Earth-abundant Electrocatalysts Research Articles

Comparison of In Situ and Postsynthetic Formation of MOF-Carbon Composites as Electrocatalysts for the Alkaline Oxygen Evolution Reaction (OER).

Mixed-metal nickel-iron, NixFe materials draw attention as affordable earth-abundant electrocatalysts for the oxygen evolution reaction (OER). Here, nickel and mixed-metal nickel-iron metal-organic framework (MOF) composites with the carbon materials ketjenblack (KB) or carbon nanotubes (CNT) were synthesized in situ in a one-pot solvothermal reaction. As a direct comparison to these in situ synthesized composites, the neat MOFs were postsynthetically mixed by grinding with KB or CNT, to generate physical mixture composites. The in situ and postsynthetic MOF/carbon samples were comparatively tested as (pre-)catalysts for the OER, and most of them outperformed the RuO2 benchmark. Depending on the carbon material and metal ratio, the in situ or postsynthetic composites performed better, showing that the method to generate the composite can influence the OER activity. The best material Ni5Fe-CNT was synthesized in situ and achieved an overpotential (η) of 301 mV (RuO2η = 354 mV), a Tafel slope (b) of 58 mV/dec (RuO2b = 91 mV/dec), a charge transfer resistance (Rct) of 7 Ω (RuO2 Rct = 39 Ω), and a faradaic efficiency (FE) of 95% (RuO2 FE = 91%). Structural changes in the materials could be seen through a stability test in the alkaline electrolyte, and chronopotentiometry over 12 h showed that the derived electrocatalysts and RuO2 have good stability.

Enhancing electrocatalytic hydrogen evolution via engineering unsaturated electronic structures in MoS2.

The search for efficient, earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) has identified unsaturated molybdenum disulfide (MoS2) as a leading candidate. This review synthesises recent advancements in the engineering of MoS2 to enhance its electrocatalytic properties. It focuses on strategies for designing an unsaturated electronic structure on metal catalytic centers and their role in boosting the efficiency of the hydrogen evolution reaction (HER). It also considers how to optimize the electronic structures of unsaturated MoS2 for enhanced catalytic performance. This review commences with an examination of the fundamental crystal structure of MoS2; it elucidates the classical unsaturated electron configurations and the intrinsic factors that contribute to such electronic structures. Furthermore, it introduces popular strategies for constructing unsaturated electronic structures at the atomic level, such as nanostructure engineering, surface chemical modification and interlayer coupling engineering. It also discusses the challenges and future research directions in the study of MoS2 electronic structures, with the aim of broadening their application in sustainable hydrogen production.

Constructing Lewis Acid-Base Pairs to Boost Electrocatalytic Hydrogenation of p-Nitrobenzoic Acid to Valuable p-Aminobenzoic Acid Using Water as the Hydrogen Source.

Electrocatalytic hydrogenation of toxic nitrobenzene to value-added aniline is of great significance in addressing the issues of energy crisis and environmental pollution. However, it is a considerable challenging and crucial to develop highly efficient and earth-abundant transition metal-based electrocatalysts with superior durability for the electro-hydrogenation of nitrobenzene due to the competitive hydrogen evolution reaction (HER). In this work, a facile approach is designed and introduced to constructing an integrated self-supported heterostructured Co1- xNix(OH)(CO3)/Al(OH)3 nanoarrays (CoNiCH/Al(OH)3) for the electrocatalytic reduction of nitrobenzoic acid (PNBA) to p-aminobenzoic acid (PABA) and its electrocatalytic mechanism for PNBA reduction is investigated. This unique Lewis acid-base pairs with abundant oxygen vacancies (OVs) can effectively regulate the adsorption energy of PNBA and active hydrogen intermediates, facilitate the proton-coupled electrocatalytic reduction process, leading to the high activity and selectivity for PNBA to PABA. The optimal CoNiCH/Al(OH)3-0.5 exhibits outstanding performance for the electrocatalytic hydrogenation of PNBA to PABA with a yield of 92%, selectivity of 95% and Faraday efficiency (FE) of 92% at -0.545V (vs reversible hydrogen electrode, RHE) under 0.1m phosphate buffered solution (PBS) neutral electrolyte. Besides, it can maintain a high electrocatalytic activity for at least eight electrocatalytic cycle-test.

Earth-abundant electrocatalysts for acidic oxygen evolution

Earth-abundant electrocatalysts for acidic oxygen evolution

Probing the synergistic effect of metal-organic framework derived Co-Nx rich interwoven hierarchical porous carbon tube encapsulated dual redox active nanoalloy for high-performance Zn-air battery and supercapacitor applications.

Rechargeable zinc-air batteries (ZABs) with high-performance and stability is desirable for encouraging the transition of the technology from academia to industries. However, achieving this balance remains a formidable challenge, primarily due to the requirement of robust, earth-abundant reversible oxygen electrocatalyst. The present study introduces a simple strategy to synthesize Co-Nx rich nanoalloy with N-doped porous carbon tubes (NiCo@NPCTs). The optimized catalyst is bestowed with high electrochemical surface area, and three dimensional (3D) interwoven N-doped PCTs. Moreover, the presence of dual redox-active sites synergistically promotes rapid mass/charge transfer for oxygen electrocatalysis. These features offer excellent reversibility for oxygen electrocatalysis with a reversible oxygen potential gap (ΔE) of 0.74V. The NiCo@NPCTs is utilized as an air-electrode for designing ZABs and using the same electrode-material asymmetric supercapacitor device (ASC) is fabricated. The assembled ZAB delivers an impressive peak power density of 298 mW cm-2 and specific capacity of 731mAh g-1 at 50mA cm-2, along with high rate-capability, durable round-trip voltaic-efficiency. The as-fabricated ASC also shows exciting performance with negligible fading in capacitance and columbic efficiency after 10,000 continuous charge-discharge cycles at a 10 A/g current density. In addition, ZAB-ASC integrated device is assembled, showing real-time application. Thus, the synthesized electrode-material holds great promise for electrocatalysis and also for diverse energy storage applications.

Using Theory to Understand the Origins of the High Activity of Earth-Abundant Transition Metal Oxide Electrocatalysts for the Hydrogen and Oxygen Evolution Reactions in Alkaline Media

A global hydrogen economy (GHE) was envisioned by Haldane in 1923 but has only recently captured wide attention. As the movement toward a GHE accelerates, the supply vs. demand of precious metals such as platinum and iridium will inevitably force their prices skyward. In order to ensure the future of the GHE, it is crucial to intensify the R&D of earth-abundant element-based electrocatalysts. We have recently focused on electrocatalysts for the oxygen evolution and hydrogen evolution reactions (OER, HER) based on Fe, Co, Ni and Mo-containing oxides.1-3 The use of density functional theory (DFT) calculations has enabled us to understand more deeply the origins of high catalytic activity.From OER experimental results, we have found that the activity is higher for Ni-Co oxides with lower structural order.1 This was explained by calculations indicating that the edges of NiOOH sheets are the active sites, at which the rate-determining step M-O + MOH  M-OOH-M is facilitated by the favorable geometry, in which the initial ) O—O distance is significantly shorter than that in the ideal structure (Fig. 1A). The presence of Co ("b" structure) further lowers the activation energy, to 0.15 eV. With the addition of Mo to NixCo1-xOOH, the rds M-O + M-O  M-O-O-M at the layer edges was found to become spontaneous, due to the electron-withdrawing effect of Mo.2 However, it was found that Mo slowly leached out of the structure during actual long-term operation. Ni-Fe oxide was found to be much more stable, and the corresponding DFT calculations showed that the activation energy for the M-O + M-OH  M-OOH-M step was lowered to 0.042 eV.3 In our work on the HER with Ni-Fe alloy/Ni-Fe oxide, we found experimentally that the activity was highest when the alloy was present in contact with a more crystalline form of the oxide.3 The DFT calculations showed that it is necessary to consider both the water dissociation step on the surface of the NixFe1-x(OH)2 sheets and the transfer of a proton to a metallic Ni-Fe alloy particle, on which two adsorbed hydrogens combine to produce H2 (Fig. 1B). This mechanism, which is similar to the bifunctional mechanism proposed by Markovic and coworkers for Pt/NiO,4 we have termed "reverse spillover."Thus, through the combination of experiment and theory, we are developing an understanding of how further increases in electrocatalytic activity for the OER and HER can be achieved with earth-abundant element-based materials.AcknowledgmentsThis work was partially based on results obtained from project JPNP20003, commissioned by the New Energy and Industrial Technology Development Organization (NEDO) of Japan and a JSPS grant, KAKENHI (23H02059).References G. Shi, et al., ACS Catal., 12, 14209 (2022).G. Shi, et al., ACS Appl. Energy Mater., 6, 10742 (2023).G. Shi, et al., ACS Omega, 8, 13068 (2023).Z. Zeng, et al., Nature Energy, 2, 17070 (2017). Figure 1. (A) Reaction profile for the rate-determining step M-O + M-OH  M-O-OH-M on defective NixCo1-xOOH sheets with (a) only Ni and (b) Ni and Co in the active site (taken from Ref 1). (B) Reverse spillover reaction in which a proton is transferred from a water molecule at the surface of the Ni(OH)2 sheet to the Ni7Fe cluster that has a high coverage of H, from which H2 can subsequently desorb (taken from Ref. 3). Figure 1

Heteroatom Engineering in Earth-Abundant Cobalt Electrocatalyst for Energy-Saving Hydrogen Evolution Coupling with Urea Oxidation.

The development of multifunctional electrocatalysts with high performance for electrocatalyzing urea oxidation-assisted water splitting is of great significance for energy-saving hydrogen production. In this work, we demonstrate a novel heteroatom engineering strategy for development of B-doped Co as a multifunctional electrocatalyst for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). Density functional theory (DFT) results suggest that a B dopant can efficiently adjust the electron reconstruction of the exposure of Co sites nearby and facilitate electron transfer, resulting in an optimal d-band center along with a lower Gibbs free energy barrier. Ultimately, the obtained B-Co exhibits pH-universal HER properties in various electrolytes. A highly efficient HER performance with overpotentials as low as 27, 163, and 430 mV to -10, -100, and -500 mA cm-2 in 1.0 M KOH, respectively, is observed for the B-Co electrode. More importantly, the UOR-assisted electrolyzer only requires a voltage input of 1.55 V to produce the current densities of 50 mA cm-2, resulting in a 200 mV saving-energy potential compared to water electrolysis, demonstrating its high efficiency of hydrogen production in industrial applications.

Customizing Bonding Affinity with Multi-Intermediates via Interfacial Electron Capture to Boost Hydrogen Evolution in Alkaline Water Electrolysis.

Developing efficient and earth-abundant alkaline HER electrocatalysts is pivotal for sustainable energy, but co-regulating its intricate multi-step process, encompassing water dissociation, OH- desorption, and hydrogen generation, is still a great challenge. Herein, we tackle these obstacles by fabricating a vertically integrated electrode featuring a nanosheet array with prominent dual-nitride metallic heterostructures characterized by impeccable lattice matching and excellent conductivity, functioning as a multi-purpose catalyst to fine-tune the bonding affinity with alkaline HER intermediates. Detailed structural characterization and theoretical calculation elucidate that charge redistribution at the heterointerface reduces the O p-W d and H s-W d interactions vs. single nitride, thereby enhancing OH- transfer and H2 release. As anticipated, the resulting WN-NiN/CFP catalyst demonstrates a gratifying low overpotential of 36.8 mV at 10 mA/cm2 for alkaline HER, while concurrently maintaining operational stability for 1300 h at 100 mA/cm2 for overall water splitting. This work presents an effective approach to meticulously optimize multiple site-intermediate interactions in alkaline HER, laying the foundation for efficient energy conversion.

Dynamic hydrogen bubble template electrodeposition of a self-supported Co-P electrocatalyst for efficient alkaline oxygen evolution reaction

The development of efficient, inexpensive, and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) represents a significant challenge for the large-scale production of hydrogen. The primary obstacle to the advancement of OER is the necessity for a considerably higher overpotential than the theoretical oxygen evolution potential, due to the sluggish kinetics of the electron transfer reaction, which involves a large amount of thermodynamic energy. In this article, amorphous and cauliflower-like Co-P electrocatalysts were in situ grown on nickel foam by dynamic hydrogen bubble template (DHBT) electrodeposition method. The Co-P electrocatalyst with Co/P ratio optimal presented excellent electrocatalytic activities with a low overpotential of 239 mV for OER at 10 mA·cm−2 and long-term stability in 1.0 M KOH. The outstanding OER performance of the catalyst is mainly attributed the synergistic effect of amorphous and cauliflower-like structure, superhydrophilicity surface, and the electronic regulation by adjusting the atomic ratio of Co to P. This research will bring fresh ideas and strategies for developing novel simple, affordable, and efficient electrocatalysts to boost OER kinetics.

Chirality Engineering of Nanostructured Copper Oxide for Enhancing Oxygen Evolution from Water Electrolysis.

The exploration of a new conceptual strategy for improving the oxygen evolution reaction (OER) of earth-abundant electrocatalysts is critical. In this study, chiral copper oxide nanoflower is explored by a self-assembly method. The characterization suggests the chiral structure originates from the crystal plane-level helical stack of the secondary nanosheets. Of note, the assembly illustrates a record-high degree of spin polarization of 96%, indicating the ideal alignment of electron spin. Moreover, density function theory calculations show the chiral structure reducing the reaction energy barrier (REB) while switching the potential-determining step from *O→*OOH to *OH→*O. Together with the enhanced electrochemical active surface area and accelerated charge transfer, the production of ground-state triplet O2 is improved via a spin-forbidden route that involves the singlet H2O/OH•. Consequently, the chiral nanoflower shows a overpotential of 308mV at 10mA cm-2 and a Tafel slope of 93.5mV dec-1, which is even superior to the commercial RuO2 (310mV, 101mV dec-1). This study presents a new strategy for improving the OER activity by simultaneously enhancing electronic properties and lowering the REB of an non-noble electrocatalyst via chirality engineering.

Hierarchical Bifunctional NiO Electrocatalyst: Highly Porous Structure Boosting the Water Splitting Activity.

The development of an efficient, low-cost and earth-abundant electrocatalyst for water splitting is crucial for the production of sustainable hydrogen energy. However their practical applications are largely restricted by their limited synthesis methods, large overpotential and low surface area. Hierarchical materials with a highly porous three-dimensional nanostructure have garnered significant attention due to their exceptional electrocatalytic properties. These hierarchical porous frameworks enable the fast electron transfer, rapid mass transport, and high density of unsaturated metal sites and maximize product selectivity. Here the process involved obtaining monodispersed microrod-shaped Ni(OH)2 through a hydrothermal reaction, followed by a heat treatment to convert it into hierarchical microrod-shaped NiO materials. N2 sorption analysis revealed that the BET surface area increased from 9 to 89 m2/g as a result of the heat treatment. The hierarchical microrod-shaped NiO materials demonstrated outstanding bifunctional electrocatalytic water splitting capabilities, excelling in both HER and OER in basic solution. Overpotential of 347 mV is achieved at 10 mA/cm2 for OER activity, with a Tafel slope of 77 mV/dec. Similarly, overpotential of 488 mV is achieved at 10 mA/cm2 for HER activity, with a Tafel slope of 62 mV/dec.

Iron, cobalt embedded nitrogen-doped carbon derived from conjugated macrocyclic polymers as electrocatalysts for oxygen reduction reaction

The synthesis of earth-abundant metal-based electrocatalysts for deploying electrochemical energy devices has become an area of considerable interest. Herein, we have illustrated a facile Friedel-Crafts reaction for designing a metalloporphyrin polymer followed by its calcination to synthesize cauliflower-like nitrogen-doped iron-cobalt bimetallic electrocatalyst (FeCoTpp-900–2) and its satisfactory performance toward reducing oxygen. The bimetallic FeCoTpp-900–2 catalyst exhibits a half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE)) and an onset potential (Eonset) of 0.95 V (vs. RHE). The notable electrocatalytic activity for oxygen reduction reaction (ORR) of FeCoTpp-900–2 is attributed to the presence of ORR active nitrogen species along with the Fe-Nx/Co-Nx sites. In addition, FeCoTpp-900–2 possesses an appreciable amount of mesopores responsible for the ORR behavior. Notably, the zinc-air battery consisting of FeCoTpp-900–2 as the catalyst for the air cathode presents a maximal power density of 127.53 mW cm−2 and robust durability for 24 h (h). Therefore, this work can contribute to the facile synthesis of bimetallic electrocatalysts with non-noble metals to explore their applications in ORR.

Chitosan–sodium Tripolyphosphate–CuO Biopolymer–nanocomposite as an Efficient Electrocatalyst for Water Splitting

Background: Fossil fuels have been used extensively as primary energy sources, which has resulted in nearly depleted reserves, a contaminated environment, and a variety of negative health effects globally. Hydrogen has been proposed by researchers as an effective “carbon neutral” fuel. Large-scale hydrogen production through electrochemical water splitting necessitates the use of inexpensive, extremely effective, and earth-abundant electrocatalysts. Method: In this study, chitosan–sodium tripolyphosphate (TPP) nanoparticles are combined with CuO nanostructures to produce chitosan–TPP–CuO (CT/CuO) nanocomposite. Chitosan–TPP nanoparticles were first synthesized using the ionic gelation method. These nanoparticles were then extracted, and CuO was synthesized in situ in polymer nanoparticles using a simple chemical precipitation method. Chitosan and CuO are abundantly available and are environmentally beneficial materials. The porous structure and open channels within the chitosan polymer matrix host the CuO nanostructures, which promote electrolyte penetration, mass transport, and charge transfer, while the metal-oxide nanostructures act as catalytic centers. The structural and morphological properties of the CT/CuO nanocomposite were investigated using XRD, HRSEM, and HRTEM. The band gap and functional groups in the material were measured by UV–Vis DRS and FTIR methods, respectively. Elemental analysis was conducted utilizing EDS, HRSEM, and XPS. Thermal characteristics of the CT/CuO nanocomposite were investigated using TG-DTA and DSC methods. Electrochemical techniques were used to investigate the activities of HER and OER. Results: The XRD examination of the CT/CuO nanocomposite revealed semi-crystalline chitosan peaks and a monoclinic CuO structure. HRSEM and HRTEM pictures indicated that chitosan–TPP nanoparticles and CuO nanostructures were evenly spread and clustered to create a nanoparticulate matrix. UV–Vis DRS indicated that the CT/CuO nanocomposite had a direct band gap of 1.702 eV. The FTIR and XPS studies revealed the various bonds and oxidation states of the nanocomposite. Thermal analyses demonstrated that the inclusion of CuO increased the thermal stability of the CT/CuO nanocomposite. CT/CuO nanocomposite exhibited excellent OER and HER activity, requiring a low overpotential of 444 mV and 379 mV at 10 mA cm−2 and -10 mA cm−2, respectively. Conclusion: Biopolymer metal-oxide nanocomposites could potentially be used as electrocatalysts in water splitting, energy conversion, storage devices, sensors, and several other fields.

Eco-friendly and facile nanomanufacturing of amorphous Co-Ce-Fe trimetallic molybdates composites for accelerated anodic oxygen evolution in alkaline water electrolysis: Evaluation of active sites performance

Currently, endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions. Here, we have prepared a series of metal-based molybdate via one-step coprecipitation method. After ingredient optimization, amorphous Co2CeFe2-MoO4 was identified as exhibiting the highest intrinsic activity among its counterparts. Modulation of electron structure enables Co2CeFe2-MoO4 to balance the adsorption behavior towards reactive intermediates. Ultimately, the obtained Co2CeFe2-MoO4 molybdate demonstrated a captivating OER performance, showcasing a low overpotential of 230 mV at 10 mA cm−2. Moreover, the alkaline electrolyzer employing the Co2CeFe2-MoO4 anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 h of continuous operation, demonstrating its favorable catalytic activity and durability. This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.

Doping-mediated interface engineered Ni3S2: Economically viable electrochemical methanol-mediated water splitting

Electrochemical water splitting is the front runner to meet the global green hydrogen demand. The development of a noble metal-free earth-abundant electrocatalyst is desired to rationalize an economically viable electrochemical water-splitting system. The sluggish anodic oxygen evolution reaction (OER) is the bottleneck of the electrochemical water-splitting system. Herein, to improve OER kinetics, group VIB elements such as chromium (Cr), molybdenum (Mo), and tungsten (W) doped nickel sulfides (Ni3S2) nanosheets (NSs) are synthesized by two-step hydrothermal method to modulate the intrinsic electrocatalytic activity of the pure Ni3S2. Among all the doped samples, the Cr-doped Ni3S2 catalyst exhibited excellent OER with an ultra-low overpotential of 248 mV and MOR with a potential of 1.36 V @ 10 mA cm−2 vs RHE achieving a lower Tafel slope of 95.5 mV/dec and 46.4 mV/dec and outstanding durability with negligible degradation respectively. Furthermore, the Pt/C||Cr-Ni3S2 (1.48 V) system outperforms commercial Pt/C||RuO2 (1.53 V @ 10 mA cm−2) in a two-electrode configuration. The methanol-mediated hybrid water splitting system only warranted a cell voltage of 1.38 V to attain 10 mA cm−2 for the Pt/C||Cr-Ni3S2 system in the presence of 0.1 M methanol (MeOH). The methanol oxidation reaction (MOR) mediated the hybrid water electrolyzer system demonstrates reduced operation cell voltage while additionally electro-synthesizing formate as a value-added chemical. The overall work is motivated to rationalize the importance of doping-mediated interface-engineered catalyst synthesis to improve the electrocatalytic efficiency of the hybrid water electrolyzer.

Probing the structural evolution of cobalt hydroxide in electrochemical water splitting.

Transition-metal hydroxides are a category of earth-abundant and stable electrocatalysts for energy storage and conversion devices involving sluggish oxygen evolution reaction (OER). Understanding dynamic evolution at the solid/liquid interface of transition-metal hydroxides is crucial for the rational design of high-performance OER electrocatalysts. This study implemented in situ electrochemical atomic force microscopy (EC-AFM) to directly image the dynamic structural evolution of α-Co(OH)2 platelets during the electrochemical OER. Reconstruction of α-Co(OH)2, accompanied by ion insertion from the electrolyte, results in a volume expansion, which can be well confirmed from the X-ray diffraction patterns. Our findings are important for the fundamental understanding of transition-metal hydroxide oxygen-evolution catalysts, illustrating the dynamic nature of Co-based nanostructures under electrochemical conditions.

Solar-driven methanol to formate conversion coupled with energy-efficient hydrogen production through Cr dopant-induced charge transfer modulation at the in-situ formed FeOOH/FeCo-LDHs interface

The goal of developing efficient electrocatalysts that can effectively accelerate both the hydrogen evolution reaction (HER) and the methanol oxidation reaction (MOR) is essential. Additionally, overcoming the sluggish anodic oxygen evolution reaction (OER) also presents a considerable challenge for achieving energy-efficient hydrogen (H2) production. Herein, we report the synthesis of self-supported hierarchical FeOOH/Fe0.5CoCr0.5-LDHs as an advanced electrocatalyst by employing simultaneous engineering strategies for producing the formate from MOR at the anode while simultaneously generating H2 at the cathode. Both the experimental and theoretical studies demonstrate the superior charge transfer enabled by the in-situ formed heterostructure. Additionally, electronic modulation due to Cr intercalation, and the presence of a superhydrophilic hybrid surface morphology promote the remarkable electrocatalytic activity and stability of the FeOOH/Fe0.5CoCr0.5-LDHs electrocatalyst. The overall water splitting process required a cell voltage of 2.01 V to achieve a current density of 50 mA cm−2, whereas a lower cell voltage of 1.76 V was sufficient for overall methanol oxidation. Remarkably, a solar-driven system prototype, consisting of a commercial Si cell combined with a methanol splitting electrolyzer comprising FeOOH/Fe0.5CoCr0.5-LDHs electrodes, achieved a photocurrent density of 8.1 mA cm−2 over 2 h. This work demonstrates the capability of earth-abundant elements-based electrocatalysts for sustainable and selective electrochemical synthesis. As a result, it enables the energy-efficient generation of clean H2 and valuable chemicals byproducts.

Surface active sites and interphase engineering into metal oxide hydrates enabled by ions substitution for efficient water splitting

The expanding requirement of energy-effective and cost-efficient water electrolysis has prompted studies of earth-abundant metal-based electrocatalysts. In this study, we study the typical substitution strategies of cation (Pt) or anion (Se) for modifying surface active sites or interphase engineering to tune electronic structure of bimetallic nickel molybdenum oxide hydrates (NiMoO4·xH2O), thus effectively improving catalytic properties toward hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). Result of the cation substitution achieves PtSA–NiMoO4·xH2O catalyst with abundant doped Pt single atoms on surface, which promotes high HER activity with a small overpotential of 73 mV at a current yield of 10 mA cm−2 in alkaline medium. Meanwhile, Se–NiMoO4·xH2O catalyst, an outcome of the anion substitution approach, has unique interfaces of NiSe-NiMoO4 heterostructure and thus exhibits a desired overpotential of only 297 mV for OER. The combination of PtSA–NiMoO4·xH2O(–)//Se–NiMoO4·xH2O(+) couple results in a two-electrode electrolyzer cell, which requires a small cell voltage of 1.48, 1.54 and 1.59 V to deliver a response of 10 mA·cm−2 at 75, 50 and 25 °C, respectively, along with negligible performance decay during 50 h operation. These results highlight the potential of our catalyst engineering strategies to achieve high-performance green hydrogen production.

Halloysite-derived hierarchical cobalt silicate hydroxide hollow nanorods assembled by nanosheets for highly efficient electrocatalytic oxygen evolution reaction

The oxygen evolution reaction (OER) is regarded as the bottleneck of electrolytic water splitting. Thus, developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge. Herein, hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets (denoted as CoSi) were successfully fabricated, using the silica nanotube derived from halloysite as a sacrificial template, via a simple hydrothermal method. The resulting cobalt silicate hydroxide nanosheets stack with thicknesses ∼10 nm, as confirmed by transmission electron microscopy. The elaborated nanoarchitecture possesses a high specific surface area (SSA) allowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthesized using sodium silicate. Among all as-prepared CoSi samples, those synthesized at 150 °C (CoSi-150) exhibited the minimum overpotential of ∼347 mV at a current density of 10 mA cm–2. In addition, CoSi-150 also exhibited superior performance against typical cobalt-based catalysts, and its surface hydroxyl groups were beneficial for the enhancement of OER performance. Furthermore, the CoSi-150 showed excellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH. This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocatalysts.

Electrolyte-Induced Fe-Doping of LaNiO3 Model Surfaces for Water Electrolysis

Renewable energy needs to be store in different energy forms for the energy transition away from fossil fuels. One of most promising forms is chemicals such as H2 and C-based fuels obtained via electrochemical reactions. The common hinderance in such reactions is the sluggish oxygen evolution reaction (OER), which causes low energy efficiency in conversion devices. Developing highly active, earth-abundant OER electrocatalysts in alkaline media is necessary to boost the performance of such devices. Fe ion content in electrolyte is known to influence the OER-activity of metal oxide electrocatalysts. For example, the Fe incorporation in NiOOH is a well-established and important effect for OER.[1] Here, we present the effect of absorbed Fe on the OER activity of the epitaxial Ni-surface terminated LaNiO3 thin films. The correlation between surface species and OER activity of electrocatalysts was investigated using surface-sensitive low-energy ion scattering and X-ray photoemission spectroscopies. We observe more than an order-of-magnitude boost in OER activity during initial cycling, from 0.15 mAcm-2 to 3.40 mAcm-2 at 1.60 V vs. reversible hydrogen electrode. The activity increase was mainly caused by the incorporation of up to 5 % Fe at the top surface of LaNiO3 film (less than ~1 nm) even though only a very trace amount of Fe ion, 30 ppb, is present in the 0.1 M electrolyte of high purity KOH 99.99 %. Our results demonstrate that the disordered active surface phase, which develops even on single crystalline surfaces, is a complex interplay between the as-prepared (surface) crystalline structure, composition of the solid electrocatalyst and the liquid electrolyte, and has strong impact on the final OER activity, implying that we need to think differently about the crystalline electrocatalysts: crystalline bulk and dynamically changing surface layer.[1] L. Trotochaud, S.L. Young, J.K. Ranney, S.W. Boettcher, Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation, J. Am. Chem. Soc. 136 (2014) 6744–6753.