A universal and scalable transformation of bulk metals into single-atom catalysts in ionic liquids.

Single-atom catalysts (SACs) with maximized metal atom utilization and intriguing properties are of utmost importance for energy conversion and catalysis science. However, the lack of a straightforward and scalable synthesis strategy of SACs on diverse support materials remains the bottleneck for their large-scale industrial applications. Herein, we report a general approach to directly transform bulk metals into single atoms through the precise control of the electrodissolution-electrodeposition kinetics in ionic liquids and demonstrate the successful applicability of up to twenty different monometallic SACs and one multimetallic SAC with five distinct elements. As a case study, the atomically dispersed Pt was electrodeposited onto Ni3N/Ni-Co-graphene oxide heterostructures in varied scales (up to 5 cm × 5 cm) as bifunctional catalysts with the electronic metal-support interaction, which exhibits low overpotentials at 10 mA cm-2 for hydrogen evolution reaction (HER, 30 mV) and oxygen evolution reaction (OER, 263 mV) with a relatively low Pt loading (0.98 wt%). This work provides a simple and practical route for large-scale synthesis of various SACs with favorable catalytic properties on diversified supports using alternative ionic liquids and inspires the methodology on precise synthesis of multimetallic single-atom materials with tunable compositions.

Operando probing and adjusting of the complicated electrode process of multivalent metals at extreme temperature.

Nearly half of the elements in the periodic table are extracted, refined, or plated using electrodeposition in high-temperature melts. However, operando observations and tuning of the electrodeposition process during realistic electrolysis operations are extremely difficult due to severe reaction conditions and complicated electrolytic cell, which makes the improvement of the process very blind and inefficient. Here, we developed a multipurpose operando high-temperature electrochemical instrument that combines operando Raman microspectroscopy analysis, optical microscopy imaging, and a tunable magnetic field. Subsequently, the electrodeposition of Ti-which is a typical polyvalent metal and generally shows a very complex electrode process-was used to verify the stability of the instrument. The complex multistep cathodic process of Ti in the molten salt at 823 K was systematically analyzed by a multidimensional operando analysis strategy involving multiple experimental studies, theoretical calculations, etc. The regulatory effect and its corresponding scale-span mechanism of the magnetic field on the electrodeposition process of Ti were also elucidated, which would be inaccessible with existing experimental techniques and is significant for the real-time and rational optimization of the process. Overall, this work established a powerful and universal methodology for in-depth analysis of high-temperature electrochemistry.

Revealing the missing puzzle piece of concentration in regulating Zn electrodeposition.

Despite achievements in suppressing dendrites and regulating Zn crystal growth, secondary aqueous Zn batteries are still rare in the market. Existing strategies mainly focus on electrode modification and electrolyte optimization, while the essential role of ion concentration in liquid-to-solid electrodeposition is neglected for a long time. Herein, the mechanism of concentration regulation in Zn electrodeposition is investigated in depth by combining electrochemical tests, post hoc characterization, and multiscale simulations. First, initial Zn electrodeposition is thermodynamically controlled epitaxial growth, whereas with the rapid depletion of ions, the concentration overpotential transcends the thermodynamic influence to kinetic control. Then, the evolution of the morphology from 2D sheets to 1D whiskers due to the concentration change is insightfully revealed by the morphological characterization and phase-field modeling. Furthermore, the depth of discharge (DOD) results in large concentration differences at the electrode-electrolyte interface, with a mild concentration distribution at lower DOD generating (002) crystal plane 2D sheets and a heavily varied concentration distribution at higher DOD yielding arbitrarily oriented 3D blocks. As a proof of concept, relaxation is introduced into two systems to homogenize the concentration distribution, revalidating the essential role of concentration in regulating electrodeposition, and two vital factors affecting the relaxation time, i.e., current density and electrode distance, are deeply investigated, demonstrating that the relaxation time is positively related to both and is more sensitive to the electrode distance. This work contributes to reacquainting aqueous batteries undergoing phase transitions and reveals a missing piece of the puzzle in regulating Zn electrodeposition.

A Holistic Additive Protocol Steers Dendrite-Free Zn(101) Orientational Electrodeposition.

Orientation guidance has shown its cutting edges in electrodeposition modulation to promote Zn anode stability toward commercialized standards. Nevertheless, large-scale orientational deposition is handicapped by the competition between Zn-ion reduction and mass transfer. Herein, a holistic electrolyte additive protocol is put forward via incorporating bio-derived dextrin molecules into a zinc sulfate electrolyte bath. Electrochemical tests in combination with molecular dynamics simulations demonstrate the alleviation of concentration polarization throughout accelerating Zn2+ diffusion and retarding their reduction. The predominant (101) texture on inert current collectors (i.e., Cu, Ti, and stainless steel) and (101)/(002) textures on Zn foils afford homogeneous electrical field distribution, which is contributed by the work difference to form the 2D nucleus and the adsorption of dextrin molecules, respectively. Consequently, the symmetric cell harvests a longevous cycling lifespan of over 4000 h at 0.5 mA cm-2 /0.5 mAh cm-2 while the Zn@Cu electrode sustains for 240 h at a high depth of discharge of 40%.

Direct Electrodeposition of Electrically Conducting Ni3(HITP)2 MOF Nanostructures for Micro-Supercapacitor Integration.

Micro-supercapacitors emerge as an important electrical energy storage technology expected to play a critical role in the large-scale deployment of autonomous microdevices for health, sensing, monitoring, and other IoT applications. Electrochemical double-layer capacitive storage requires a combination of high surface area and high electronic conductivity, with these being attained only in porous or nanostructured carbons, and recently found also in conducting metal-organic frameworks (MOFs). However, techniques for conformal deposition at micro- and nanoscale of these materials are complex, costly, and hard to upscale. Herein, the study reports direct, one step non-sacrificial anodic electrochemical deposition of Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 - Ni3(HITP)2, a porous and electrically conducting MOF. Employing this strategy enables the growth of Ni3(HITP)2 films on a variety of 2D substrates as well as on 3D nanostructured substrates to form Ni3(HITP)2 nanotubes and Pt@ Ni3(HITP)2 core-shell nanowires. Based on the optimal electrodeposition protocols, Ni3(HITP)2 films interdigitated micro-supercapacitors are fabricated and tested as a proof of concept.

A Reversible MnO2 Deposition-Enabled Multicolor Electrochromic Device with Efficient Tunability of Ultraviolet-Visible Light.

Electrochromic technology offers exciting opportunities for smart applications such as energy-saving and interactive systems. However, achieving dual-band regulation together with the multicolor function is still an unmet challenge for electrochromic devices. Herein, an ingenious electrochromic strategy based on reversible manganese oxide (MnO2) electrodeposition, different from traditional ion intercalation/deintercalation-type electrochromic materials is proposed. Such a deposition/dissolution-based MnO2 brings an intriguing electrochromic feature of dual-band regulation for the ultraviolet (UV) and visible lights with high optical modulation (93.2% and 93.6% at 400 and 550 nm, respectively) and remarkable optical memory. Moreover, a demonstrative smart window assembled by MnO2 and Cu electrodes delivers the electrochromic properties of effective dual-band regulation accompanied by multicolor changes (transparent, yellow, and brown). The robust redox deposition/dissolution process endows the MnO2-based electrochromic device with excellent rate capability and an areal capacity of 570 mAh m-2 at 0.1 mA cm-2. It is believed that the metal oxide-based reversible electrodeposition strategy would be an attractive and promising electrochromic technology and provide a train of thought for the development of multifunctional electrochromic devices and applications.

Electrochemical Deposition for Cultivating Nano- and Microstructured Electroactive Materials for Supercapacitors: Recent Developments and Future Perspectives.

The globe is currently dealing with serious issues related to the world economy and population expansion, which has led to a significant increase in the need for energy. One of the most promising energy devices for the next generation of energy technology is the supercapacitor (SC). Among the numerous nanostructured materials examined for SC electrodes, inorganic nanosheets are considered to be the most favorable electrode materials because of their excellent electrochemical performance due to their large surface area, very low layer thickness, and tunable diverse composition. Various inorganic nanosheets (NS) such as metal oxides, metal chalcogenides, metal hydroxides, and MXenes show substantial electrochemical activity. Herein, a comprehensive survey of inorganic NS arrays synthesized through the electrodeposition method is reported with the discussion on detailed growth mechanism and their application in the fabrication of SC electrodes/devices for powering flexible and wearable electronics appliances. To begin with, the first section will feature the various types of electrodeposition working mechanism, SC types and their working mechanisms, importance of nanosheet structure for SCs. This review gives a profound interpretation of supercapacitor electrode materials and their performances in different domains. Finally, a perspective on NS array through electrodeposition method applications in diverse fields is extensively examined.

In Situ Fast Construction of Ni3S4/FeS Catalysts on 3D Foam Structure Achieving Stable Large-Current-Density Water Oxidation.

By increasing the content of Ni3+, the catalytic activity of nickel-based catalysts for the oxygen evolution reaction (OER), which is still problematic with current synthesis routes, can be increased. Herein, a Ni3+-rich of Ni3S4/FeS on FeNi Foam (Ni3S4/FeS@FNF) via anodic electrodeposition to direct obtain high valence metal ions for OER catalyst is presented. XPS showed that the introduction of Fe not only further increased the Ni3+ concentration in Ni3S4/FeS to 95.02%, but also inhibited the dissolution of NiOOH by up to seven times. Furthermore, the OER kinetics is enhanced by the combination of the inner Ni3S4/FeS heterostructures and the electrochemically induced surface layers of oxides/hydroxides. Ni3S4/FeS@FNF shows the most excellent OER activity with a low Tafel slope of 11.2 mV dec-1 and overpotentials of 196 and 445 mV at current densities of 10 and 1400 mA cm-2, respectively. Furthermore, the Ni3S4/FeS@FNF catalyst can be operated stably at 1500 mA cm-2 for 200 h without significant performance degradation. In conclusion, this work has significantly increased the high activity Ni3+ content in nickel-based OER electrocatalysts through an anodic electrodeposition strategy. The preparation process is time-saving and mature, which is expected to be applied in large-scale industrialization.

Cs-treatments in Kesterite Thin-Film Solar Cells for Efficient Perovskite Tandems.

Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells are an attractive choice for a bottom cell of the low-cost and environmental tandem solar cells with perovskite. However, the progress in developing efficient perovskite/CZTSSe tandem solar cells has been hindered by the lack of high performance of the CZTSSe bottom cell. Here, an efficient CZTSSe bottom cell is demonstrated by adopting a facile and effective CsF treatment process. It is found that the CsF treatment not only facilitates grain growth and improves phase homogeneity by suppressing the detrimental deep-level defects and secondary phases, but also induces larger band bending and stronger drift force at the P-N junction. As a result, the carrier extraction/transport can be effectively accelerated, while reducing the interfacial recombination. These combined effects eventually result in a significant performance enhancement from 8.38% to 10.20%. The CsF-treated CZTSSe solar cell is finally applied to the mechanically-stacked perovskite/CZTSSe 4-terminal tandem cell by coupling a semi-transparent perovskite top cell, which exhibits the highest reported tandem efficiency of 23.01%.

Design Strategies toward High-Utilization Zinc Anodes for Practical Zinc-Metal Batteries.

Aqueous Zn-metal batteries (AZMBs) hold a promise as the next-generation energy storage devices due to their low cost and high specific energy. However, the actual energy density falls far below the requirements of commercial AZMBs due to the use of excessive Zn as anode and the associated issues including dendritic growth and side reactions. Reducing the N/P ratio (negative capacity/positive capacity) is an effective approach to achieve high energy density. A significant amount of research has been devoted to increasing the cathode loading and specific capacity or tuning the Zn anode utilization to achieve low N/P ratio batteries. Nevertheless, there is currently a lack of comprehensive overview regarding how to enhance the utilization of the Zn anode to balance the cycle life and energy density of AZMBs. In this review, we summarize the challenges faced in achieving high-utilization Zn anodes and elaborate on the modifying strategies for the Zn anode to lower the N/P ratio. The current research status and future prospects for the practical application of high-performance AZMBs are proposed at the end of the review.

Recent Developments in Electrodeposition of Transition Metal Chalcogenides-Based Electrode Materials for Advance Supercapacitor Applications: A Review.

High-performance supercapacitive electrode materials have received significant attention from researchers worldwide, thus aiming for comparable performance similar to the extensively used rechargeable batteries. For emerging energy storage technologies like flexible supercapacitors, transition metal chalcogenides (TMCs) have been in the spotlight due to their promising electrochemical features compared to other electrode materials. Among the synthesis techniques, electrodeposition-mediated preparation of thin films of TMCs offered an affordable binder-free approach for electrode fabrication that effectively improved the supercapacitor performance. Hence, this review mainly focussed on the electrodeposition-based syntheses of single/ multinary chalcogenides and their composites for supercapacitors applications. Further, the effects of different deposition parameters were discussed for boosting the supercapacitor performance. Finally, this review outlined the existing challenges and future perspectives in this research domain, which will assist the upcoming exploration in the energy storage field.

Density-controlled electrochemical synthesis of ZnO nanowire arrays using nanotextured cathode.

Zinc oxide (ZnO) nanowires fabricated via wet chemical synthesis on flexible polymer substrates are inherently unstable against mechanical bending stress because of their high density and weak adhesion to the substrate. We introduce a novel method for controlling the density of such ZnO nanowire arrays using a three-dimensional corrugated metal substrate. These metal substrates, featuring extruded and recessed patterns fabricated via nanoimprint lithography, were employed as cathodes during the electrochemical deposition of ZnO nanowire arrays. The ZnO nanowire arrays synthesized on the patterned metal thin film exhibited smaller diameters and lower densities compared to those on non-patterned metal films. This reduction in density can be attributed to aligned nucleation and limited growth on the patterned metal surface. Crucially, ZnO nanowires synthesized on patterned metal substrates displayed remarkable mechanical robustness against external forces, a direct consequence of their reduced density. In contrast, nanowires synthesized on non-patterned metal substrates were broken under mechanical bending. Detailed morphological analyses performed after mechanical bending tests confirm that ZnO nanowires synthesized on nanoimprinted metal electrodes exhibited enhanced mechanical characteristics compared to those on non-patterned metal electrodes. These findings clearly demonstrate the promise of utilizing density-controlled ZnO nanowires in piezoelectric devices.

Proving the automatic benchtop electrochemical station for the development of dopamine and paracetamol sensors.

The introduced work represents an implementation of the automatic benchtop electrochemical station (BES) as an effective tool for the possibilities of high-throughput preparation of modified sensor/biosensors, speeding up the development of the analytical method, and automation of the analytical procedure for the determination of paracetamol (PAR) and dopamine (DOP) as target analytes. Within the preparation of gold nanoparticles modified screen-printed carbon electrode (AuNPs-SPCE) by electrodeposition, the deposition potential EDEP, the deposition time tDEP, and the concentration of HAuCl4 were optimized and their influence was monitored on 1 mM [Ru(NH3)6]3+/2+ redox probe and 50 µM DOP. The morphology of the AuNPs-SPCE prepared at various modification conditions was observed by SEM. The analytical performance of the AuNPs-SPCE prepared at different modification conditions was evaluated by a construction of the calibration curves of DOP and PAR. SPCE and AuNPs-SPCE at modification condition providing the best sensitivity to PAR and DOP, were successfully used to determine PAR and DOP in tap water by "spike-recovery" approach. The BES yields better reproducibility of the preparation of AuNPs-SPCE (RSD = 3.0%) in comparison with the case when AuNPs-SPCE was prepared manually by highly skilled laboratory operator (RSD = 7.0%).

Position Feedback-Control of an Electrothermal Microactuator Using Resistivity Self-Sensing Technique.

The self-sensing technology of microactuators utilizes a smart material to concurrently actuate and sense in a closed-loop control system. This work aimed to develop a position feedback-control system of nickel electrothermal microactuators using a resistivity self-sensing technique. The system utilizes the change in heating/sensing elements' resistance, due to the Joule heat, as the control parameter. Using this technique, the heating/sensing elements would concurrently sense and actuate in a closed loop control making the structures of microactuators simple. From a series of experiments, the proposed self-sensing feedback control system was successfully demonstrated. The tip's displacement error was smaller than 3 µm out of the displacement span of 60 µm. In addition, the system was less sensitive to the abrupt temperature change in surroundings as it was able to displace the microactuator's tip back to the desired position within 5 s, which was much faster than a feed-forward control system.

Enhancing the Deposition Rate and Uniformity in 3D Gold Microelectrode Arrays via Ultrasonic-Enhanced Template-Assisted Electrodeposition.

In the pursuit of refining the fabrication of three-dimensional (3D) microelectrode arrays (MEAs), this study investigates the application of ultrasonic vibrations in template-assisted electrodeposition. This was driven by the need to overcome limitations in the deposition rate and the height uniformity of microstructures developed using conventional electrodeposition methods, particularly in the field of in vitro electrophysiological investigations. This study employs a template-assisted electrodeposition approach coupled with ultrasonic vibrations to enhance the deposition process. The method involves utilizing a polymeric hard mask to define the shape of electrodeposited microstructures (i.e., micro-pillars). The results show that the integration of ultrasonic vibrations significantly increases the deposition rate by up to 5 times and substantially improves the uniformity in 3D MEAs. The key conclusion drawn is that ultrasonic-enhanced template-assisted electrodeposition emerges as a powerful technique and enables the development of 3D MEAs at a higher rate and with a superior uniformity. This advancement holds promising implications for the precision of selective electrodeposition applications and signifies a significant stride in developing micro- and nanofabrication methodologies for biomedical applications.

Influence of Double-Pulse Electrodeposition Parameters on the Performance of Ag/AgCl Electrochemical Electrode for Marine Electric Field.

This paper describes a Ag/AgCl electrochemical electrode for marine electric field measurements, which was prepared by depositing silver chloride on a silver foil substrate using double-pulse electrodeposition. The impact of positive direction peak current density and deposition time on electrode performance in the preparation of Ag/AgCl electrodes through double-pulse electrodeposition was investigated. Scanning electron microscopy and voltammetry have been used to study the properties of the prepared electrodes. This work reveals the correlation between the electrochemical behavior of electrodes and the physical properties of their surfaces, especially specific surface area and porosity. The study verified the characteristics of Ag/AgCl marine electric field electrodes obtained with different pulse parameters by analyzing the potential stability and noise level of the electrode in salt water. The study's results have positive significance for improving the accuracy of marine electric field measurements.

Production of Noble-Metal Nanohelices Based on Nonlinear Dynamics in Electrodeposition of Binary Copper Alloys.

Spatiotemporal pattern formation is dynamic self-organization widely observed in nature and drives various functions. Among these functions, chirality plays a central role. The relationship between dynamic self-organization and chirality has been an open question; therefore, the production of chiral nanomaterials by dynamic self-organization has not been achieved. Here, we show that the confinement of a two-dimensional spatiotemporal micropattern via the electrodeposition of a binary Cu alloy into a nanopore induces mirror symmetry breaking to produce a helical nanostructure of the noble-metal component although it is still not yet possible to control the handedness at this stage. This result suggests that spatiotemporal symmetry breaking functions as a mirror symmetry breaking if cylindrical pores are given as the boundary condition. This study can be a model system of how spatiotemporal symmetry breaking plays a role in mirror symmetry breaking, and it proposes a new approach to producing helical nanomaterials through dynamic self-organization.

Efficient Delivery of Biological Cargos into Primary Cells by Electrodeposited Nanoneedles via Cell-Cycle-Dependent Endocytosis.

Nanoneedles are a useful tool for delivering exogenous biomolecules to cells. Although therapeutic applications have been explored, the mechanism regarding how cells interact with nanoneedles remains poorly studied. Here, we present a new approach for the generation of nanoneedles, validated their usefulness in cargo delivery, and studied the underlying genetic modulators during delivery. We fabricated arrays of nanoneedles based on electrodeposition and quantified its efficacy of delivery using fluorescently labeled proteins and siRNAs. Notably, we revealed that our nanoneedles caused the disruption of cell membranes, enhanced the expression of cell-cell junction proteins, and downregulated the expression of transcriptional factors of NFκB pathways. This perturbation trapped most of the cells in G2 phase, in which the cells have the highest endocytosis activities. Taken together, this system provides a new model for the study of interactions between cells and high-aspect-ratio materials.

Molybdenum-Modified Titanium Dioxide Nanotube Arrays as an Efficient Electrode for the Electroreduction of Nitrate to Ammonia.

Electrochemical nitrate reduction (NO3-RR) has been recognized as a promising strategy for sustainable ammonia (NH3) production due to its environmental friendliness and economical nature. However, the NO3-RR reaction involves an eight-electron coupled proton transfer process with many by-products and low Faraday efficiency. In this work, a molybdenum oxide (MoOx)-decorated titanium dioxide nanotube on Ti foil (Mo/TiO2) was prepared by means of an electrodeposition and calcination process. The structure of MoOx can be controlled by regulating the concentration of molybdate during the electrodeposition process, which can further influence the electron transfer from Ti to Mo atoms, and enhance the binding energy of intermediate species in NO3-RR. The optimized Mo/TiO2-M with more Mo(IV) sites exhibited a better activity for NO3-RR. The Mo/TiO2-M electrode delivered a NH3 yield of 5.18 mg h-1 cm-2 at -1.7 V vs. Ag/AgCl, and exhibited a Faraday efficiency of 88.05% at -1.4 V vs. Ag/AgCl. In addition, the cycling test demonstrated that the Mo/TiO2-M electrode possessed a good stability. This work not only provides an attractive electrode material, but also offers new insights into the rational design of catalysts for NO3-RR.

Electrografting of Phenyl Phosphate Layers onto Glassy Carbon for Tuning Catalytic Activity toward the Hydrogen Evolution Reaction.

In this study, we explored the surface modification of a glassy carbon electrode through the electrografting of 4-Aminophenyl phosphate, which features heteroatoms and ionic properties. The electrochemical grafting process involves reducing in situ-generated diazonium derivatives. The primary objective of this research was to immobilize organic layers and assess their electrochemical and surface properties. Subsequently, the generated surface serves as a template for the electrochemical growth of Pd and Co nanoparticles on functionalized electrodes. The electrocatalytic performances of these hybrid electrodes in driving the hydrogen evolution reaction were investigated. The obtained results indicate an enhancement in the electrocatalytic activity of the modified electrodes, where lower overpotential and higher stability were observed when the catalyst was electrodeposited onto the attached ionic layer. These findings highlight the synergistic effect between the attached phenyl phosphate moieties and electrocatalysts.