Silica-Derived Nanostructured Electrode Materials for ORR, OER, HER, CO2RR Electrocatalysis, and Energy Storage Applications: A Review.

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords "silica", "electrocatalysts", "ORR", "OER", "HER", "HOR", "CO2RR", "batteries", and "supercapacitors". The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

One-Pot Synthesis of Melamine Formaldehyde Resin-Derived N-Doped Porous Carbon for CO2 Capture Application.

The design and synthesis of porous carbons for CO2 adsorption have attracted tremendous interest owing to the ever-soaring concerns regarding climate change and global warming. Herein, for the first time, nitrogen-rich porous carbon was prepared with chemical activation (KOH) of commercial melamine formaldehyde resin (MF) in a single step. It has been shown that the porosity parameters of the as-prepared carbons were successfully tuned by controlling the activating temperature and adjusting the amount of KOH. Thus, as-prepared N-rich porous carbon shows a large surface area of 1658 m2/g and a high N content of 16.07 wt%. Benefiting from the unique physical and textural features, the optimal sample depicted a CO2 uptake of up to 4.95 and 3.30 mmol/g at 0 and 25 °C under 1 bar of pressure. More importantly, as-prepared adsorbents show great CO2 selectivity over N2 and outstanding recyclability, which was prominently important for CO2 capture from the flue gases in practical application. An in-depth analysis illustrated that the synergetic effect of textural properties and surface nitrogen decoration mainly determined the CO2 capture performance. However, the textural properties of carbons play a more important role than surface functionalities in deciding CO2 uptake. In view of cost-effective synthesis, outstanding textural activity, and the high adsorption capacity together with good selectivity, this advanced approach becomes valid and convenient in fabricating a unique highly efficient N-rich carbon adsorbent for CO2 uptake and separation from flue gases.

Microdroplet-Based Potentiometric Redox Measurements on Gold Nanoporous Electrodes.

Potentiometric redox measurements were made in subnanoliter droplets of solutions using an optically transparent nanoporous gold electrode strategically mounted on the stage of an inverted microscope. Nanoporous gold was prepared via dealloying gold leaf with concentrated nitric acid and was chemisorbed to a standard microscope coverslip with (3-mercaptopropyl)trimethoxysilane. The gold surface was further modified with 1-hexanethiol to optimize hydrophobicity of the surface to allow for redox measurements to be made in nanoscopic volumes. Time traces of the open-circuit potential (OCP) were used to construct Nernst plots to evaluate the applicability of the droplet-based potentiometric redox measurement system. Two poised one-electron transfer systems (potassium ferricyanide/ferrocyanide and ferrous/ferric ammonium sulfate) yielded Nernstian slopes of -58.5 and -60.3 mV, respectively, with regression coefficients greater than 0.99. The y-intercepts of the two agreed well to the formal potential of the two standard oxidation-reduction potential (ORP) calibrants, ZoBell's and Light's solution. The benzoquinone and hydroquinone redox couple was examined as a representative two-electron redox system; a Nernst slope of -30.8 mV was obtained. Additionally, two unpoised systems (potassium ferricyanide and ascorbic acid) were studied to evaluate the system under conditions where only one form of the redox couple is present in appreciable concentrations. Again, slopes near the Nernstian values of -59 and -29 mV, respectively, were obtained. All experiments were carried out using solution volumes between 280 and 1400 pL with injection volumes between 8 and 100 pL. The miniscule volumes allowed for extremely rapid mixing (<305 ms) as well. The small volumes and rapid mixing along with the high accuracy and sensitivity of these measurements lend support to the use of this approach in applications where time is a factor and only small volumes are available for testing.

Mesoporous Hybrid Polypyrrole-Silica Nanocomposite Films with a Strata-Like Structure.

Using a single-potential-step coelectrodeposition route, Ppy-SiO2 nanocomposite films characterized by a multimodal porous structure were cathodically deposited from ethanolic solutions on oxidizable and nonoxidizable substrates for the first time. The materials produced have an interesting and unique strata-like pore structure along their depth. With the exception of a silica-rich inner region, the nanocomposite films are homogeneous in composition. Because the region closest to the electrode surface is silica-rich, the fabrication of Ppy-SiO2 and Ppy free-standing films become possible using a multistep etching strategy. Such films can be captured on a variety of different supports depending on the application, and they maintain their conductivity when interfaced with an electrode surface. These mesoporous composite films form through a unique mechanism that involves the production of two catalysts, OH(-) and NO(+). Through the process of understanding the reaction mechanism, we highlighted the effect of two simultaneous competing redox reactions occurring at the electrode interface on the morphology of the electrodeposited Ppy nanocomposite films and how solvent can influence the Ppy electropolymerization reaction mechanism and hence control the morphology of the final material. In an ethanolic solvent system, the pyrrole monomers undergo a step-growth polymerization, and particulate-like nanostructured films were obtained even upon changing the monomer or acid concentration. In an aqueous-based system, nanowire-like structures were produced, which is consistent with a chain-growth mechanism. Such materials are promising candidates for a wide range of applications including electrochemical sensing, energy storage, and catalysis.

Monoclinic Hydroxyapatite Nanoplates Hybrid Composite with Improved Compressive Strength, and Porosity for Bone Defect Repair: Biomimetic Synthesis and Characterization.

Calcium phosphate cement (CPC) has been used for bone restoration despite its intrinsic fragile property. In order to enhance the CPC mechanical properties, biopolymers were introduced as filler to prepare CPC based cements. Chitosan/tetracalcium phosphate (TTCP)/dicalcium phosphate anhydrous (DCPA) based cement for bone repair has been prepared in the study. Solidification of the prepared cement was carried out in a simulate body fluid at 37 degrees C. The introduction of chitosan improved the mechanical performance of the as-prepared CPC hybrid nanocomposite. FTIR, SEM, TEM, HRTEM, XRD, and SAED were used to characterize the CPC nanocomposite. Data simulations have been performed to assist in determining the crystalline phase/s in the CPC hybrid nanocomposite. Based on the SAED, HRTEM measurements and data simulations, a monoclinic phase of hydroxyapatite (HAP) with a plate-like structure was obtained in the CPC system, which is believed to be responsible for the observed enhancement in CPC mechanical properties. The obtained composite has a biocompatibility comparable to that of commercial sample.

Electroassisted codeposition of sol-gel derived silica nanocomposite directs the fabrication of coral-like nanostructured porous gold.

Herein, we report on a one-step coelectrodeposition method to form gold-silica nanocomposite materials from which high surface area nanostructured gold electrodes can be produced. The as-prepared Au-SiO2 films possess an interconnected three-dimensional porous framework with different silica-gold ratios depending on the deposition solutions and parameters. Chemical etching of the nanocomposite films using hydrofluoric acid resulted in the formation of nanostructured porous gold films with coral-like structures and pores in the nanometer range. The cross-linkage of the gold coral branches resulted in the generation of a porous framework. X-ray photoelectron spectroscopy confirms the complete removal of silica. Well-controlled surface area enhancement, film thickness, and morphology were achieved by manipulating the deposition parameters, such as potential, time, and gold ion and sol-gel monomer concentrations in the deposition solution. An enhancement in the surface area of the electrode up to 57 times relative to the geometric area has been achieved. The thickness of the as-prepared Au-SiO2 nanocomposite films is relatively high and varied from 8 to 15 µm by varying the applied deposition potential while the thickness of the coral-like nanostructured porous gold films ranged from 0.22 to 2.25 µm. A critical sol-gel monomer concentration (CSGC) was determined at which the deposited silica around the gold coral was able to stabilize the coral-like gold nanostructures, while below the CSGC, the coral-like gold nanostructures were unstable and the surface area of the nanostructured porous gold electrodes decreased.

Biofouling-Resistant Platinum Bimetallic Alloys.

A new electrosynthetic approach for the fabrication of three-dimensional bicontinuous nanoporous platinum-based (3D-BC-NP-Pt(Au)) electrodes is described. Binary Pt-Ag alloys are first electrodeposited on gold substrates from appropriately formulated plating solutions. Following annealing and dealloying, a new family of nanoporous platinum-based electrodes emerges whose morphology, porosity, and chemical compositions depend on electrodeposition parameters and plating solution composition. Scanning electron microscopy images reveal an interesting and distinctive nanoporous gold-like microstructure with pores and ligaments in the 10-30 nm range arranged in a bicontinuous fashion throughout the thickness of the film. X-ray photoelectron spectroscopy (XPS) confirms that the as-formed electrodeposited films are silver-rich platinum binary alloys. Interestingly, XPS also reveals that after annealing and dealloying, the electrodes are actually ternary alloys containing platinum, gold, and a small amount of residual silver that remains after dealloying. Electrochemical measurements are consistent with this result and disclose a high surface area with roughness factors of 15-24. The ability to successfully conduct electrochemical measurements in biofouling solutions via a unique biosieving-like mechanism is demonstrated by exposure of the unique 3D bicontinuous nanoporous platinum-based electrode to fibrinogen in phosphate buffer and in a solution containing red blood cells. The work described herein has the potential to enrich the fields of electrochemical sensing and biosensing via the introduction of new 3D bicontinuous nanostructured porous platinum-based electrodes that can be easily and reliably fabricated.

Conducting polymer-silk biocomposites for flexible and biodegradable electrochemical sensors.

Approaches to form flexible biosensors require strategies to tune materials for various biomedical applications. We report a facile approach using photolithography to fabricate poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) ( PEDOT: PSS) sensors on a fully biodegradable and flexible silk protein fibroin support. A benchtop photolithographic setup is used to fabricate high fidelity and high resolution PEDOT: PSS microstructures over a large (cm) area using only water as the solvent. Using the conductive micropatterns as working electrodes, we demonstrate biosensors with excellent electrochemical activity and stability over a number of days. The fabricated biosensors display excellent nonspecific detection of dopamine and ascorbic acid with high sensitivity. These devices are mechanically flexible, optically transparent, electroactive, cytocompatible and biodegradable. The benign fabrication protocol allows the conducting ink to function as a matrix for enzymes as shown by a highly sensitive detection of glucose. These sensors can retain their properties under repeated mechanical deformations, but are completely degradable under enzymatic action. The reported technique is scalable and can be used to develop sensitive, robust, and inexpensive biosensors with controllable biodegradability, leading to applications in transient or implantable bioelectronics and optoelectronics.

Photolithographic Micropatterning of Conducting Polymers on Flexible Silk Matrices.

High-resolution micropatterning of a PEDOT: PSS conducting-polymer-silksericin composite is presented using a water-based, benchtop photolithographic process. Conducting microstructures formed on a flexible silk fibroin sheet allow a fully organic, flexible bioelectronic device. Large-area microfabricated devices such as biosensors that are biocompatible and degradable over a controlled period of time can be formed.