Rapid Synthesis of Nickel Hydroxide/Pt-Based Alloy Heterointerface for Hydrogen Evolution in Full pH Range.

The huge application potential of nanoelectrocatalysts can become available only under the condition of scalable and reproducible preparation of nanomaterials (NMs). It is easily overlooked that most of the preparation methods for efficient platinum (Pt)-based electrocatalysts are complicated in process and time-/energy-consuming, which is not conducive to scalable and sustainable production. Herein, we propose a rapid and facile method to in situ construct a heterointerface between nickel hydroxide (Ni(OH)2) and NiPt alloy, in which the preparation steps are easy-to-operate and can be finished in 1 h. Furthermore, the ensemble effect between the Ni(OH)2 substrate and NiPt active sites benefits the water dissociation process in nonacidic conditions, while the electronic effect in NiPt contributes to the downshifted d-band center of Pt and the proper Gibbs free energy of hydrogen species. As a result, the well-designed and quickly constructed Ni(OH)2-Ni3Pt heterointerfaces reveal lower overpotentials for HER compared with most reported Pt-based and commercial Pt/C catalysts in nonacidic conditions. This study is expected to provide useful reference information for the development of facile and robust methods for the preparation of more efficient Pt-based electrocatalysts.

Facile Synthesis of Multifunctional Ni(OH)2 -Supported Core-Shell Ni@Pd Nanocomposites for the Electro-Oxidation of Small Organic Molecules.

In the domain of proton exchange membrane fuel cells (PEMFCs), the development of efficient and durable catalysts for the electro-oxidation of small organic molecules, especially of alcohols (methanol, ethanol, ethylene glycol, et al.) has always been a hot topic. A large number of related electrocatalysts with splendid performance have been designed and synthesized till now, while the preparation processes of most of them are demanding on experimental operations and conditions. Herein, we put forward a facile and handy method for the preparation of multifunctional Ni(OH)2 -supported core-shell Ni@Pd nanocomposites (Ni(OH)2 /Ni@Pd NCs) with the assistance of galvanic replacement reaction (GRR) at room temperature and ambient pressure. As expected, the Ni(OH)2 substrate can prevent the aggregation of core-shell (CS) Ni@Pd nanoparticles (NPs) and inhibit the formation of COads and further prevent Pd from being poisoned. The synergistic effect between CS Ni@Pd NPs and Ni(OH)2 substrate and the electronic effect between Pd shell and Ni core contribute to the outstanding electrocatalytic performance for methanol, ethanol, and ethylene glycol oxidation in alkaline condition. This study provides a succinct method for the design and preparation of efficient Pd-based electrocatalysts for alcohol electro-oxidation.

CRISPR-Cas13a-powered electrochemical biosensor for the detection of the L452R mutation in clinical samples of SARS-CoV-2 variants.

Since the end of 2019, a highly contagious disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has deprived numerous lives worldwide, called COVID-19. Up to date, omicron is the latest variant of concern, and BA.5 is replacing the BA.2 variant to become the main subtype rampaging worldwide. These subtypes harbor an L452R mutation, which increases their transmissibility among vaccinated people. Current methods for identifying SARS-CoV-2 variants are mainly based on polymerase chain reaction (PCR) followed by gene sequencing, making time-consuming processes and expensive instrumentation indispensable. In this study, we developed a rapid and ultrasensitive electrochemical biosensor to achieve the goals of high sensitivity, the ability of distinguishing the variants, and the direct detection of RNAs from viruses simultaneously. We used electrodes made of MXene-AuNP (gold nanoparticle) composites for improved sensitivity and the CRISPR/Cas13a system for high specificity in detecting the single-base L452R mutation in RNAs and clinical samples. Our biosensor will be an excellent supplement to the RT-qPCR method enabling the early diagnosis and quick distinguishment of SARS-CoV-2 Omicron BA.5 and BA.2 variants and more potential variants that might arise in the future.

Synthesis of Uniform Gold Nanorods with Large Width to Realize Ultralow SERS Detection.

In this work, we successfully demonstrate high-yield synthesis of high-quality gold nanorods (Au NRs) with width ranging from 6.5 nm to 175 nm by introducing heptanol molecules as secondary templating agents during cetyltrimethylammonium bromide-templated, seeded growth method. The results show that an appropriate concentration of heptanol molecules not only alter the micellization behavior of CTAB in water, but also help silver ions impact the symmetry-breaking efficiency of additional Au-NP seeds in addition to enhancing the utilization of gold precursors. Moreover, the generality and versatility of the present strategy for synthesis of Au NRs with flexible controlled dimensions are further demonstrated by successful synthesis of Au NRs with the assistance of other fatty alcohols with properly long alkyl chains. Furthermore, when arrays of vertically aligned Au NRs with large width (AVA-Au120×90 NRs) are used as SERS substrates, they can achieve the ultralow limit of detection for crystal violet (10-16  M) with good reliability and reproducibility, and the rapid detection and identification of residual harmful substances.

Rational Design and Facile Preparation of Palladium-Based Electrocatalysts for Small Molecules Oxidation.

Direct liquid fuel cells (DLFCs) can convert the chemical energy of small organic molecules directly into electrical energy, which is a promising technique and always calls for electrocatalysts with high activity, stability and selectivity. Palladium (Pd)-based catalysts for DLFCs have been widely studied with the pursuit of ultra-high performance, however, most of the preparation routes require complex agents, multi-operation steps, even extreme experimental conditions, which are high-cost, energy-consuming, and not conducive to the scalable and sustainable production of catalysts. In this review, the recent progresses on not only the rational design strategies, but also the facile preparation methods of Pd-based electrocatalysts for small molecules oxidation reaction (SMOR) are comprehensively summarized. Based on the principles of green chemistry in material synthesis, the basic rules of "facile method" have been restricted, and the fabrication processes, perks and drawbacks, as well as practical applications of the "real" facile methods have been highlighted. The landscape of this review is to facilitate the mild preparation of efficient Pd-based electrocatalysts for SMOR, that is, to achieve a balance between "facile preparation" and "outstanding performance", thereby to stimulate the huge potential of sustainable nano-electrocatalysts in various research and industrial fields.

Dislocation Effect Boosting the Electrochemical Properties of Prussian Blue Analogues for 2.6 V High-Voltage Aqueous Zinc-Based Batteries.

Prussian blue analogues (PBAs) have attracted increasing attention in aqueous zinc-based batteries (AZBs) with the advantages of an open framework, adjustable redox potential, and easy synthesis. However, they exhibited a low specific capacity and a poor cycle performance. In this work, crystalline potassium iron hexacyanoferrate (FeHCF) with dislocation was designed and prepared by a poly(vinylpyrrolidone) (PVP) additive. The metastable state provided by PVP would cause an electrostatic interaction between cyanogen and water molecules. The reduced force increases the steric resistance of the water molecules entering the crystal. The low content of crystal water in FeHCF is associated with the formation of dislocation. The dislocation effect effectively improves the electrochemical reactivity and reaction kinetics of FeHCF. Thus, it presents a high reversible capacity of 131 mAh g-1 with a superior capacity retention of 85% after 550 cycles at 0.5 A g-1. When used as a cathode, the AZBs display a high voltage of 2.6 V, a fast charging capability (<5 min), and a satisfactory cycle stability with a capacity retention of 82% after 400 cycles at 0.2 A g-1 in decoupling electrolytes. This work provides an effective strategy for the design of high-performance PBA-based cathodes for 2.6 V AZBs.

CRISPR-Cas12a-Empowered Electrochemical Biosensor for Rapid and Ultrasensitive Detection of SARS-CoV-2 Delta Variant.

Coronavirus disease 2019 (COVID-19) is a highly contagious disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). The gold standard method for the diagnosis of SARS-CoV-2 depends on quantitative reverse transcription-polymerase chain reaction till now, which is time-consuming and requires expensive instrumentation, and the confirmation of variants relies on further sequencing techniques. Herein, we first proposed a robust technique-methodology of electrochemical CRISPR sensing with the advantages of rapid, highly sensitivity and specificity for the detection of SARS-CoV-2 variant. To enhance the sensing capability, gold electrodes are uniformly decorated with electro-deposited gold nanoparticles. Using DNA template identical to SARS-CoV-2 Delta spike gene sequence as model, our biosensor exhibits excellent analytical detection limit (50 fM) and high linearity (R2 = 0.987) over six orders of magnitude dynamic range from 100 fM to 10 nM without any nucleic-acid-amplification assays. The detection can be completed within 1 h with high stability and specificity which benefits from the CRISPR-Cas system. Furthermore, based on the wireless micro-electrochemical platform, the proposed biosensor reveals promising application ability in point-of-care testing.

2D materials for bone therapy.

Due to their prominent physicochemical properties, 2D materials are broadly applied in biomedicine. Currently, 2D materials have achieved great success in treating many diseases such as cancer and tissue engineering as well as bone therapy. Based on their different characteristics, 2D materials could function in various ways in different bone diseases. Herein, the application of 2D materials in bone tissue engineering, joint lubrication, infection of orthopedic implants, bone tumors, and osteoarthritis are firstly reviewed comprehensively together. Meanwhile, different mechanisms by which 2D materials function in each disease reviewed below are also reviewed in detail, which in turn reveals the versatile functions and application of 2D materials. At last, the outlook on how to further broaden applications of 2D materials in bone therapies based on their excellent properties is also discussed.

Facet-Dependent Long-Term Stability of Gold Aerogels toward Ethylene Glycol Oxidation Reaction.

In this work, a series of AuPNR6 - 50 aerogels with different percentages of {110} facets (from ∼12 to 36%) were controllably prepared and then used to investigate their performance (specific activity and long-term stability) toward ethylene glycol oxidation reaction (EGOR), in which PNR represents the particle number ratio of 6 nm Au NPs to 50 nm Au NPs. It is found that their specific activity and long-term stability highly depend on the sum of the percentage of the {100} and {111} facets and the percentage of {110} facets, respectively. In addition, Au246 - 50 aerogels with the highest percentage of {110} facets can possess excellent long-term stability (retaining about 95% of the initial current) but still have excellent specific activity (about 90.42 mA cm-2). Thus, the specific activity and long-time stability of AuPNR6 - 50 aerogels toward EGOR can be well balanced by controlling the proper percentage of {110} facets on their surfaces. Therefore, the successful fabrication of AuPNR6 - 50 aerogels with greatly improved long-term stability and excellent specific activity not only provides a novel method for the design of electrocatalysts but also would boost the commercial development of direct ethylene glycol fuel cells.

Synthesis of large gold nanoparticles with deformation twinnings by one-step seeded growth with Cu(ii)-mediated Ostwald ripening for determining nitrile and isonitrile groups.

In this work, uniform and large gold nanoparticles (Au NPs) including quasi-spherical (QS) Au NPs with average diameters of 70 to 196 nm and trisoctahedral (TOH) Au NPs with average diameters of 140 to 195 nm were successfully synthesized by controlling the concentration of Cu2+ ions and the particle number of 3 nm Au-NP seeds, respectively, using a one-step seeded growth method with Cu2+-mediated Ostwald ripening. It is found that because of the concentration-dependent under-potential deposition of Cu2+ ions (CuUPD), 3 nm Au-NP seeds are firstly changed into Au NPs with a controlled QS- or TOH shape at the initial growth stage, followed by the conformal growth of Au atoms onto the initially formed Au NPs due to Cu2+-mediated Ostwald ripening, in which the extra Au atoms come from the dissolution of in situ Au nuclei by the unavoidable self-nucleation. Moreover, the as-prepared QS Au NPs with a rough surface exhibit a better SERS performance for physically adsorbed probes (crystal violet, CV) than the TOH Au NPs with sharp tips and with a comparable size. Furthermore, the as-prepared QS Au NPs can be used to distinguish nitrile and isonitrile groups by surface-enhanced Raman scattering (SERS) due to the presence of deformation twinnings. Thus, the as-prepared QS Au NPs with a rough surface and deformation twinnings can be further used as templates for the fabrication of bimetallic materials with multi-functionalities.

Compressive Strain in Core-Shell Au-Pd Nanoparticles Introduced by Lateral Confinement of Deformation Twinnings to Enhance the Oxidation Reduction Reaction Performance.

In this work, quasi-spherical, uniform gold nanoparticles with rich deformation twinning (Audt NPs) were first synthesized with the assistance of copper(II) ions. Then, these Audt NPs were used as the cores for the fabrication of core-shell (CS) Audt-Pd NPs with ultrathin Pd layers, which also can bear compressive strain because of the formation of corrugated structured Pd shells led by the lateral confinement imposed by deformation twinning in the Au cores. The presence of compressive strain in the CS Audt-Pd NPs can result in the widening of the d-band width of the Pd shell and further the downshift of their d-band center, which can then improve the desorption ability of intermediates and still maintain the adsorption ability of the reactants because of the broad adsorption potential range. Taking the oxidation reduction reaction and the ethanol oxidation reaction as examples, the as-prepared Audt-Pd NPs indeed exhibited superior catalytic performances because of the synergism of compressive strain and the electronic effect. Thus, our work opens a new way to introduce compressive strain in the Pd-based CS NP catalysts, which can achieve the enhancement in the electrocatalytic performance by combining the merit of compressive strain and the electronic effect.

pH-Dependent growth of atomic Pd layers on trisoctahedral gold nanoparticles to realize enhanced performance in electrocatalysis and chemical catalysis.

In this work, the controlled epitaxial growth of ultrathin Pd shells of a few atomic layers (denoted as nL) on the surfaces of gold nanoparticle (Au NP) cores of different morphologies (trisoctahedral, cubic, and spherical shapes) in the presence of cetyltrimethylammonium chloride (CTAC) was achieved by regulating the pH value of the aqueous CTAC solution and finely tuning the amount of the Pd precursor. It was found that the critical shell thickness for epitaxial Pd growth at the optimal pH value was 4 atomic layers, taking {331}-faceted trisoctahedral (TOH) Au@PdnL NPs as an example, on the basis of the results of atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. Moreover, the resulting TOH Au@Pd1L NPs (100.9 m2 g-1, 13.2 A mgPd-1 and 13.1 mA cm-2) exhibited excellent electrocatalytic performance and long-term electrocatalytic activity for ethanol oxidation, around 4.8-fold, 66-fold, and 21.8-fold better than commercial Pd/C catalysts (31 m2 g-1, 0.2 A mgPd-1, and 0.6 mA cm-2). Furthermore, the resulting TOH Au@Pd1L NPs not only markedly enhance the chemical catalytic activity for the reduction of 4-nitrophenol (4-NP), but also allow the in situ surface-enhanced Raman spectroscopy (SERS) monitoring of the reaction process of the Pd-catalyzed reduction of 4-NTP. Thus, our work may provide a new way to fabricate core-shell (CS) bimetallic NPs with the merits of both metal outer shells (excellent catalytic performance in electrocatalysis and chemical catalysis) and Au NP cores (reaction process by in situ SERS monitoring).