In Situ Self Assembly of Thiolated ortho‐Quinone Capped Electrocatalysts for Bioanalytical Applications

Thiolated o‐quinone‐capped electrocatalysts modeled on the naturally occurring o‐quinone cofactor pyrroloquinoline quinone (PQQ) were designed and synthesized for the development of biosensor devices. The o‐quinone‐capped electrocatalysts self assembled on gold electrodes through a thiolated phenyleneethynylene linkage to form a monolayer less than 2 nm in thickness. Cyclic voltammetric measurements demonstrated reversible electrochemical properties between the quinone and hydroquinone forms of the head group. In an amperometric sensing mode, the modified electrodes reproducibly detected ethanethiol at micromolar levels demonstrating their robust electrocatalytic activity toward thiols. Their redox cycling and electrocatalytic properties show promise for detection of biologically important thiols and other nucleophiles.     

Preparation of a Dual-MOF Heterostructure (ZIF@MIL) for Enhanced Oxygen Evolution Reaction Activity

Although metal-organic frameworks have proven to be excellent electrocatalytic materials, their application as electrode materials remains limited. The preparation of heterostructures is considered an effective method to improve catalytic activity. Herein, we describe the design and assembly of a dual-MOF heterostructure (CoNi−ZIF-67@Fe−MIL-100, denoted ZIF@MIL). Specifically, we grew a layer of MIL-100 in situ on a bimetallic ZIF-67 surface using a solvothermal method. We demonstrate that the ZIF@MIL has remarkable OER electrocatalytic performance, requiring a low overpotential and showing a small Tafel slope, compared to pure ZIF-67 and MIL-100 in 1.0 m KOH. More importantly, it has excellent operational durability for 50 h at 100 mA cm⁻². The high catalytic activity of ZIF@MIL can be attributed to the heterostructure that can expose more active sites, the synergistic effect between ZIF-67 and MIL-100, and improvement of electron transfer ability. Our work provides a new way to design and prepare dual-MOF crystals with different structures as electrocatalysts.     

Exfoliated nickel hydroxide nanosheets for urea electrolysis

Two-dimensional nickel hydroxide nanosheets were synthesized by exfoliating surfactant intercalated layered nickel hydroxides and developed as electrocatalysts for urea electro-oxidation. The electro-oxidation of urea on Ni(OH)₂ nanosheet modified electrodes shows a decrease of 100 mV in overpotential and an enhancement in current density, which reaches ca.154 mA cm^{− 2} mg^{− 1}, by a factor of ca. 170 compared to bulk Ni(OH)₂ powder modified electrodes. The Ni(OH)₂ nanosheets have promising applications in urea-rich wastewater remediation, hydrogen production, electrochemical sensors, and fuel cells due to their ability to promote the urea electrolysis reaction.     

Ru−FeNi Alloy Heterojunctions on Lignin-derived Carbon as Bifunctional Electrocatalysts for Efficient Overall Water Splitting

Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru−FeNi@NLC) encapsulated via lignin-derived carbon was prepared by self-assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm⁻² with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N-doped lignin-derived carbon layer and Ru−FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate-determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on renewable biomass for the construction of highly active, stable and cost-effective catalysts.     

Ni-O4 species anchored on N-doped graphene-based materials as molecular entities and electrocatalytic performances for oxygen reduction reaction

The generation of molecular active species on the surface of nano-materials has become promising routes to produce efficient electrocatalysts. Development of cost-effective catalysts with high performances for oxygen reduction reaction (ORR) is an important challenge for fuel cell and metal-air battery applications. In this work, we report a novel hybrid produced by room-temperature solution processes using Ni-based organometallic molecules and N-doped graphene-based materials. Chemical and structural characterizations reveal that Ni-containing species are well-dispersed on the surface of graphene network as molecular entity. The hybrid shows excellent electrocatalytic performances for ORR in basic medium with an onset potential of 0.87 V (vs. RHE), superior durability and good methanol tolerance.     

Self-assembled cotton-like copper–molybdenum sulfide and phosphide as a bifunctional electrode for green energy storage and production

As the world's energy needs grow and environmental concerns intensify, there is an increasing need for research into developing new materials that may be used in energy production and storage. Herein, we developed copper-molybdenum (Cu–Mo) sulfide and phosphide-based cotton-like nanoarchitectures via hydrothermal strategy and they were characterized using various analytical techniques. The prepared sulfide and phosphide-based materials showed HER overpotentials of 207 mV and 147 mV, respectively, as well as Tafel slope values of 118 mV/dec and 109 mV/dec at 10 mA/cm². While OER at the same current density showed 270 mV and 213 mV overpotentials with 82 mV/dec and 48 mV/dec Tafel slope, respectively. In addition, the prepared sulfide and phosphide-based materials showed significant performance towards supercapacitors, displaying specific capacitances of 3.5 and 5.2 F/cm² at 3 mA/cm², and retaining their specific capacitances by 86.9 and 69.4%, respectively, after 4,000 cycles with 100% Coulombic efficiency. These materials have the potential to be employed for energy production and storage because of their excellent electrochemical characteristics and bifunctional performance.     

First-principles study on Fe2B2 as efficient catalyst for nitrogen reduction reaction

Ammonia (NH₃) is considered an attractive candidate as a clean, highly efficient energy carrier. The electrocatalytic nitrogen reduction reaction (NRR) can reduce energy input and carbon footprint; therefore, rational design of effective electrocatalysts is essential for achieving high-efficiency electrocatalytic NH₃ synthesis. Herein, we report that the enzymatic mechanism is the more favourable pathway for NRR, due to lower limiting potential (−0.44 V), lower free energy (only 0.02 eV) of the first hydrogenation step (*N–N to *NH–N), and more electron transfer from Fe₂B₂ to the reaction species. In addition, both vacancies and dopants can be helpful in reducing the reaction energy barrier of the potential-determining step. Therefore, we have demonstrated that Fe₂B₂ is a potential new candidate for effective NRR and highlighted its potential for applications in electrocatalytic NH₃ synthesis.     

Air-Stable Mn doped CuCl/CuO Hybrid Triquetrous Nanoarrays as Bifunctional Electrocatalysts for Overall Water Splitting

The development of highly efficient non-precious metal catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is key for large-scale hydrogen evolution through water splitting technology. Here, we report an air-stable Cu-based nanostructure consisting of Mn doped CuCl and CuO (CuCl/CuO(Mn)-NF) as a dual functional electrocatalyst for water splitting. CuCl is identified as the main active component, together with Mn doping and the synergistic effect between CuCl and CuO are found to make responsibility for the excellent OER and HER catalytic activity and stability. The assembled electrolyzes also exhibit decent water splitting performance. This work not only provides a simple method for preparing Cu-based composite catalyst, but also demonstrates the great potential of Cu-based non-noble metal electrocatalysts for water splitting and other renewable energy conversion technologies.     

Enhanced Carbon Monoxide Electroreduction to >1 A cm−2 C2+ Products Using Copper Catalysts Dispersed on MgAl Layered Double Hydroxide Nanosheet House-of-Cards Scaffolds

Cu catalysts are most apt for reducing CO₍₂₎ to multi-carbon products in aqueous electrolytes. To enhance the product yield, we can increase the overpotential and the catalyst mass loading. However, these approaches can cause inadequate mass transport of CO₍₂₎ to the catalytic sites, which will then lead to H₂ evolution dominating the product selectivity. Herein, we use a MgAl LDH nanosheet ‘house-of-cards’ scaffold to disperse CuO-derived Cu (OD-Cu). With this support-catalyst design, at −0.7 V_RHE, CO could be reduced to C₂₊ products with a current density (j_C2+) of −1251 mA cm⁻². This is 14× that of the j_C2+ shown by unsupported OD-Cu. The current densities of C₂₊ alcohols and C₂H₄ were also high at −369 and −816 mA cm⁻² respectively. We propose that the porosity of the LDH nanosheet scaffold enhances CO diffusion through the Cu sites. The CO reduction rate can thus be increased, while minimizing H₂ evolution, even when high catalyst loadings and large overpotentials are used.     

Recent Advances and Future Perspectives of Metal-Based Electrocatalysts for Overall Electrochemical Water Splitting

Recently, the growing demand for a renewable and sustainable fuel alternative is contingent on fuel cell technologies. Even though it is regarded as an environmentally sustainable method of generating fuel for immediate concerns, it must be enhanced to make it extraordinarily affordable, and environmentally sustainable. Hydrogen (H₂) synthesis by electrochemical water splitting (ECWS) is considered one of the foremost potential prospective methods for renewable energy output and H₂ society implementation. Existing massive H₂ output is mostly reliant on the steaming reformation of carbon fuels that yield CO₂ together with H₂ and is a finite resource. ECWS is a viable, efficient, and contamination-free method for H₂ evolution. Consequently, developing reliable and cost-effective technology for ECWS was a top priority for scientists around the globe. Utilizing renewable technologies to decrease total fuel utilization is crucial for H₂ evolution. Capturing and transforming the fuel from the ambient through various renewable solutions for water splitting (WS) could effectively reduce the need for additional electricity. ECWS is among the foremost potential prospective methods for renewable energy output and the achievement of a H₂-based economy. For the overall water splitting (OWS), several transition-metal-based polyfunctional metal catalysts for both cathode and anode have been synthesized. Furthermore, the essential to the widespread adoption of such technology is the development of reduced-price, super functional electrocatalysts to substitute those, depending on metals. Many metal-premised electrocatalysts for both the anode and cathode have been designed for the WS process. The attributes of H₂ and oxygen (O₂) dynamics interactions on the electrodes of water electrolysis cells and the fundamental techniques for evaluating the achievement of electrocatalysts are outlined in this paper. Special emphasis is paid to their fabrication, electrocatalytic performance, durability, and measures for enhancing their efficiency. In addition, prospective ideas on metal-based WS electrocatalysts based on existing problems are presented. It is anticipated that this review will offer a straight direction toward the engineering and construction of novel polyfunctional electrocatalysts encompassing superior efficiency in a suitable WS technique.