(Keynote) Noble-Metal-Free Nanostructured and Graphene Supported Electrocatalysts for Water Splitting
Authors: Wan Wenchao , Zhao Yonggui , Triana Carlos A. , Li Jingguo , Mavrokefalos Christos , Patzke Greta Ricarda 
Published: May 2020

Clean hydrogen production through water splitting is a direct and promising sustainable energy pathway to access and store non-fossil chemical fuels. Synthetic design strategies to access low cost, robust and high performance noble metal-free electrocatalysts are vital for forthcoming water splitting applications. To accomplish this goal, the nanoscale design of multifunctional catalysts based on cost-effective graphene supports, hollow nano-architectures and well-coordinated hybrid organic-inorganic structures has been attracting increasing research interest because of the flexible tuning options of their electronic states, chemical composition and local coordination environments.

Over the last years, we have been implementing systematic investigations based on synthetic design, spectroscopy approaches and computational modeling toward the understanding of the mechanism of action in a series of novel, robust and efficient bi-functional electrocatalysts.

Recently, we explored synergistic effects of NiFe alloys encapsulated into N-doped carbon nanotubes (N-CNTs) supported on reduced graphene (rGO) nanoshets for overall water splitting.[1] This so-called NiFe-N-CNT-rGO electrocatalyst was synthesized through a direct and flexible strategy using g-C3N4 as precursor, where thermally reduced NiFe nanoparticles act as surface nucleation sites for C species to assist N-CNT growth through an unconventional reduction-nucleation-growth mechanism. The catalyst has a low overpotential of 270 mV for oxygen evolution reaction (OER), being superior in performance to a wide range of reported noble-metal-free catalysts. As revealed from density functional theory (DFT) calculations, N-doping and charge transfer at the CNT walls tune the free energy in the electronic structure toward adsorption of intermediates, which greatly enhanced catalytic performance. This synthetic strategy not only leads to excellent performance and opens up new avenues for other carbon-supported alloy catalysts, but its scalability and easy applicability also render it quite promising for large-scale water splitting applications.

In parallel, we explored molecular strategies to conjugate single active sites of metal-phthalocyanine molecules MPc (M=Ni, Co, Fe) on GO.[2] We aim for a thorough understanding of the role of the local coordination environment around the single metal site in the synergistic mechanisms and the catalytic performance. With an advanced combination of ADF (annular dark field)-STEM, operando X-ray absorption spectroscopy and DFT calculations, we observed changes in the electronic and local structure environment of MPc-GO under operando electrochemical OER conditions. Single active metal Ni, Co, Fe sites attain high valence states due to chemisorbed OH− species upon catalytic activation, while the local orders suffer from structural distortion. These changes in the electronic and structural properties lead to the formation of HO-M-N4 moieties with high OER reactivity under operando conditions. These results provides new insight into the fundamental understanding of structure-performance relationships for single active site catalysts.

Likewise, we studied hollow transition metal sulfide nanoboxes synthesized through anion exchange processes[3] between S2- and CN- species that lead to formation of Prussian blue (PB), M-S@PB (M=Co, Fe, Ni) heterostructures. We found that the high performance of those nanostructures arises from in situ formation of active Co-Fe oxide/hydroxide species during OER, attaining a superior performance compared to noble-metal-catalysts such as RuO2, with low overpotential of 286 mV and high durability over longer operational periods. The flexible tuning options of the electronic, chemical and local-atomic coordination of those nanostructures render them promising hybrid catalysts for dual OER and HER over an extended pH range.

We have further explored new soft templating strategies for the first 1D cobalt coordination polymer electrocatalyst with bio-inspired features, and we applied state-of-the-art analytical techniques and computational modeling to monitor its formation in situ and to unravel its structure.[4] The highly durable 1D-cobalt coordination polymer catalyst implements strategies to transfer key motifs of inorganic materials into a hydrogen bonded ligand environment, namely the embedment of the essential {H2O-Co2(OH)2-OH2} edge-site motif of cobalt oxide catalysts into a flexible and robust organic matrix. While this unconventional catalyst shows exceptional performance in commercial alkaline electrolyzers and organic transformations, its flexible structure offers new pathways toward the rational design of mixed molecular-solid disordered catalysts.

[1] W. Wan, S. Wei, J. Li, C. A. Triana, Y. Zhou, G. R. Patzke, J. Mater. Chem. A
2019 (7) 15145.

[2] W. Wan, C. A. Triana, J. Lan, J. Li, C. S. Allen, Y. Zhao, M. Iannuzzi, G. R. Patzke, in preparation.

[3] Y. Zhao, C. K. Mavrokefalos, P. Zhang, R. Erni, J. Li, C. A. Triana, G. R. Patzke, submitted.

[4] C.A. Triana, R. More, A. J. Bloomfield, P. V. Petrovic, S. G. Ferroon, G. Stanley, S. D. Zaric, T. Fox, E. N. Brothers, S. W. Sheehan, P. T. Anastas, G. R. Patzke, Matter
2019 (1) 1354.