compounds on Supported Gold Nanoparticles by Visible and Ultraviolet Light
journal, November 2010


Gold-Catalyzed Direct Hydrogenative Coupling of Nitroarenes To Synthesize Aromatic Azo Compounds
journal, June 2014


In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method
journal, September 2012

  • Cantillo, David; Baghbanzadeh, Mostafa; Kappe, C. Oliver
  • Angewandte Chemie, Vol. 124, Issue 40
  • DOI: 10.1002/ange.201205792

Pd-Pb Alloy Nanocrystals with Tailored Composition for Semihydrogenation: Taking Advantage of Catalyst Poisoning
journal, May 2015


Works referencing / citing this record:

Low‐Temperature Fast Production of Carbon and Acetic Acid Dual‐Promoted Pd/C Catalysts
journal, September 2019

  • Yao, Xiuchao; Ni, Lin; Yu, Chang
  • Chemistry – A European Journal, Vol. 25, Issue 60
  • DOI: 10.1002/chem.201902328

Hydrogenation of Functionalized Nitroarenes Catalyzed by Single‐Phase Pyrite FeS 2 Nanoparticles on N,S‐Codoped Porous Carbon
journal, September 2019


Ultrathin 2D Ni‐UMOF Composites for Highly‐Efficient 4‐Nitrophenol Hydrogenation
journal, December 2019

  • Yang, Xian‐Feng; Xiong, Ren‐Jie; Chang, Xue
  • ChemistrySelect, Vol. 4, Issue 48
  • DOI: 10.1002/slct.201904028

Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes
journal, April 2019


Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst
journal, October 2019


Tuning of catalytic sites in Pt/TiO2 catalysts for the chemoselective hydrogenation of 3-nitrostyrene
journal, September 2019

  • Macino, Margherita; Barnes, Alexandra J.; Althahban, Sultan M.
  • Nature Catalysis, Vol. 2, Issue 10
  • DOI: 10.1038/s41929-019-0334-3

A comparative study of nitrobenzene reduction using model catalysts
journal, January 2019

  • Wu, Shuchang; Lin, Yangming; Zhong, Bingwei
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 3
  • DOI: 10.1039/c8cp06175k

Cobalt nanocomposites on N-doped hierarchical porous carbon for highly selective formation of anilines and imines from nitroarenes
journal, January 2018

  • Song, Tao; Ren, Peng; Duan, Yanan
  • Green Chemistry, Vol. 20, Issue 20
  • DOI: 10.1039/c8gc01374h

Noble metal-free upgrading of multi-unsaturated biomass derivatives at room temperature: silyl species enable reactivity
journal, January 2018

  • Li, Hu; Zhao, Wenfeng; Dai, Wenshuai
  • Green Chemistry, Vol. 20, Issue 23
  • DOI: 10.1039/c8gc02934b

First-principles study on the mechanism of photocatalytic reduction of nitrobenzene on the rutile TiO 2 (110) surface
journal, January 2020

  • Ji, Yongfei; Fan, Ting; Luo, Yi
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 3
  • DOI: 10.1039/c9cp05010h

A redox interaction-engaged strategy for multicomponent nanomaterials
journal, January 2020

  • Wang, Xiao; Song, Shuyan; Zhang, Hongjie
  • Chemical Society Reviews, Vol. 49, Issue 3
  • DOI: 10.1039/c9cs00379g

Platinum single-atom catalysts: a comparative review towards effective characterization
journal, January 2019

  • Liu, Qing; Zhang, Zailei
  • Catalysis Science & Technology, Vol. 9, Issue 18
  • DOI: 10.1039/c9cy01028a

Differences in the selective reduction mechanism of 4-nitroacetophenone catalysed by rutile- and anatase-supported ruthenium catalysts
journal, January 2020

  • Zhang, Jin; Pei, Linjuan; Wang, Jie
  • Catalysis Science & Technology, Vol. 10, Issue 5
  • DOI: 10.1039/c9cy02260k

Reactivity of a gold( i )/platinum(0) frustrated Lewis pair with germanium and tin dihalides
journal, January 2019

  • Hidalgo, Nereida; Bajo, Sonia; Moreno, Juan José
  • Dalton Transactions, Vol. 48, Issue 25
  • DOI: 10.1039/c9dt00702d

Heterogeneous gold catalysts for selective hydrogenation: from nanoparticles to atomically precise nanoclusters
journal, January 2019

  • Zhao, Jianbo; Ge, Liming; Yuan, Haifeng
  • Nanoscale, Vol. 11, Issue 24
  • DOI: 10.1039/c9nr03182k

Single-atom catalyst: a rising star for green synthesis of fine chemicals
journal, August 2018

  • Zhang, Leilei; Ren, Yujing; Liu, Wengang
  • National Science Review, Vol. 5, Issue 5
  • DOI: 10.1093/nsr/nwy077

Ni/NiO Nanocomposites with Rich Oxygen Vacancies as High-Performance Catalysts for Nitrophenol Hydrogenation
journal, November 2019


Hydrogenation of Functionalized Nitroarenes Catalyzed by Single‐Phase Pyrite FeS 2 Nanoparticles on N,S‐Codoped Porous Carbon
journal, September 2019