membraneless-hydrogen-peroxide-fuel-cells-as-promising-clean-energy

Membraneless Hydrogen Peroxide Fuel Cells as a Promising Clean Energy Source

In an in-depth investigation of membraneless hydrogen peroxide-based fuel cells (H2O2 FCs), hydrogen peroxide (H2O2), a carbon-neutral compound, is ...

Fudan University

In this tutorial review we describe the recent progress on catalytic microtubular engines fabricated by rolled-up nanotech on polymers. We summarize the technical aspects of the technology and the basic principles that cause the catalytic microengines to self-propel in fuel solutions. The control over speed, directionality and interactions of the microengines to perform tasks such as cargo transportation is also discussed. We compare this technology to other fabrication techniques of catalytic micro-/nanomotors and outline challenges and opportunities for such engines in future studies. Since rolled-up nanotech on polymers can easily integrate almost any type of inorganic material, huge potential and advanced performance such as high speed, cargo delivery, motion control, and dynamic assembly are foreseen--ultimately promising a practical way to construct versatile and intelligent catalytic tubular microrobots.

Rolled-up nanotech on polymers: from basic perception to self-propelled catalytic microengines.

Site-selective growth on non-spherical seeds provides an indispensable route to hierarchical complex nanostructures that are interesting for diverse applications. However, this has only been achieved through epitaxial growth, which is restricted to crystalline materials with similar crystal structures and physicochemical properties. A non-epitaxial growth strategy is reported for hierarchical nanostructures, where site-selective growth is controlled by the curvature of non-spherical seeds. This strategy is effective for site-selective growth of silica nanorods from non-spherical seeds of different shapes and materials, such as α-Fe O , NaYF , and ZnO. This growth strategy is not limited by the stringent requirements of epitaxy and is thus a versatile general method suitable for the preparation of hierarchical nanostructures with controlled morphologies and compositions to open up a verity of applications in self-assembly, nanorobotics, catalysis, electronics, and biotechnology.

Local-Curvature-Controlled Non-Epitaxial Growth of Hierarchical Nanostructures.

We demonstrate a new type of gaseous fuel for rolled-up tubular Ti/Cr microengine powered by carbon dioxide microbubbles in carbonated water and brewed beverages. Existence of microbubble pockets is revealed using on-chip integrated transparent microtubes. Vertical position, angle of rotation and buoyancy of ferromagnetic Ti/Fe/Cr microengines are controlled using an external magnetic field.

Carbon dioxide bubble-propelled microengines in carbonated water and beverages.

Discovery of bio-inspired, self-propelled and externally-powered nano-/micro-motors, rotors and engines (micromachines) is considered a potentially revolutionary paradigm in nanoscience. Nature knows how to combine different elements together in a fluidic state for intelligent design of nano-/micro-machines, which operate by pumping, stirring, and diffusion of their internal components. Taking inspirations from nature, scientists endeavor to develop the best materials, geometries, and conditions for self-propelled motion, and to better understand their mechanisms of motion and interactions. Today, microfluidic technology offers considerable advantages for the next generation of biomimetic particles, droplets and capsules. This review summarizes recent achievements in the field of nano-/micromotors, and methods of their external control and collective behaviors, which may stimulate new ideas for a broad range of applications.

Geometry Design, Principles and Assembly of Micromotors.

Methacrylic anhydride-derived hydrogel microcapsules have unique properties, including reversibly tunable permeation, purification, and separation of dissolved molecular species. Endowing these dynamic encapsulant systems with autonomous motion will significantly enhance their efficiency and applicability. Here, hydrogel micromotors are realized using complex water-in-oil-in-water double emulsion drops and oil-in-water emulsion drops from glass capillary microfluidics and subsequent photopolymerization. Three hydrogel micromotor strategies are explored: microcapsules with thin shells and liquid cores with dispersed catalytic Pt nanoparticles, as well as water-cored microcapsules and homogeneous microparticles selectively coated with Ti/Pt catalytic layers. Autonomous motion of hydrogel particles and capsules is realized in hydrogen peroxide solutions, where generated oxygen microbubbles propel the dynamically responsive micromotors. The micromotors are balanced by weight, buoyancy, lateral capillary forces and show specific autonomous behaviours that significantly extend short range dynamic responses of hydrogels. Drop-based microfluidics represent a paradigm shift in the integration of multifunctional subsystems and high-throughput design of chemical micromachines in reasonable quantities towards their desired biomedical, environmental and flow/diffusion microreactor applications.

Hydrogel micromotors with catalyst-containing liquid core and shell.

Rolled-up catalytic Ti/Cr/Pt microtubes, consisting of inorganic nanomembranes integrated on-chip, are used to generate oxygen microbubbles in solutions of hydrogen peroxide. Oxygen bubble parameters (frequency, radius and volumetric flow rate) are optimized at different concentrations of hydrogen peroxide and common dish soap. Increasing the aspect ratio of the microtube (e.g., tube length/diameter) leads to the formation of smaller bubbles, but at higher frequencies. Longer tubes produce less total oxygen volume in comparison to shorter tubes. We attribute this observation to the specific dynamic behaviours of bubbles in tubes.

Oxygen Microbubble Generator Enabled by Tunable Catalytic Microtubes.

A controllable generation of oxygen gas during the decomposition of hydrogen peroxide by the microreactors made of tubular catalytic nanomembranes has recently attracted considerable attention. Catalytic microtubes play simultaneous roles of the oxygen bubble producing microreactors and oxygen bubble-driven micropumps. An autonomous pumping of peroxide fuel takes place through the microtubes by the recoiling microbubbles. Due to optimal reaction-diffusion processes, gas supersaturation, leading to favorable bubble nucleation conditions, strain-engineered catalytic microtubes with longer length produce oxygen microbubbles at concentrations of hydrogen peroxide in approximately ×1000 lower in comparison to shorter tubes. Dynamic regimes of tubular nanomembrane-based oxygen microbubble generators reveal that this depends on microtubes' aspect ratio, hydrogen peroxide fuel concentration and fuel compositions. Different dynamic regimes exist, which produce specific bubble frequencies, bubble size and various amounts of oxygen. In this study, the rolled-up Ti/Cr/Pd microtubes integrated on silicon substrate are used to study oxygen evolution in different concentrations of hydrogen peroxide and surfactants. Addition of Sodium dodecyl sulfate (SDS) surfactants leads to a decrease of bubble diameter and an increase of frequencies of bubble recoil. Moreover, an increase of temperature (from 10 to 35 °C) leads to higher frequencies of oxygen bubbles and larger total volumes of produced oxygen.

Parameters Optimization of Catalytic Tubular Nanomembrane-Based Oxygen Microbubble Generator.

Microbubbles have already reached clinical practice as ultrasound contrast agents for angiography. However, modification of the bubbles' shell is needed to produce probes for ultrasound and multimodal (fluorescence/photoacoustic) imaging methods in combination with theranostics (diagnostics and therapeutics). In the present work, hybrid structures based on microbubbles with an air core and a shell composed of bovine serum albumin, albumin-coated gold nanoparticles, and clinically available photodynamic dyes (zinc phthalocyanine, indocyanine green) were shown to achieve multimodal imaging for potential applications in photodynamic therapy. Microbubbles with an average size of 1.5 ± 0.3 μm and concentration up to 1.2 × 10 microbubbles/mL were obtained and characterized. The introduction of the dye into the system reduced the solution's surface tension, leading to an increase in the concentration and stability of bubbles. The combination of gold nanoparticles and photodynamic dyes' influence on the fluorescent signal and probes' stability is described. The potential use of the obtained probes in biomedical applications was evaluated using fluorescence tomography, raster-scanning optoacoustic microscopy and ultrasound response measurements using a medical ultrasound device at the frequency of 33 MHz. The results demonstrate the impact of microbubbles' stabilization using gold nanoparticle/photodynamic dye hybrid structures to achieve probe applications in theranostics.

Air-Filled Bubbles Stabilized by Gold Nanoparticle/Photodynamic Dye Hybrid Structures for Theranostics.

Wireless nano-/micromotors powered by chemical reactions and/or external fields generate motive forces, perform tasks, and significantly extend short-range dynamic responses of passive biomedical microcarriers. However, before micromotors can be translated into clinical use, several major problems, including the biocompatibility of materials, the toxicity of chemical fuels, and deep tissue imaging methods, must be solved. Nanomaterials with enzyme-like characteristics (e.g., catalase, oxidase, peroxidase, superoxide dismutase), that is, nanozymes, can significantly expand the scope of micromotors' chemical fuels. A convergence of nanozymes, micromotors, and microfluidics can lead to a paradigm shift in the fabrication of multifunctional micromotors in reasonable quantities, encapsulation of desired subsystems, and engineering of FDA-approved core-shell structures with tuneable biological, physical, chemical, and mechanical properties. Microfluidic methods are used to prepare stable bubbles/microbubbles and capsules integrating ultrasound, optoacoustic, fluorescent, and magnetic resonance imaging modalities. The aim here is to discuss an interdisciplinary approach of three independent emerging topics: micromotors, nanozymes, and microfluidics to creatively: 1) embrace new ideas, 2) think across boundaries, and 3) solve problems whose solutions are beyond the scope of a single discipline toward the development of micro-bio-chemo-mechanical-systems for diverse bioapplications.

Micro-Bio-Chemo-Mechanical-Systems: Micromotors, Microfluidics, and Nanozymes for Biomedical Applications.

Microbubbles are intravascular contrast agents clinically used in diagnostic sonography, echocardiography, and radiology imaging applications. However, up to date, the idea of creating microbubbles with multiple functionalities (e.g., multimodal imaging, photodynamic therapy) remained a challenge. One possible solution is the modification of bubble shells by introducing specific compounds responsible for such functions. In the present work, air-core microbubbles with the shell consisting of bovine serum albumin, albumin-coated gold nanocages, and zinc phthalocyanine were prepared using the sonication method. Various physicochemical parameters such as stability over time, size, and concentration were investigated to prove the potential use of these microbubbles as contrast agents. This work shows that hybrid microbubbles have all the necessary properties for multimodal imaging (ultrasound, raster-scanning microscopy, and fluorescence tomography), which demonstrate superior characteristics for potential theranostic and related biomedical applications.

Air-Filled Microbubbles Based on Albumin Functionalized with Gold Nanocages and Zinc Phthalocyanine for Multimodal Imaging.

Gaseous oxygen plays a vital role in driving the metabolism of living organisms and has multiple agricultural, medical, and technological applications. Different methods have been discovered to produce oxygen, including plants, oxygen concentrators and catalytic reactions. However, many such approaches are relatively expensive, involve challenges, complexities in post-production processes or generate undesired reaction products. Catalytic oxygen generation using hydrogen peroxide is one of the simplest and cleanest methods to produce oxygen in the required quantities. Chemically powered micro/nanomotors, capable of self-propulsion in liquid media, offer convenient and economic platforms for on-the-fly generation of gaseous oxygen on demand. Micromotors have opened up opportunities for controlled oxygen generation and transport under complex conditions, critical medical diagnostics and therapy. Mobile oxygen micro-carriers help better understand the energy transduction efficiencies of micro/nanoscopic active matter by careful selection of catalytic materials, fuel compositions and concentrations, catalyst surface curvatures and catalytic particle size, which opens avenues for controllable oxygen release on the level of a single catalytic microreactor. This review discusses various micro/nanomotor systems capable of functioning as mobile oxygen generators while highlighting their features, efficiencies and application potentials in different fields.

Oxygen Generation Using Catalytic Nano/Micromotors.

Nano/-micromotors self-assembling into static and dynamic clusters are of considerable promise to study smart, interactive, responsive, and adaptive nano/-micromaterials that can mimic spatio-temporal patterns, swarming, and collective behaviors widely observed in nature. Previously, the dynamic self-assembly of bubble-propelled catalytic micromotors initiated by capillary forces has been reported. This manuscript shows novel self-assembly modes of magnetic/catalytic Ti/FeNi/Pt tubular micromotors. When chemical fuel (hydrogen peroxide) is added it is decomposed on contact with Pt catalyst into oxygen and water. Here, the non-bubbling motion and autonomous assembly of catalytic/magnetic nanomembranes,  without nucleation/generation of oxygen bubbles, are shown. Moreover, magnetic Ti/FeNi/Pt micromotors are spun using an external magnetic field and they form dynamic clusters balanced by attractive magnetic and repulsive hydrodynamic interactions. Micromotors form dynamic clusters, undergo precession and rapidly propagate through the solution.

Catalytic/magnetic assemblies of rolled-up tubular nanomembrane-based micromotors.

In this work, UV light-controlled two-dimensional (2D) TiO plate micromotors are demonstrated for the first time. The 2D TiO micromotors are produced by the well-known anodic oxidation method in combination with a cracking and separation process. When the motor is placed in HO aqueous solution under UV irradiation, oxygen bubbles are generated in the holes of the TiO membrane. The 2D micromotor thus moves upon O bubbles under its own weight. In contrast to bubble-propelled micromotors, which require an addition of surfactants to chemical fuels, the 2D micromotor is capable of moving in aqueous HO solution without surfactants. Moreover, speed of the 2D TiO micromotor can be controlled by the intensity of the UV light. Such surfactant-free micromotors and their facile fabrication hold considerable promise for diverse practical applications in the biomedical and energy fields, for example, and in new materials.

Light-controlled two-dimensional TiO plate micromotors.

Gas-liquid interfaces are reaching a particular interest in biomedicine. Microbubbles, ultrasound contrast agents of clinical routine, gained increasing attention as theranostic platforms due to the preserved acoustic response, drug conjugation capabilities, and applicability in biological barrier opening. A combination of microbubbles and photodynamic therapy agents can enhance the photodynamic effect, yet the evaluation of agent conjugation on microbubble stabilization and photodynamic effect is needed. Hence, two commercially available phthalocyanine photosensitizers - Holosens® (ZnPc) and Photosens® (AlPc) - were coupled with bovine serum albumin before microbubble synthesis. We demonstrated an albumin: phthalocyanine ratio of 1:1 and covalent attachment for ZnPc, a ratio of 1:3 with electrostatic binding for AlPc. Submicron-sized microbubbles (air- and SF- filled) had a diameter of 0.8 µm. Albumin-phthalocyanine conjugates increased the microbubble concentration and shelf-life stability compared to plain ones. We hypothesized that phthalocyanine fluorescence lifetime values decreased after conjugation with microbubbles due to narrow distance between conjugates in the shell. Agents based on AlPc demonstrated higher photodynamic activity than agents based on ZnPc, and microbubbles preserved acoustic stability in human blood plasma. The biodistribution of AlPc-conjugated microbubbles was evaluated. We conclude that our microbubble platforms demonstrate greater photodynamic activity and prolonged stability for further applications in photodynamic therapy.

Article	Year
Rolled-up nanotech on polymers: from basic perception to self-propelled catalytic microengines. Chemical Society reviews\| PubMed ID: 21340080	2011
Local-Curvature-Controlled Non-Epitaxial Growth of Hierarchical Nanostructures. Angewandte Chemie (International ed. in English)\| PubMed ID: 29415319	2018
Carbon dioxide bubble-propelled microengines in carbonated water and beverages. Chemical communications (Cambridge, England)\| PubMed ID: 29662979	2018
Geometry Design, Principles and Assembly of Micromotors. Micromachines\| PubMed ID: 30393351	2018
Hydrogel micromotors with catalyst-containing liquid core and shell. Journal of physics. Condensed matter : an Institute of Physics journal\| PubMed ID: 30777936	2019
Oxygen Microbubble Generator Enabled by Tunable Catalytic Microtubes. Chemistry, an Asian journal\| PubMed ID: 31087618	2019
Parameters Optimization of Catalytic Tubular Nanomembrane-Based Oxygen Microbubble Generator. Micromachines\| PubMed ID: 32610688	2020
Air-Filled Bubbles Stabilized by Gold Nanoparticle/Photodynamic Dye Hybrid Structures for Theranostics. Nanomaterials (Basel, Switzerland)\| PubMed ID: 33562017	2021
Micro-Bio-Chemo-Mechanical-Systems: Micromotors, Microfluidics, and Nanozymes for Biomedical Applications. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 33893682	2021
Air-Filled Microbubbles Based on Albumin Functionalized with Gold Nanocages and Zinc Phthalocyanine for Multimodal Imaging. Micromachines\| PubMed ID: 34683212	2021
Oxygen Generation Using Catalytic Nano/Micromotors. Micromachines\| PubMed ID: 34683302	2021
Catalytic/magnetic assemblies of rolled-up tubular nanomembrane-based micromotors. RSC advances\| PubMed ID: 35517949	2020
Light-controlled two-dimensional TiO plate micromotors. RSC advances\| PubMed ID: 35528446	2019
Albumin microbubbles conjugated with zinc and aluminum phthalocyanine dyes for enhanced photodynamic activity. Colloids and surfaces. B, Biointerfaces\| PubMed ID: 36150237	2022

Alexander A. Solovev

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