Understanding the “Anti-Catalyst” Effect with Added CoO_<i>x</i> Water Oxidation Catalyst in Dye-Sensitized Photoelectrolysis Cells: Carbon Impurities in Nanostructured SnO₂ Are the Culprit

In 2017, we reported a dye-sensitized, photoelectrolysis cell consisting of fluorine-doped tin oxide (FTO)-coated glass covered by SnO2 nanoparticles coated with N,N′-bis­(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) dye and then a photoelectrochemically deposited CoOx water oxidation catalyst (WOCatalyst), FTO/nano-SnO2/PMPDI/CoOx. This system employed nanostructured SnO2 stabilized by a polyethyleneglycol bisphenol A epichlorohydrin (PEG-BAE) copolymer and other C-containing additives based on a literature synthesis to achieve a higher surface area and thus greater PMPDI dye absorption and resultant light collection. Surprisingly, the addition of the well-established WOCatalyst CoOx resulted in a decrease in the photocurrent, an unexpected “anti-catalyst” effect. Two primary questions addressed in the present study are (1) what is the source of this “anti-catalyst” effect? and (2) are the findings of broader interest? Reflection on the synthesis of nano-SnO2 stabilized by PEG-BAE, and the large, ca. 10:1 ratio of C to Sn in synthesis, led to the hypothesis that even the annealing step at 450 °C in of the FTO/SnO2 anode precursors was unlikely to remove all the carbon initially present. Indeed, residual carbon impurities are shown to be the culprit in the presently observed “anti-catalyst” effect. The implication and anticipated broader impact of the results of answering the two abovementioned questions are also presented and discussed along with a section entitled “Perspective and Suggestions for the Field Going Forward.

Enhanced Hybridization and Nanopatterning via Heated Liquid-Phase Infiltration into Self-Assembled Block Copolymer Thin Films

Organic–inorganic hybrids featuring tunable material properties can be readily generated by applying vapor- or liquid-phase infiltration (VPI or LPI) of inorganic materials into organic templates, with resulting properties controlled by type and quantity of infiltrated inorganics. While LPI offers more diverse choices of infiltratable elements, it tends to yield smaller infiltration amount than VPI, but the attempt to address the issue has been rarely reported. Here, we demonstrate a facile temperature-enhanced LPI method to control and drastically increase the quantity and kinetics of Pt infiltration into self-assembled polystyrene-block-poly­(2-vinylpyridine) block copolymer (BCP) thin films. By applying LPI at mildly elevated temperatures (40–80 °C), we showcase controllable optical functionality of hybrid BCP films along with conductive three-dimensional (3D) inorganic nanostructures. Structural analysis reveals enhanced metal loading into the BCP matrix at higher LPI temperatures, suggesting multiple metal ion infiltration per monomer of P2VP. Combining temperature-enhanced LPI with hierarchical multilayer BCP self-assembly, we generate BCP-metal hybrid optical coatings featuring tunable antireflective properties as well as scalable conductive 3D Pt nanomesh structures. Enhanced material infiltration and control by temperature-enhanced LPI not only enables tunability of organic–inorganic hybrid nanostructures and properties but also expands the application of BCPs for generating uniquely functional inorganic nanostructures

Potentiometric Biosensors Based on Molecular-Imprinted Self-Assembled Monolayer Films for Rapid Detection of Influenza A Virus and SARS-CoV‑2 Spike Protein

Rapid, yet accurate and sensitive testing has been shown to be critical in the control of spreading pandemic diseases such as COVID-19. Current methods which are highly sensitive and can differentiate different strains are slow and cannot be conveniently applied at the point of care. Rapid tests, meanwhile, require a high titer and are not sufficiently sensitive to discriminate between strains. Here, we report a rapid and facile potentiometric detection method based on nanoscale, three-dimensional molecular imprints of analytes on a self-assembled monolayer (SAM), which can deliver analyte-specific detection of both whole virions and isolated proteins in microliter amounts of bodily fluids within minutes. The detection substrate with nanoscale inverse surface patterns of analytes formed by a SAM identifies a target analyte by recognizing its surface nano- and molecular structures, which can be monitored by temporal measurement of the change in substrate open-circuit potential. The sensor unambiguously detected and differentiated H1N1 and H3N2 influenza A virions as well as the spike proteins of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and Middle-East respiratory syndrome (MERS) coronavirus in human saliva with limits of detection reaching 200 PFU/mL and 100 pg/mL for the viral particles and spike proteins, respectively. The demonstrated speed and specificity of detection, combined with a low required sample volume, high sensitivity, ease of potentiometric measurement, and simple sample collection and preparation, suggest that the technique can be used as a highly effective point-of-care diagnostic platform for a fast, accurate, and specific detection of various viral pathogens and their variants

Suppression of Carbon Monoxide Poisoning in Proton Exchange Membrane Fuel Cells via Gold Nanoparticle/Titania Ultrathin Film Heterogeneous Catalysts

Titania (TiO2)-supported gold (Au) nanoparticles (NPs) have long been considered as a promising solution for carbon monoxide (CO) poisoning in proton exchange membrane fuel cells (PEMFCs) as they can efficiently catalyze CO oxidation reaction. Nevertheless, the actual application in functioning PEMFCs has been rarely reported primarily due to the challenges of synthesizing and incorporating the oxidation catalyst in manners compatible with the structure and fabrication of PEMFCs. Here we successfully incorporate the Au NPs/TiO2 catalyst into PEMFCs and demonstrate an excellent CO elimination function, improving the performance and CO tolerance of PEMFCs; we combine an ultrathin TiO2 layer (<1 nm) deposited on a Nafion membrane via the low-temperature atomic layer deposition (ALD) and a monolayer of Au NPs assembled on the top of the ultrathin TiO2 using the Langmuir–Blodgett method. An over 30% enhanced maximum power output is achieved under the presence of a trace amount of CO. Even under highly concentrated CO (0.1%), a less than 10% performance decrease occurs with the incorporation of Au NPs/TiO2, in contrast to a nearly 70% performance decrease observed in the control device. The results represent the first experimental implementation of Au NPs/TiO2 catalysts in PEMFCs and the confirmation of their effectiveness for mitigating the CO poisoning effect

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl– species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl– passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl– species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl– passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl– species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl– passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl– species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl– passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl– species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl– passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials