Molecularly dispersed nickel complexes on N-doped graphene for electrochemical CO2 reduction.

In this work, new hybrid catalysts based on molecularly dispersed nickel complexes on N-doped graphene were developed for electrochemical CO2 reduction (ECR). Nickel(II) complexes (1-Ni, 2-Ni), and a new crystal structure ([2-Ni]Me), featuring N4-Schiff base macrocycles, were synthesized and investigated for their potential in ECR. Cyclic voltammetry (CV) in NBu4PF6/CH3CN solution demonstrated that the nickel complexes bearing N-H groups (1-Ni and 2-Ni) showed a substantial current enhancement in the presence of CO2, while the absence of N-H groups ([2-Ni]Me) resulted in an almost unchanged voltammogram. This indicated the necessity of the N-H functionality towards ECR in aprotic media. All three nickel complexes were successfully immobilized on nitrogen-doped graphene (NG) via non-covalent interactions. All three Ni@NG catalysts exhibited satisfactory CO2-to-CO reduction in aqueous NaHCO3 solution with the faradaic efficiency (FE) of 60-80% at the overpotential of 0.56 V vs. RHE. The ECR activity of [2-Ni]Me@NG also suggested that the N-H moiety from the ligand is less important in the heterogeneous aqueous system owing to viable hydrogen-bond formation and proton donors from water and bicarbonate ions. This finding could pave the way for understanding the effects of modifying the ligand framework at the N-H position toward fine tuning the reactivity of hybrid catalysts through molecular-level modulation.

[1]  Xin Zhao,et al.  Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation , 2023, Molecules.

[2]  Xiang-Kui Gu,et al.  Advances of Cobalt Phthalocyanine in Electrocatalytic CO2 Reduction to CO: a Mini Review , 2022, Electrocatalysis.

[3]  Christopher J. Chang,et al.  Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO2 Reduction Catalyzed by Iron Porphyrins. , 2022, Journal of the American Chemical Society.

[4]  J. Luis,et al.  The dual effect of coordinating –NH groups and light in the electrochemical CO2 reduction with pyridylamino Co complexes , 2021 .

[5]  Hailiang Wang,et al.  Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO2 Reduction Reactions. , 2021, Accounts of chemical research.

[6]  Alexander J. Cowan,et al.  Noncovalent Immobilization of a Nickel Cyclam Catalyst on Carbon Electrodes for CO2 Reduction Using Aqueous Electrolyte , 2021 .

[7]  F. Stavale,et al.  CO2 and H2 adsorption on 3D nitrogen-doped porous graphene: Experimental and theoretical studies , 2021 .

[8]  C. McCrory,et al.  Enhancing a Molecular Electrocatalyst's Activity for CO2 Reduction by Simultaneously Modulating Three Substituent Effects. , 2021, Journal of the American Chemical Society.

[9]  Nengwen Ding,et al.  Advances in Metal Phthalocyanine based Carbon Composites for Electrocatalytic CO2 Reduction , 2020 .

[10]  N. S. Sariciftci,et al.  High-performance CoII-phthalocyanine-based polymer for practical heterogeneous electrochemical reduction of carbon dioxide , 2020 .

[11]  H. Dai,et al.  Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction , 2020, Nature Energy.

[12]  T. Lu,et al.  Non-noble metal-based molecular complexes for CO2 reduction: From the ligand design perspective , 2020 .

[13]  K. Ray,et al.  Electrochemical CO2 Reduction — The Effect of Chalcogenide Exchange in Ni-Isocyclam Complexes , 2020 .

[14]  Sean C. Smith,et al.  Antipoisoning Nickel–Carbon Electrocatalyst for Practical Electrochemical CO2 Reduction to CO , 2019, ACS Applied Energy Materials.

[15]  Hongzhi Zheng,et al.  Revealing the hidden performance of metal phthalocyanines for CO2 reduction electrocatalysis by hybridization with carbon nanotubes , 2019, Nano Research.

[16]  Jonah W. Jurss,et al.  Robust and Selective Cobalt Catalysts Bearing Redox-Active Bipyridyl-N-heterocyclic Carbene Frameworks for Electrochemical CO2 Reduction in Aqueous Solutions , 2019, ACS Catalysis.

[17]  C. Machan,et al.  Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction , 2019, Front. Chem..

[18]  A. Aukauloo,et al.  Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins. , 2019, Angewandte Chemie.

[19]  R. Gargano,et al.  CO2 adsorption in nitrogen-doped single-layered graphene quantum dots: a spectroscopic investigation , 2019, Journal of Molecular Modeling.

[20]  G. Wallace,et al.  Steric Modification of a Cobalt Phthalocyanine/Graphene Catalyst To Give Enhanced and Stable Electrochemical CO2 Reduction to CO , 2019, ACS Energy Letters.

[21]  B. Liu,et al.  Single-Atom Catalysis toward Efficient CO2 Conversion to CO and Formate Products. , 2018, Accounts of chemical research.

[22]  Christopher J. Chang,et al.  Iron Porphyrins Embedded into a Supramolecular Porous Organic Cage for Electrochemical CO2 Reduction in Water. , 2018, Angewandte Chemie.

[23]  Christopher J. Chang,et al.  Urea-Based Multipoint Hydrogen-Bond Donor Additive Promotes Electrochemical CO2 Reduction Catalyzed by Nickel Cyclam , 2018, Organometallics.

[24]  D. Nocera,et al.  Carbon Dioxide Reduction by Iron Hangman Porphyrins , 2018, Organometallics.

[25]  Ruquan Ye,et al.  Elucidating the Reactivity and Mechanism of CO2 Electroreduction at Highly Dispersed Cobalt Phthalocyanine , 2018 .

[26]  M. Sabat,et al.  Electrocatalytic Reduction of CO2 to Formate by an Iron Schiff Base Complex. , 2018, Inorganic chemistry.

[27]  Y. Surendranath,et al.  Bicarbonate Is Not a General Acid in Au-Catalyzed CO2 Electroreduction. , 2017, Journal of the American Chemical Society.

[28]  Wenjun Zhang,et al.  Progress and Perspective of Electrocatalytic CO2 Reduction for Renewable Carbonaceous Fuels and Chemicals , 2017, Advanced science.

[29]  Jingguang G. Chen,et al.  The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold. , 2017, Journal of the American Chemical Society.

[30]  Robert Kutz,et al.  Electrochemical generation of syngas from water and carbon dioxide at industrially important rates , 2016 .

[31]  R. Haiges,et al.  Proton-Assisted Reduction of CO2 by Cobalt Aminopyridine Macrocycles. , 2016, Journal of the American Chemical Society.

[32]  Jing Shen,et al.  Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide. , 2015, The journal of physical chemistry letters.

[33]  Jian Zhang,et al.  Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution , 2015, Nature Communications.

[34]  Douglas R. Kauffman,et al.  Efficient electrochemical CO2 conversion powered by renewable energy. , 2015, ACS applied materials & interfaces.

[35]  J. Savéant,et al.  Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water , 2015, Proceedings of the National Academy of Sciences.

[36]  F. Neese,et al.  Bio-inspired mechanistic insights into CO₂ reduction. , 2015, Current opinion in chemical biology.

[37]  C. Kubiak,et al.  The homogeneous reduction of CO₂ by [Ni(cyclam)]⁺: increased catalytic rates with the addition of a CO scavenger. , 2015, Journal of the American Chemical Society.

[38]  Charles C. L. McCrory,et al.  Studies of Cobalt-Mediated Electrocatalytic CO2 Reduction Using a Redox-Active Ligand , 2014, Inorganic chemistry.

[39]  Michele Aresta,et al.  Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2. , 2014, Chemical reviews.

[40]  Michel Dupuis,et al.  Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation. , 2013, Chemical reviews.

[41]  S. Brooker,et al.  Complexes of a porphyrin-like N4-donor Schiff-base macrocycle. , 2013, Dalton transactions.

[42]  A. Majumdar,et al.  Opportunities and challenges for a sustainable energy future , 2012, Nature.

[43]  C. Kubiak,et al.  Homogeneous CO2 reduction by Ni(cyclam) at a glassy carbon electrode. , 2012, Inorganic chemistry.

[44]  S. Brooker,et al.  Synthesis and complexes of an N4 Schiff-base macrocycle derived from 2,2'-iminobisbenzaldehyde. , 2011, Dalton transactions.

[45]  V. Thoi,et al.  Nickel N-heterocyclic carbene-pyridine complexes that exhibit selectivity for electrocatalytic reduction of carbon dioxide over water. , 2011, Chemical communications.

[46]  P. Kenis,et al.  Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction , 2010 .

[47]  Jae-Hun Jeoung,et al.  Carbon Dioxide Activation at the Ni,Fe-Cluster of Anaerobic Carbon Monoxide Dehydrogenase , 2007, Science.

[48]  Manfred Rudolph,et al.  Macrocyclic [N42-] Coordinated Nickel Complexes as Catalysts for the Formation of Oxalate by Electrochemical Reduction of Carbon Dioxide , 2000 .

[49]  Kelley J. Rountree,et al.  A Practical Beginner’s Guide to Cyclic Voltammetry , 2017 .