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Title: CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

Abstract

Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-free catalyst for hydrogenation reactions in a green environment without using pure hydrogen.

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Brown Univ., Providence, RI (United States). Dept. of Chemistry
  2. Nanjing Univ. of Technology (China). State Key Lab. of of Analytical Chemistry for Life Science, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Nanjing Univ. of Technology (China). State Key Lab. of of Analytical Chemistry for Life Science, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Army Research Office (ARO); National Science Foundation (NSF)
OSTI Identifier:
1344224
Report Number(s):
BNL-113495-2017-JA
Journal ID: ISSN 0897-4756; R&D Project: 16060; 16060; TRN: US1700987
Grant/Contract Number:
SC0012704; 1644760; W911NF-15-1-0147
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY, AND ECONOMY; CuNi Nanoparticles; Catalytic Methanolysis; Center for Functional Nanomaterials

Citation Formats

Yu, Chao, Fu, Jiaju, Muzzio, Michelle, Shen, Tunli, Su, Dong, Zhu, Junjie, and Sun, Shouheng. CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.6b05364.
Yu, Chao, Fu, Jiaju, Muzzio, Michelle, Shen, Tunli, Su, Dong, Zhu, Junjie, & Sun, Shouheng. CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds. United States. doi:10.1021/acs.chemmater.6b05364.
Yu, Chao, Fu, Jiaju, Muzzio, Michelle, Shen, Tunli, Su, Dong, Zhu, Junjie, and Sun, Shouheng. Thu . "CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds". United States. doi:10.1021/acs.chemmater.6b05364. https://www.osti.gov/servlets/purl/1344224.
@article{osti_1344224,
title = {CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds},
author = {Yu, Chao and Fu, Jiaju and Muzzio, Michelle and Shen, Tunli and Su, Dong and Zhu, Junjie and Sun, Shouheng},
abstractNote = {Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu36Ni64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 molH2 molCuNi-1 min-1 and Ea = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-free catalyst for hydrogenation reactions in a green environment without using pure hydrogen.},
doi = {10.1021/acs.chemmater.6b05364},
journal = {Chemistry of Materials},
number = 3,
volume = 29,
place = {United States},
year = {Thu Jan 12 00:00:00 EST 2017},
month = {Thu Jan 12 00:00:00 EST 2017}
}

Journal Article:
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Cited by: 10works
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  • In the process of catalytic hydrogenation of nitrotrifluoromethylbenzene (NTB) as a model nitro compound, they investigated the pressure region of 0-5 bars. The catalyst was 5% palladium on carbon (BP-5M) with a grain size less than 60 ..mu..M. The hydrogen was 99.9% purity cylinder type. The industrial NTB was distilled under vacuum. In the experiments, they took the freshly distilled substance containing 89% meta isomer, 8% ortho isomer, and 3% para isomer. The reaction orders with respect to hydrogen were calculated by the van't Hoff method with the assumption that over a 1-min interval the reaction order with respect tomore » hydrogen did not change, which is valid for a residual substrate concentration not less than 16.6 mole-%. The single-interval reaction orders with respect to hydrogen n/sub H/sub 2// were treated statistically.« less
  • Tremendous effort has been devoted to the study of complex and chemical hydrides for hydrogen storage in the past decade [1, 2]. Ammonia Borane (NH 3BH 3, AB) with a hydrogen content of 19.6 wt % has received significant attention [3-5]. Methods to improve the kinetics of the step-wise dehydrogenation of AB are diverse including the uses of mesoporous frameworks [6], catalysts [7-16], and additives [17]. It was reported that when dissolving in organic solvents AB released hydrogen readily in the presence of transition metal catalysts through the formation of M∙∙∙HBH 2NH 3 complex (where M is Ir, Ru, ormore » Ni etc.) [8-10]; Lewis or Brønsted acids, on the other hand, react with AB in solution to form the initiating species (BH 2NH 3) + [11], which may have the similar function as the [BH 2(NH 3) 2] +BH 4 - (DADB) in the dehydrogenation of solid AB [17, 18]. However, comparatively little study has been reported on the catalytic dehydrogenation of AB in solid form. Other important but less investigated aspects in the solid-state reaction are the characterizations of functional catalytic species and products from the step-wise dehydrogenation.« less
  • Highlights: • We study influence of preparation conditions on activity of hollow titania–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Ti + Ni content. • The activity depends on the amount of PS residue in the hollow spheres. - Abstract: The present work reports influence of preparation conditions of hollow titania–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}). The as-prepared hollow titania–nickel composite spheres were characterized by transmission electron microscopy (TEM). Catalytic activities of the hollow spheres for hydrolytic dehydrogenation ofmore » aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution improve with the decrease of Ti + Ni content. From the results of FTIR spectra and elemental analysis, the amount of residual polystyrene (PS) templates is able to be reduced by increasing aging time for the preparation, and the catalytic activity of the hollow spheres increases when the amount of residual PS templates decreases. The carbon content in the hollow spheres prepared with aging time = 24 h is 17.3 wt.%, and the evolution of 62 mL hydrogen is finished in about 22 min in the presence of the hollow spheres from aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution. The molar ratio of the hydrolytically generated hydrogen to the initial NH{sub 3}BH{sub 3} in the presence of the hollow spheres is 2.7.« less
  • Atomization energies at 0 K and heats of formation at 0 K and 298 K are predicted for (CH3)H2N-BH3, (CH3)HN=BH2, (BH3)HN=CH2, (CH3)H2B-NH3, (CH3)HB=NH2, and (NH3)HB=CH2, as well as various molecules involved in the different bond breaking processes, from coupled cluster theory (CCSD(T)) calculations. In order to achieve near chemical accuracy (±1 kcal/mol), three corrections were added to the complete basis set binding energies based on frozen core CCSD(T) energies: corrections for core-valence, scalar relativistic, and first order atomic spin-orbit effects. Scaled vibrational zero point energies were computed with the MP2 method. The heats of formation were predicted for the respectivemore » dimethyl- and trimethyl- substituted ammonia boranes, their dehydrogenated derivatives, and the various molecules involved in the different bond breaking processes, based on isodesmic reaction schemes calculated at the G3(MP2) level. Thermodynamics for dehydrogenation pathways in the monomethyl substituted molecules were predicted. Dehydrogenation across the B-N bond is more favorable as opposed to dehydrogenation across the B-C and N-C bonds. Methylation at N reduces the exothermocity of the dehydrogenation reaction and makes the reaction more thermoneutral while methylation at B moves it away from thermoneutral. This work was supported by the US Department of Energy Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less