Spectroelectrochemical investigations of nickel cyclam indicate different reaction mechanisms for electrocatalytic CO2 and H+ reduction

Behnke, Shelby L.; Manesis, Anastasia C.; Shafaat, Hannah S.

doi:10.1039/c8dt02873g

Title: Spectroelectrochemical investigations of nickel cyclam indicate different reaction mechanisms for electrocatalytic CO₂ and H⁺ reduction

Journal Article · 04 October 2018 · Dalton Transactions

DOI: https://doi.org/10.1039/c8dt02873g · OSTI ID:1612813

Behnke, Shelby L. ^[1];

^[2];

^[2]

The Ohio State Univ., Columbus, OH (United States); DOE/OSTI
The Ohio State Univ., Columbus, OH (United States)

Rising levels of atmospheric carbon dioxide continue to motivate the development of catalysts that can efficiently convert CO₂ to useful products in water without substantial amounts of H₂ formed as a byproduct. In addition to synthetic efforts, mechanistic investigations on existing catalysts are necessary to understand the molecular factors contributing to activity and selectivity, which can guide rational improvements and increase catalyst robustness. [Ni(cyclam)]²⁺ (cyclam = 1,4,8,11-tetraazacyclotetradecane) is one such catalyst, known for decades to be capable of selective CO₂ reduction to CO in water, but with little mechanistic information experimentally established or catalytic intermediates characterized. To better understand the mechanisms of aqueous H⁺ and CO₂ reduction by [Ni(cyclam)]²⁺, spectroelectrochemical investigations were performed in conjunction with activity assays. Both large surface area glassy carbon and amorphous graphite rod working electrodes were tested, with the latter found to be significantly more active and selective for CO production. Optical, resonance Raman, and EPR spectroelectrochemical experiments on [Ni(cyclam)]²⁺ during catalysis under N₂, CO₂, and CO gases show the appearance of a single species, independent of electrode used. Identical signals are observed under oxidizing potentials. Spectroscopic and electrochemical analysis coupled with density functional theory calculations suggest that the signals observed originate from [Ni(cyclam)(H₂PO4)]²⁺. The generation of a NiIII species under catalytic, reducing conditions suggests an ECCE mechanism for H⁺ reduction by [Ni(cyclam)]²⁺, which differs from the proton-coupled, ECEC pathway proposed for CO₂ reduction. The divergent mechanisms seen for the two reactions may underlie the differential reactivity of [Ni(cyclam)]²⁺ towards each substrate, with implications for the design of increasingly selective molecular catalysts. Finally, this observation also highlights the substantial impact of buffer and electrode choice when characterizing and benchmarking the catalytic properties of new compounds.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018020

OSTI ID:: 1612813

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 42 Vol. 47; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

Raman Spectroscopy for Chemical Analysis McCreery, Richard L. John Wiley & Sons, Inc. https://doi.org/10.1002/0471721646	book	January 2000
Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh Angewandte Chemie, Vol. 130, Issue 30 https://doi.org/10.1002/ange.201802756	journal	July 2018
Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh Angewandte Chemie International Edition, Vol. 57, Issue 30 https://doi.org/10.1002/anie.201802756	journal	July 2018
Mechanism of Isomerization of Ni(cyclam) in Aqueous Solutions Maimon, Eric; Zilbermann, Israel; Cohen, Haim European Journal of Inorganic Chemistry, Vol. 2005, Issue 24 https://doi.org/10.1002/ejic.200500523	journal	December 2005
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
TD-DFT benchmarks: A review Laurent, Adèle D.; Jacquemin, Denis International Journal of Quantum Chemistry, Vol. 113, Issue 17 https://doi.org/10.1002/qua.24438	journal	April 2013
Tetraaza-macrocyclic cobalt(II) and nickel(II) complexes as electron-transfer agents in the photo(electro)chemical and electrochemical reduction of carbon dioxide Tinnemans, A. H. A.; Koster, T. P. M.; Thewissen, D. H. M. W. Recueil des Travaux Chimiques des Pays-Bas, Vol. 103, Issue 10 https://doi.org/10.1002/recl.19841031004	journal	January 1984
A critical evaluation of DFT, including time-dependent DFT, applied to bioinorganic chemistry Neese, Frank JBIC Journal of Biological Inorganic Chemistry, Vol. 11, Issue 6 https://doi.org/10.1007/s00775-006-0138-1	journal	July 2006
Electrocatalytic process of CO selectivity in electrochemical reduction of CO₂ at metal electrodes in aqueous media Hori, Yoshio; Wakebe, Hidetoshi; Tsukamoto, Toshio Electrochimica Acta, Vol. 39, Issue 11-12, p. 1833-1839 https://doi.org/10.1016/0013-4686(94)85172-7	journal	August 1994
Electrocatalytic reduction of CO2 by nickel(II) cyclam Fujihira, Masamichi; Hirata, Yoshiki; Suga, Kosaku Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 292, Issue 1-2 https://doi.org/10.1016/0022-0728(90)87336-I	journal	October 1990
The adsorption of Ni(cyclam)+ at mercury electrodes and its relation to the electrocatalytic reduction of CO2 Balazs, G. Bryan; Anson, Fred C. Journal of Electroanalytical Chemistry, Vol. 322, Issue 1-2 https://doi.org/10.1016/0022-0728(92)80086-J	journal	January 1992
Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling Neese, Frank Coordination Chemistry Reviews, Vol. 253, Issue 5-6 https://doi.org/10.1016/j.ccr.2008.05.014	journal	March 2009
Nickel complexes as molecular catalysts for water splitting and CO2 reduction Wang, Jia-Wei; Liu, Wen-Ju; Zhong, Di-Chang Coordination Chemistry Reviews, Vol. 378 https://doi.org/10.1016/j.ccr.2017.12.009	journal	January 2019
“Deactivation of copper electrode” in electrochemical reduction of CO2 Hori, Y.; Konishi, H.; Futamura, T. Electrochimica Acta, Vol. 50, Issue 27 https://doi.org/10.1016/j.electacta.2005.03.015	journal	September 2005
Anions as stabilizing ligands for Ni(III)(cyclam) in aqueous solutions Shamir, Dror; Zilbermann, Israel; Maimon, Eric Inorganica Chimica Acta, Vol. 363, Issue 12 https://doi.org/10.1016/j.ica.2010.03.057	journal	October 2010
A review of the aqueous electrochemical reduction of CO₂ to hydrocarbons at copper Gattrell, M.; Gupta, N.; Co, A. Journal of Electroanalytical Chemistry, Vol. 594, Issue 1, p. 1-19 https://doi.org/10.1016/j.jelechem.2006.05.013	journal	August 2006
A study of the modification of glassy carbon and edge and basal plane highly oriented pyrolytic graphite electrodes modified with anthraquinone using diazonium coupling and solid phase synthesis and their use for oxygen reduction Kocak, Izzet; Ghanem, Mohamed A.; Al-Mayouf, Abdullah Journal of Electroanalytical Chemistry, Vol. 706 https://doi.org/10.1016/j.jelechem.2013.07.035	journal	October 2013
EasySpin, a comprehensive software package for spectral simulation and analysis in EPR Stoll, Stefan; Schweiger, Arthur Journal of Magnetic Resonance, Vol. 178, Issue 1, p. 42-55 https://doi.org/10.1016/j.jmr.2005.08.013	journal	January 2006
Selective Transformation of CO ₂ to CO at a Single Nickel Center Yoo, Changho; Kim, Yeong-Eun; Lee, Yunho Accounts of Chemical Research, Vol. 51, Issue 5 https://doi.org/10.1021/acs.accounts.7b00634	journal	April 2018
Experimental and DFT Investigations Reveal the Influence of the Outer Coordination Sphere on the Vibrational Spectra of Nickel-Substituted Rubredoxin, a Model Hydrogenase Enzyme Slater, Jeffrey W.; Marguet, Sean C.; Cirino, Sabrina L. Inorganic Chemistry, Vol. 56, Issue 7 https://doi.org/10.1021/acs.inorgchem.6b02934	journal	March 2017
Electrode-Ligand Interactions Dramatically Enhance CO ₂ Conversion to CO by the [Ni(cyclam)](PF ₆ ) ₂ Catalyst Wu, Yueshen; Rudshteyn, Benjamin; Zhanaidarova, Almagul ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01109	journal	July 2017
Tracking a Common Surface-Bound Intermediate during CO ₂ -to-Fuels Catalysis Wuttig, Anna; Liu, Can; Peng, Qiling ACS Central Science, Vol. 2, Issue 8 https://doi.org/10.1021/acscentsci.6b00155	journal	August 2016
Transition Metal Hydride Catalysts for Sustainable Interconversion of CO ₂ and Formate: Thermodynamic and Mechanistic Considerations Waldie, Kate M.; Brunner, Felix M.; Kubiak, Clifford P. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 5 https://doi.org/10.1021/acssuschemeng.8b00628	journal	March 2018
Redox Chemistry of Nickel Complexes in Aqueous Solutions Zilbermann, Israel; Maimon, Eric; Cohen, Haim Chemical Reviews, Vol. 105, Issue 6 https://doi.org/10.1021/cr030717f	journal	June 2005
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300463y	journal	June 2013
Efficient Structure Optimization with Second-Order Many-Body Perturbation Theory: The RIJCOSX-MP2 Method Kossmann, Simone; Neese, Frank Journal of Chemical Theory and Computation, Vol. 6, Issue 8 https://doi.org/10.1021/ct100199k	journal	July 2010
All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R. Journal of Chemical Theory and Computation, Vol. 4, Issue 6 https://doi.org/10.1021/ct800047t	journal	May 2008
Stabilization of the monovalent nickel complex with 1,4,8,11-tetraazacyclotetradecane in aqueous solutions by N- and C-methylation. An electrochemical and pulse radiolysis study Jubran, Nusrallah; Ginzburg, Gregory; Cohen, Haim Inorganic Chemistry, Vol. 24, Issue 3 https://doi.org/10.1021/ic00197a002	journal	January 1985
Homogeneous CO ₂ Reduction by Ni(cyclam) at a Glassy Carbon Electrode Froehlich, Jesse D.; Kubiak, Clifford P. Inorganic Chemistry, Vol. 51, Issue 7 https://doi.org/10.1021/ic3001619	journal	March 2012
Complexes of Nickel(II)with a Cyclic Tetradentate Secondary Amine Bosnich, B.; Tobe, M. L.; Webb, G. A. Inorganic Chemistry, Vol. 4, Issue 8 https://doi.org/10.1021/ic50030a004	journal	August 1965
The Mechanism of Homogeneous CO ₂ Reduction by Ni(cyclam): Product Selectivity, Concerted Proton–Electron Transfer and C–O Bond Cleavage Song, Jinshuai; Klein, Eric L.; Neese, Frank Inorganic Chemistry, Vol. 53, Issue 14 https://doi.org/10.1021/ic500829p	journal	June 2014
Kinetics of CO Addition to Ni(cyclam) ⁺ in Aqueous Solution Kelly, Craig A.; Mulazzani, Quinto G.; Blinn, Elliott L. Inorganic Chemistry, Vol. 35, Issue 18 https://doi.org/10.1021/ic951527t	journal	January 1996
Local Density Functional Theory Analysis of the Structures and Energies of the Isomers of Low-Spin [Ni(cyclam)] ²⁺ Adam, Kenneth R.; Atkinson, Ian M.; Lindoy, Leonard F. Inorganic Chemistry, Vol. 36, Issue 3 https://doi.org/10.1021/ic960864e	journal	January 1997
Photochemical reduction of carbon dioxide using nickel tetraazamacrocycles Craig, Carl A.; Spreer, Larry O.; Otvos, John W. The Journal of Physical Chemistry, Vol. 94, Issue 20 https://doi.org/10.1021/j100383a038	journal	October 1990
Electrocatalytic reduction of carbon dioxide by nickel cyclam2+ in water: study of the factors affecting the efficiency and the selectivity of the process Beley, Marc.; Collin, Jean Paul.; Ruppert, Romain. Journal of the American Chemical Society, Vol. 108, Issue 24 https://doi.org/10.1021/ja00284a003	journal	November 1986
Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt Fisher, Barbara J.; Eisenberg, Richard Journal of the American Chemical Society, Vol. 102, Issue 24, p. 7361-7363 https://doi.org/10.1021/ja00544a035	journal	September 1980
The Hydrophilic Phosphatriazaadamantane Ligand in the Development of H ₂ Production Electrocatalysts: Iron Hydrogenase Model Complexes Mejia-Rodriguez, Rosario; Chong, Daesung; Reibenspies, Joseph H. Journal of the American Chemical Society, Vol. 126, Issue 38 https://doi.org/10.1021/ja039394v	journal	September 2004
The Homogeneous Reduction of CO ₂ by [Ni(cyclam)] ⁺ : Increased Catalytic Rates with the Addition of a CO Scavenger Froehlich, Jesse D.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/ja512575v	journal	March 2015
Relative Stability of Hydrogen and Deuterium Bonds Scheiner, Steve; Čuma, Martin Journal of the American Chemical Society, Vol. 118, Issue 6 https://doi.org/10.1021/ja9530376	journal	January 1996
Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni–Fe Oxide Water Splitting Electrocatalysts Görlin, Mikaela; Chernev, Petko; Ferreira de Araújo, Jorge Journal of the American Chemical Society, Vol. 138, Issue 17 https://doi.org/10.1021/jacs.6b00332	journal	April 2016
Activation of Small Molecules at Nickel(I) Moieties Zimmermann, Philipp; Limberg, Christian Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.6b12434	journal	February 2017
Direct CO ₂ Addition to a Ni(0)–CO Species Allows the Selective Generation of a Nickel(II) Carboxylate with Expulsion of CO Sahoo, Dipankar; Yoo, Changho; Lee, Yunho Journal of the American Chemical Society, Vol. 140, Issue 6 https://doi.org/10.1021/jacs.7b11074	journal	February 2018
Removal of a Cationic Dye from Aqueous Solution Using Graphene Oxide Nanosheets: Investigation of Adsorption Parameters Sharma, Ponchami; Das, Manash R. Journal of Chemical & Engineering Data, Vol. 58, Issue 1 https://doi.org/10.1021/je301020n	journal	December 2012
Combined X-ray Absorption Near-Edge Structure and X-ray Photoelectron Study of the Electrocatalytically Active Cobalt(I) Cage Complexes and the Clathrochelate Cobalt(II)- and Cobalt(III)-Containing Precursors and Analogs Kochubey, Dmitry; Kaichev, Vasily; Saraev, Andrey The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp3085606	journal	January 2013
Man-made Carbon Dioxide and the “Greenhouse” Effect Sawyer, J. S. Nature, Vol. 239, Issue 5366 https://doi.org/10.1038/239023a0	journal	September 1972
Design of functional metalloproteins Lu, Yi; Yeung, Natasha; Sieracki, Nathan Nature, Vol. 460, Issue 7257 https://doi.org/10.1038/nature08304	journal	August 2009
The edge- and basal-plane-specific electrochemistry of a single-layer graphene sheet Yuan, Wenjing; Zhou, Yu; Li, Yingru Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02248	journal	July 2013
Electrocatalysis of hydrogen production by active site analogues of the iron hydrogenase enzyme: structure/function relationships Chong, Daesung; Georgakaki, Irene P.; Mejia-Rodriguez, Rosario Dalton Trans., Issue 21 https://doi.org/10.1039/B304283A	journal	January 2003
Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2reductioncatalysts Schneider, Jacob; Jia, Hongfei; Muckerman, James T. Chem. Soc. Rev., Vol. 41, Issue 6 https://doi.org/10.1039/C1CS15278E	journal	January 2012
Protein secondary-shell interactions enhance the photoinduced hydrogen production of cobalt protoporphyrin IX Sommer, Dayn Joseph; Vaughn, Michael David; Ghirlanda, Giovanna Chem. Commun., Vol. 50, Issue 100 https://doi.org/10.1039/C4CC06700B	journal	January 2014
Poisoning effect of adsorbed CO during CO ₂ electroreduction on late transition metals Akhade, Sneha A.; Luo, Wenjia; Nie, Xiaowa Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP03340J	journal	January 2014
A functionalised nickel cyclam catalyst for CO ₂ reduction: electrocatalysis, semiconductor surface immobilisation and light-driven electron transfer Neri, Gaia; Walsh, James J.; Wilson, Calum Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/C4CP04871G	journal	January 2015
Electrochemistry for the generation of renewable chemicals: electrochemical conversion of levulinic acid dos Santos, Tatiane R.; Nilges, Peter; Sauter, Waldemar RSC Advances, Vol. 5, Issue 34 https://doi.org/10.1039/C4RA16303F	journal	January 2015
Environmental applications of graphene-based nanomaterials Perreault, François; Fonseca de Faria, Andreia; Elimelech, Menachem Chemical Society Reviews, Vol. 44, Issue 16 https://doi.org/10.1039/C5CS00021A	journal	January 2015
A highly active nickel electrocatalyst shows excellent selectivity for CO ₂ reduction in acidic media Neri, Gaia; Aldous, Iain M.; Walsh, James J. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC03225C	journal	January 2016
An internal electron reservoir enhances catalytic CO ₂ reduction by a semisynthetic enzyme Schneider, Camille R.; Shafaat, Hannah S. Chemical Communications, Vol. 52, Issue 64 https://doi.org/10.1039/C6CC03901D	journal	January 2016
Ru–protein–Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function Soltau, Sarah R.; Dahlberg, Peter D.; Niklas, Jens Chemical Science, Vol. 7, Issue 12 https://doi.org/10.1039/C6SC03121H	journal	January 2016
A photoactive semisynthetic metalloenzyme exhibits complete selectivity for CO ₂ reduction in water Schneider, Camille R.; Manesis, Anastasia C.; Stevenson, Michael J. Chemical Communications, Vol. 54, Issue 37 https://doi.org/10.1039/C8CC01297K	journal	January 2018
Electrocatalysis by metal phthalocyanines in the reduction of carbon dioxide Meshitsuka, Shunsuke; Ichikawa, Masaru; Tamaru, Kenzi Journal of the Chemical Society, Chemical Communications, Issue 5 https://doi.org/10.1039/c39740000158	journal	January 1974
Nickel(II)-cyclam: an extremely selective electrocatalyst for reduction of CO2 in water Beley, Marc; Collin, Jean-Paul; Ruppert, Romain Journal of the Chemical Society, Chemical Communications, Issue 19 https://doi.org/10.1039/c39840001315	journal	January 1984
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
Inhibited proton transfer enhances Au-catalyzed CO ₂ -to-fuels selectivity Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta Proceedings of the National Academy of Sciences, Vol. 113, Issue 32 https://doi.org/10.1073/pnas.1602984113	journal	July 2016
Mercury Electrodes–Possibilities and Limitations in Environmental Electroanalysis Vyskočil, Vlastimil; Barek, Jiří Critical Reviews in Analytical Chemistry, Vol. 39, Issue 3 https://doi.org/10.1080/10408340903011820	journal	July 2009
Raman Spectroscopy for Chemical Analysis McCreery, Richard L. Measurement Science and Technology, Vol. 12, Issue 5 https://doi.org/10.1088/0957-0233/12/5/704	journal	April 2001
A review of protein adsorption on bioceramics Wang, Kefeng; Zhou, Changchun; Hong, Youliang Interface Focus, Vol. 2, Issue 3 https://doi.org/10.1098/rsfs.2012.0012	journal	March 2012
The Redox Potential of Dithionite and SO-2 from Equilibrium Reactions with Flavodoxins, Methyl Viologen and Hydrogen plus Hydrogenase Mayhew, Stephen G. European Journal of Biochemistry, Vol. 85, Issue 2 https://doi.org/10.1111/j.1432-1033.1978.tb12269.x	journal	April 1978
An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media Becker, René; Amirjalayer, Saeed; Li, Ping Science Advances, Vol. 2, Issue 1 https://doi.org/10.1126/sciadv.1501014	journal	January 2016
A perspective on applications of ligand-field analysis: inspiration from electron paramagnetic resonance spectroscopy of coordination complexes of transition metal ions Telser, Joshua Journal of the Brazilian Chemical Society, Vol. 17, Issue 8 https://doi.org/10.1590/S0103-50532006000800005	journal	January 2006

Cited By (3)

New Photosensitizers Based on Heteroleptic Cu ^I Complexes and CO ₂ Photocatalytic Reduction with [Ni ^II (cyclam)]Cl ₂ Gracia, Lisa‐Lou; Luci, Luisa; Bruschi, Cecilia Chemistry – A European Journal https://doi.org/10.1002/chem.202001279	journal	July 2020
Ligand-centered electrochemical processes enable CO ₂ reduction with a nickel bis(triazapentadienyl) complex Dubrawski, Zachary; Heidebrecht, Joshua; Puerta Lombardi, Braulio M. Sustainable Energy & Fuels, Vol. 3, Issue 5 https://doi.org/10.1039/c8se00623g	journal	January 2019
The good, the neutral, and the positive: buffer identity impacts CO ₂ reduction activity by nickel( ii ) cyclam Schneider, Camille R.; Lewis, Luke C.; Shafaat, Hannah S. Dalton Transactions, Vol. 48, Issue 42 https://doi.org/10.1039/c9dt03114f	journal	January 2019

Similar Records

High electrocatalytic activity of RRSS-[Ni{sup II}HTIM](ClO{sub 4}){sub 2} and [Ni{sup II}DMC](ClO{sub 4}){sub 2} for carbon dioxide reduction (HTIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane, DMC = C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane)

Journal Article · 1994 · Inorganic Chemistry · OSTI ID:421003

Fujita, Etsuko; Sanzenbacher, R; Elias, H

Electrocatalytic reduction of nitrate in sodium hydroxide solution in the presence of low-valent cobalt-cyclam species

Journal Article · 1989 · Inorganic Chemistry; (USA) · OSTI ID:5080107

Li, Hulin; Anderson, W C; Chambers, J Q; +1 more

Electrocatalytic reduction of CO/sub 2/ by Ni cyclam/sup 2 +/ in water: study of the factors affecting the efficiency and the selectivity of the process

Journal Article · 1986 · J. Am. Chem. Soc.; (United States) · OSTI ID:7031898

Beley, M; Collin, J P; Ruppert, R; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry

Title: Spectroelectrochemical investigations of nickel cyclam indicate different reaction mechanisms for electrocatalytic CO2 and H+ reduction

Citation Formats

References (69)

Cited By (3)

Similar Records

Related Subjects

Title: Spectroelectrochemical investigations of nickel cyclam indicate different reaction mechanisms for electrocatalytic CO₂ and H⁺ reduction