Edge-selective decoration with ruthenium at graphitic nanoplatelets for efficient hydrogen production at universal pH

doi:10.1016/j.nanoen.2020.105114

Nano Energy

Volume 76, October 2020, 105114

https://doi.org/10.1016/j.nanoen.2020.105114 Get rights and content

Highlights

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The Ru-ENG catalyst was designed with modification of edge sites of graphitic nanoplatelets induces high doping ratio without severing damages on the carbon basal plane.
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Interestingly, direct nitrogen(N) fixation at the broken edge sites of graphitic nanoplatelets was induced simply physicochemical radicalization process. Ru nanoparticles were self-grown with forming the N–Ru interaction at edge-sites of ENG and derived excellent catalytic activities.
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The X-ray absorption fine structure (XAFS) of Ru-ENG catalyst was placed between metallic Ru and RuO₂, confirming the reconstructed electron configuration of metallic Ru on ENG.
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Notably, the Ru-ENG catalyst showed comparable Tafel slope for the HER comparing with the commercial Pt/C in a wide-pH window, along with stable performance over 1500 h for water splitting system.

Abstract

Although the electrochemical reaction is an effective and great promise to produce hydrogen, the realization of efficient and stable catalysts is still a significant challenge in the various electrochemical systems, such as water splitting and Zn-CO₂ system. Herein, we report Ru nanoparticles anchored at edge-selectively nitrogenated graphitic nanoplatelets (Ru-ENG) instead of on the basal plane in two-dimensional (2D) graphitic substrate. The Ru nanoparticles interacted with both of armchair-ENG and zigzag-ENG substrate lead to favorable hydrogen evolution activities of icosahedron cluster Ru₁₃ in Ru-ENG at a universal pH, compared to Ru metal cluster. The spontaneous electron re-construction between edge-site of N and ruthenium particles in Ru-ENG catalyst is attributed to the faster reaction kinetics with lower Tafel slopes and higher turnover frequencies than the benchmark Pt/C catalyst in any pH conditions. More importantly, the Ru-ENG electrocatalyst exhibited superior long-term consecutive stability (over 1,500 h) at a high current density of 100 mA cm⁻² in the practical water-splitting system.

Graphical abstract

This work represents the edge-sites design of graphitic nanoplatelets with ruthenium nanoparticles for an efficient and stable HER electrocatalyst at universal pH.

Introduction

Hydrogen (H₂) is regarded as a clean and high gravimetric density energy source to replace traditional fossil fuels [[1], [2], [3]]. The hydrogen evolution reaction (HER) in electrochemical water splitting is one of the promising ways to economically produce high-purity hydrogen. Currently, the state-of-the-art electrocatalyst for hydrogen production is composed of platinum (Pt)-based catalysts and it has several drawbacks such as high-cost, limited reserves, and poor electrochemical stability. Even though non-noble metal materials have been widely explored as enhanced catalysts for hydrogen production, the greatest challenge for the use of non-noble metal materials so far is that their HER activities still underperform Pt-based catalysts and they are susceptible to debase stability in a wide pH range [4,5]. In view of the inevitable local pH change of the electrolyte near the electrode surface during the prolonged electrolysis process, the ideal catalyst should perform equally well in different pH conditions for energy-efficient water splitting. Though there has been some progress in recent years, the development of cost-effective catalysts with long-term stability and pH tolerance still remains challenging.

To date owing to their Pt-like catalytic properties, ruthenium (Ru)-based compounds, such as Ru/C₃N₄/C, Ru@C₂N, and RuP₂/NPC have recently attention as promising electrocatalysts with efficient electrochemical activities for hydrogenation reactions [[6], [7], [8]]. Especially, Ru has similar electronic features with Pt and thus exhibits promising potential in electrocatalytic water splitting due to a suitable hydrogen adsorption/desorption energy balance. The reported Ru-based catalysts, however, have still far from satisfactory at wide pH in terms of undesirable aggregation or inevitable active-sites decay during the electrochemical process. From the viewpoint of the substrate to enhance the electrocatalytic activity and stability, a two-dimensional (2D) graphitic substrate can provide great opportunities for enhancing the electrochemical performances from rationally engineering [[9], [10], [11], [12], [13]]. From the numerous researches about the graphitic-based substrate, it is well-known that substitution of heteroatoms could lead to the activation of graphitic surface for electrochemical reactions and edge-sites of graphitic heteroatom exhibited much superior (electro)catalytic properties than those of basal carbons [[14], [15], [16], [17]]. Furthermore, the modification of the edge sites induces favorable local electronic structure toward electrochemical activity and high doping ratio of substitution.

Encouraged by this consideration, in this work, we report Ru nanoparticles anchored at edge-selectively nitrogenated graphitic nanoplatelets (Ru-ENG) via physicochemical radicalization process. The edge-selectively nitrogenated graphitic nanoplatelets (ENG) exposed to an abundant anchoring edge-sites for Ru metal without severe damages on the carbon basal plane, leading to superior conductivities and electrochemical activities for HER. A series of practical experiments, XAFS, XPS, and DFT calculations suggested that enhancement of HER in universal-pH media was attributed to the spontaneous electron re-construction between N of edge-site and ruthenium particles (Ru–N) in Ru-ENG catalyst. In addition, the active edge sites in both of armchair (AC)- and zigzag (ZZ)-ENG lead to favorable hydrogen binding energy (-ΔE_bind, H₂) and the water decomposition energy (-ΔE_rxn, H₂O) of the icosahedron cluster, Ru₁₃, in Ru-ENG. With these unique advantages, the Ru-ENG catalyst exhibited faster reaction kinetics with lower Tafel slope and higher turnover frequency (TOF) than those of benchmark Pt/C catalyst in universal-pH conditions. In the application of water-splitting, the Ru-ENG electrode exhibited exceptional electrocatalytic activities for HER over 1,500 h at a high current density of 100 mA cm⁻², which is far superior and stable performance compared to the benchmark Pt/C and other reported electrodes. This physicochemical approach of edge-selectively hetero-atom substitution for HER electrocatalyst offers great potential to be used as the industrial viability of electrochemical HER in various pH-conditions.

Section snippets

Synthesis of ENG [18]

ENG was synthesized by the ball-milling process using the pristine graphite flake in the ball-mill machine (Pulverisette 6, Fritsch) in the presence of nitrogen (N₂). The stainless-steel balls (500.0 g, diameter 5 mm) and the pristine graphite (5.0 g, Alfa Aesar, natural graphite, 100 mesh (<150 mm), 99.9995% metals basis, Lot#14735) were put into a stainless-steel ball-mill capsule (500 mL). After five charging-discharging cycles with N₂, the capsule was sealed and fully charged with N₂ (8 bar

Structural characterization

As shown in schematic illustration (Fig. 1), the physicochemical radicalization process induces a direct nitrogen fixation at the physically broken edges of graphitic frameworks. The cleavage of graphitic C–C bonds by ball-milling method created active radical species to react with nitrogen to form C–N bonds along the edges. Thermodynamically, the preferred edge formation of ENG is to maintain the aromatic configuration from reaction with nitrogen. With an exothermic (spontaneous) reaction from

Conclusions

In summary, we have reported rationally anchored Ru nanoparticles at edge-selectively nitrogenated graphitic nanoplatelets (Ru-ENG) via physicochemical ball-milling method. The edge-selectively nitrogenated graphitic nanoplatelets (ENG) exposed to an abundant anchoring edge-sites for Ru metal without severe damages on the carbon basal plane, which leads to superior conductivities and electrochemical activities for HER. The specific interaction of Ru–N bonds in both of armchair-ENG and

Author contributions

Y. Y. and J. K. conducted the overall experiments. A. S. conducted structural experiments. C. K. and O. K. have discussed electrochemical and structural analysis. J. H. L. and I. K. conducted DFT calculations. L. Z., J. Z., and J.-Q. W. conducted the XAFS measurements and analysis. J.-B. B., S. K. K. and G. K. discussed the results, analyzed the data and wrote the manuscript. The work was conceived, planned, and supervised by G. K. All authors contributed to writing the manuscript.

CRediT authorship contribution statement

Yejin Yang: Formal analysis, Conceptualization, Data curation, Writing - original draft, Writing - review & editing. Jeongwon Kim: Formal analysis, Conceptualization, Data curation, Writing - original draft, Writing - review & editing. Changmin Kim: Formal analysis, Writing - review & editing. Arim Seong: Formal analysis, Investigation. Ohhun Kwon: Formal analysis, Software. Jeong Hyeon Lee: Resources, Methodology, Writing - original draft. Imanuel Kristanto: Resources, Methodology, Writing -

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the 2020 Research Fund of KOREA East-West Power.co., LTD. (EWP) (2.190769.01). This work was also supported by “Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences, Grant No. XDA21000000; the K. C. Wong Education Foundation, Grant No. GJTD-2018-10, and Youth Innovation Promotion Association (grant No. 2014237), Chinese Academy of Sciences. S.K.K. acknowledges the financial support

Yejin Yang received her bachelor's degree in mechanical technology from Korea maritime & ocean university, Republic of Korea. She is currently a Ph.D. candidate in Department of Energy Engineering at UNIST. Her research interests lie in electrochemical catalysts based on transition metal aiming to develop efficient energy storage and conversion devices, such as metal-air batteries, and CO₂ utilization.

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Citation Excerpt :
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Jeongwon Kim received his bachelor's degree in advanced materials chemistry from Korea university, Republic of Korea. He is currently a Ph.D. candidate in Department of Energy Engineering at UNIST. His research interests lie in electrochemical catalysts based on transition metal aiming to develop efficient energy storage and conversion devices, such as metal-air batteries, polymer electrolyte membrane fuel cell, and CO₂ utilization.

Changmin Kim received his Ph.D. degree in energy engineering from Ulsan Institute of Science and Technology (UNIST), Republic of Korea. He is currently performing postdoctoral study in School of Chemical Engineering at University of New South Wale (UNSW). His research interests lie in electrochemical catalysts based on layered perovskites aiming to develop efficient energy storage and conversion devices, such as metal-air batteries, water splitting, and CO₂ conversion.

Arim Seong received her bachelor's degree in energy conversion and storage and chemical engineering from Ulsan Institute of Science and Technology (UNIST), Republic of Korea. She is currently a Ph.D. candidate in Department of Energy Engineering at UNIST. Her research interests lie in electrochemical catalysts based on perovskites aiming to develop efficient energy storage and conversion devices, such as protonic ceramic fuel cell, metal-air batteries, atomic layer deposition (ALD), and CO₂ utilization.

Ohhun Kwon received his bachelor's degree in energy conversion and storage and chemical engineering from Ulsan Institute of Science and Technology (UNIST), Republic of Korea. He is currently a Ph.D. candidate in Department of Energy Engineering at UNIST. His research interests lie in electrochemical catalysts based on layered perovskites aiming to develop efficient energy storage and conversion devices, such as solid oxide fuel cell, metal-air battery, and high temperature energy conversion system.

Jeong Hyeon Lee is currently a Ph.D. candidate in the School of Energy and Chemical Engineering at Ulsan National Institute of Science and Technology (UNIST). He received his bachelor's degree in nanochemistry and chemical engineering from UNIST in 2016. His research interests focus on the application of multiscale-simulation method for the separation and purification of the gas mixture using porous materials, and for the mechanistic studies of adsorption and reaction involving organic or inorganic molecules on catalysts.

Imanuel Kristanto is currently a Ph.D. candidate at Ulsan National Institute of Science and Technology (UNIST). He received his bachelor's degree in Chemical and Biomolecular Engineering at Nanyang Technological University in 2014. His research interests focus on theoretical study of metal nanoparticles crystallization and surface phenomena in energy materials.

Linjuan Zhang is a professor at Shanghai Institute of Applied Physics, Chinese Academy of Sciences, China. She received a Bachelor's Degree from Beihang University in 2007, a Ph.D. degree from Institute of High Energy Physics, Chinese Academy of Sciences in 2012, and worked as a visiting scholar in SLAC National Accelerator Laboratory at Stanford University in 2017. Her research interests lie in advanced energy materials and the application of X-ray absorption spectroscopy.

Jing Zhou is an associate professor at Shanghai Institute of Applied Physics, Chinese Academy of Sciences, China. He received a Bachelor's Degree from University of Science and Technology of China in 2007, and a Ph.D. degree from Institute of High Energy Physics, Chinese Academy of Sciences in 2012. His research expertise and interests mainly lie in developing the novel catalysts of hydrogen-production by electrolysis water and the studying on reaction mechanism using advanced X-ray absorption spectroscopy and density functional theory calculation.

Jian-Qiang Wang is a full professor at Shanghai Institute of Applied Physics and director of Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, China. He received a Bachelor's Degree from Heilongjiang University in 1998, and a Ph.D. degree from Fudan University in 2006. From 2006 to 2009, he performed postdoctoral study in Technische Universität München as Humboldt Research Fellow. His research expertise and scholarly activities lie in energy conversion and storage, such as hydrogen production by high temperature steam electrolysis with SOEC, molten salt chemistry, X-ray absorption spectra technique.

Jong-Beom Baek is a professor/director at the School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), South Korea. After receiving his Ph.D. degree from Polymer Science, University of Akron (USA, 1998), he joined the Wright-Patterson Air Force Research Laboratory (AFRL). He returned to his home country to take up a position as an assistant professor at Chungbuk National University in 2003, before moving to UNIST in 2008. His current research interests include the synthesis of two-dimensional (2D) and three-dimensional (3D) porous network frameworks and the chemical modifications of carbon-based materials for multifunctional.

Sang Kyu Kwak has received his Ph.D. degree in Chemical Engineering from the State University of New York at Buffalo (University at Buffalo) in 2005. He worked as an assistant professor at Nanyang Technological University (NTU) in Singapore for 6 years and moved to the Ulsan National Institute of Science and Technology (UNIST) in South Korea in 2012. His expertise lies in multiscale-simulation principles based on statistical thermodynamics, chemical physics, physical chemistry, and molecular physics.

Guntae Kim received his Ph.D. in Chemistry from University of Houston in 2005. He is a Professor in the School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Republic of Korea. His research interests include materials for new energy technologies and their applicability in powering or conversion, storage devices. A particular field of interest is the development of layered perovskite oxides for fuel cell applications, metal-air batteries, proton-conducting oxides for SOFCs, and oxygen membrane reactors.

¹: These authors contributed equally to this work.

View full text

Edge-selective decoration with ruthenium at graphitic nanoplatelets for efficient hydrogen production at universal pH

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of ENG [18]

Structural characterization

Conclusions

Author contributions

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgements

iScience

Nat. Commun.

Nano Energy

Appl. Catal. B Environ.

Carbon N. Y.

Carbon N. Y.

Nano Energy

Ternary NiCo2Px nanowires as pH-universal electrocatalysts for highly efficient hydrogen evolution reaction

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Angew. Chem. Int. Ed.

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J. Am. Chem. Soc.

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Sci. Rep.

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Adv. Mater.

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ChemElectroChem

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Angew. Chem. Int. Ed.

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Sci. Rep.

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Ternary NiCo₂P_x nanowires as pH-universal electrocatalysts for highly efficient hydrogen evolution reaction

RuP₂-based catalysts with platinum-like activity and higher durability for the hydrogen evolution reaction at all pH values