Metallic nanostructures with low dimensionality for electrochemical water splitting
26 May 2020-Chemical Society Reviews (The Royal Society of Chemistry)-Vol. 49, Iss: 10, pp 3072-3106
TL;DR: This review article introduces several typical methods for synthesizing one-dimensional and two-dimensional metallic nanostructures including organic ligand-assisted synthesis, hydrothermal/solvothermal synthesis, carbon monoxide confined growth, topotactic reduction, and templated growth.
Abstract: Metallic nanostructures with low dimensionality (one-dimension and two-dimension) possess unique structural characteristics and distinctive electronic and physicochemical properties including high aspect ratio, high specific surface area, high density of surface unsaturated atoms and high electron mobility. These distinctive features have rendered them remarkable advantages over their bulk counterparts for surface-related applications, for example, electrochemical water splitting. In this review article, we highlight the recent research progress in low-dimensional metallic nanostructures for electrochemical water splitting including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Fundamental understanding of the electrochemistry of water splitting including HER and OER is firstly provided from the aspects of catalytic mechanisms, activity descriptors and property evaluation metrics. Generally, it is challenging to obtain low-dimensional metallic nanostructures with desirable characteristics for HER and OER. We hereby introduce several typical methods for synthesizing one-dimensional and two-dimensional metallic nanostructures including organic ligand-assisted synthesis, hydrothermal/solvothermal synthesis, carbon monoxide confined growth, topotactic reduction, and templated growth. We then put emphasis on the strategies adopted for the design and fabrication of high-performance low-dimensional metallic nanostructures for electrochemical water splitting such as alloying, structure design, surface engineering, interface engineering and strain engineering. The underlying structure–property correlation for each strategy is elucidated aiming to facilitate the design of more advanced electrocatalysts for water splitting. The challenges and perspectives for the development of electrochemical water splitting and low-dimensional metallic nanostructures are also proposed.
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TL;DR: The Pt18Ni26Fe15Co14Cu27/C catalyst exhibits excellent electrocatalytic performance for hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR) and is the efficient catalyst ever reported for MOR in alkaline solution.
Abstract: Designing electrocatalysts with high-performance for both reduction and oxidation reactions faces severe challenges. Here, the uniform and ultrasmall (~3.4 nm) high-entropy alloys (HEAs) Pt18Ni26Fe15Co14Cu27 nanoparticles are synthesized by a simple low-temperature oil phase strategy at atmospheric pressure. The Pt18Ni26Fe15Co14Cu27/C catalyst exhibits excellent electrocatalytic performance for hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR). The catalyst shows ultrasmall overpotential of 11 mV at the current density of 10 mA cm−2, excellent activity (10.96 A mg−1Pt at −0.07 V vs. reversible hydrogen electrode) and stability in the alkaline medium. Furthermore, it is also the efficient catalyst (15.04 A mg−1Pt) ever reported for MOR in alkaline solution. Periodic DFT calculations confirm the multi-active sites for both HER and MOR on the HEA surface as the key factor for both proton and intermediate transformation. Meanwhile, the construction of HEA surfaces supplies the fast site-to-site electron transfer for both reduction and oxidation processes. The design of nanostructured catalysts plays a key role in the electrocatalytic redox reaction performances. Here, authors prepared uniform and small-sized high-entropy alloy PtNiFeCoCu nanoparticles that showed improved activities for H2 evolution methanol oxidation reactions.
221 citations
TL;DR: In this article, a review of transition metal-based OER electrocatalysts is presented to reveal the novel design principles and perspectives for further catalytic performance enhancement and deeper understanding of catalyst design.
Abstract: Oxygen evolution reaction (OER) is an important half-reaction involved in many electrochemical applications, such as water splitting and rechargeable metal-air batteries. However, the sluggish kinetics of its four-electron transfer process becomes a bottleneck to the performance enhancement. Thus, rational design of electrocatalysts for OER based on thorough understanding of mechanisms and structure-activity relationship is of vital significance. This review begins with the introduction of OER mechanisms which include conventional adsorbate evolution mechanism and lattice-oxygen-mediated mechanism. The reaction pathways and related intermediates are discussed in detail, and several descriptors which greatly assist in catalyst screen and optimization are summarized. Some important parameters suggested as measurement criteria for OER are also mentioned and discussed. Then, recent developments and breakthroughs in experimental achievements on transition metal-based OER electrocatalysts are reviewed to reveal the novel design principles. Finally, some perspectives and future directions are proposed for further catalytic performance enhancement and deeper understanding of catalyst design. It is believed that iterative improvements based on the understanding of mechanisms and fundamental design principles are essential to realize the applications of efficient transition metal-based OER electrocatalysts for electrochemical energy storage and conversion technologies.
179 citations
176 citations
TL;DR: In this article, the authors provide an overview of the progress in the design and synthesis of advanced acidic oxygen evolution reaction (OER) electrocatalysts in terms of catalyst category, i.e., metallic nanostructures (Ir and Ru based), precious metal oxides, nonprecious metal oxide, and carbon based nanomaterials.
Abstract: Proton exchange membrane (PEM) water electrolyzers hold great significance for renewable energy storage and conversion. The acidic oxygen evolution reaction (OER) is one of the main roadblocks that hinder the practical application of PEM water electrolyzers. Highly active, cost-effective, and durable electrocatalysts are indispensable for lowering the high kinetic barrier of OER to achieve boosted reaction kinetics. To date, a wide spectrum of advanced electrocatalysts has been designed and synthesized for enhanced acidic OER performance, though Ir and Ru based nanostructures still represent the state-of-the-art catalysts. In this Progress Report, recent research progress in advanced electrocatalysts for improved acidic OER performance is summarized. First, fundamental understanding about acidic OER including reaction mechanisms and atomic understanding to acidic OER for rational design of efficient electrocatalysts are discussed. Thereafter, an overview of the progress in the design and synthesis of advanced acidic OER electrocatalysts is provided in terms of catalyst category, i.e., metallic nanostructures (Ir and Ru based), precious metal oxides, nonprecious metal oxides, and carbon based nanomaterials. Finally, perspectives to the future development of acidic OER are provided from the aspects of reaction mechanism investigation and more efficient electrocatalyst design.
174 citations
TL;DR: In this article, the progress of non-van der Waals (non-vdW) 2D materials with numerous chemical bonds in all three dimensions and novel chemical and electronic properties beyond those of vdW 2D material have been studied increasingly over the past decades.
Abstract: The exploration of efficient electrocatalysts for energy conversion is important for green energy development. Owing to their high surface areas and unusual electronic structure, 2D electrocatalysts have attracted increasing interest. Among them, non-van der Waals (non-vdW) 2D materials with numerous chemical bonds in all three dimensions and novel chemical and electronic properties beyond those of vdW 2D materials have been studied increasingly over the past decades. Herein, the progress of non-vdW 2D electrocatalysts is critically reviewed, with a special emphasis on electronic structure modulation. Strategies for heteroatom doping, vacancy engineering, pore creation, alloying, and heterostructure engineering are analyzed for tuning electronic structures and achieving intrinsically enhanced electrocatalytic performances. Lastly, a roadmap for the future development of non-vdW 2D electrocatalysts is provided from material, mechanism, and performance viewpoints.
157 citations
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TL;DR: In this paper, the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations was analyzed and a detailed description of the free energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias was presented.
Abstract: We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...
7,711 citations
TL;DR: A unified theoretical framework highlights the need for catalyst design strategies that selectively stabilize distinct reaction intermediates relative to each other, and opens up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions.
Abstract: BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.
7,062 citations
TL;DR: The active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) is determined by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution.
Abstract: The identification of the active sites in heterogeneous catalysis requires a combination of surface sensitive methods and reactivity studies. We determined the active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution. By preparing MoS2 nanoparticles of different sizes, we systematically varied the distribution of surface sites on MoS2 nanoparticles on Au(111), which we quantified with scanning tunneling microscopy. Electrocatalytic activity measurements for hydrogen evolution correlate linearly with the number of edge sites on the MoS2 catalyst.
4,930 citations
TL;DR: This review highlights the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER), and summarizes some important examples showing that non-Pt HER electrocatsalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalyst.
Abstract: Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.
4,351 citations
TL;DR: In this paper, a method for extracting a unique set of atomic hybrids and bond orbitals for a given molecule, thereby constructing its Lewis structure in an a priori manner, is described.
Abstract: From the information contained in the (exact or approximate) first-order density matrix, we describe a method for extracting a unique set of atomic hybrids and bond orbitals for a given molecule, thereby constructing its “Lewis structure” in an a priori manner. These natural hybrids are optimal in a certain sense, are efficiently computed, and seem to agree well with chemical intuition (as summarized, for example, in Bent’s Rule) and with hybrids obtained by other procedures. Using simple INDO-SCF-MO wave functions, we give applications of the natural hybrid orbital analysis to molecules exhibiting a variety of bonding features, including lone pairs, multiple bonds, strained rings, and “bent bonds”, multiple resonance structures, hydrogen bonds, and three-center bonds. Three examples are described in greater detail: (i) “orbital following” during ammonia umbrella inversion, (ii) the dimerization of water molecules, and (iii) the hydrogen-bridged bonds of diborane.
4,338 citations