Charge-Storage Nickel Substrate-Boosted CuP2 Nanosheet for the Electrochemical Oxygen Evolution Reaction.

The electrochemical oxygen evolution reaction (OER) is an essential anodic reaction that converts sustainable energy into chemical fuels, as it can provide protons and electrons. One of the most challenging research directions for the practical application of the OER is the elevation of the activity of noble-metal-free electrocatalysts. Here, we report that the nickel foam can be used as an electron-deficient substrate to tune the surface oxidation state of catalytic electrodes and thus boost the OER activity of CuP2 nanosheets via a charge-storage mechanism. The as-obtained self-standing CuP2/Ni electrodes delivered a current density of 220 mA cm-2 at 370 mV overpotential, which is approximately 5.5 times higher than the benchmarked IrO2 on nickel foam. This work sheds some new light on the design of low-cost electrocatalysts or electrodes with high activity for the electrochemical OER.

A label-free and modification-free ratiometric electrochemical strategy for enhanced natural enzyme detection using a bare electrode and nanozymes system.

Ratiometric electrochemical assays have been demonstrated to be more sensitive and selective in various sensing events, mainly due to their affordable built-in correction and good self-reference capability. But it is known that complicated modification and labeling operations usually are necessary for the construction of ratiometric electrochemical assays, therefore is a hot and important issue needing consideration carefully. We herein report a new yet simple bare electrode-based ratiometric electrochemical bioassay to achieve sensitive and selective analysis of alkaline phosphatase (ALP), using a liquid phase system that contains CoOOH nanozymes and commercially available indicator substrate. This proposed bioassay works based on the ratiometric change of dual electrochemical signals, arising from an exclusive target ALP-triggered hydrolysis of electrochemical substrate p-nitrophenyl phosphate (PNPP). In this design, the two hydrolyzed products of electrochemically active p-nitrophenol (PNP) and electrochemically inactive phosphate anion (PO43-) are responsible together for the ratiometric electrochemical analysis of ALP. PNP exhibits a straightforward current response toward ALP content; however, PO43- cannot show a direct electrochemical signal thus is rationally designed to offer an alternative response by linking it with the specific CoOOH nanozyme-catalyzed reaction of 3,3',5,5'-tetramethylbenzidine (TMB) and H2O2, in which the nanozyme-catalyzed product oxTMB shows a direct reduction current at the GCE, and significantly decreases with increasing PO43- species due to the good inhibition of PO43- toward CoOOH nanozyme activity. As a result, a ratiometric electrochemical strategy for ALP analysis with a low limit of detection of 0.366 U/L (S/N = 3) was successfully achieved by integrating the above direct and indirect dual electrochemical responses. This developed bioassay can allow the quantitative diagnosis of ALP activity especially with a label-free and modification-free merit, therefore paving the way for simple, convenient, and portable electroanalytical tools in biosensing design and application.

A Fenton-like reaction system with analyte-activated catfish effect as an enhanced colorimetric and photothermal dopamine bioassay.

Fenton-like reaction systems have been proven to be efficient as powerful promoters in advanced oxidation processes (AOPs) due to their generated reactive oxygen species (ROS), such as ˙OH and ˙O2-, which can further oxidize a specific chromogenic substrate like 3,3',5,5'-tetramethylbenzidine (TMB) to generate sensitive color readout and thereby demonstrate more potential in the colorimetric analysis field. However, the inherent drawback of the low rate-limiting step of Fe3+/Fe2+ conversion in the Fenton-like reaction and its resultant inefficiency for H2O2 decomposition hinder its practical applications. We herein communicate an analyte-activated catfish effect based catalysis strategy to promote the Fenton-like reaction, in which dopamine, like a catfish, was added to activate the Fenton-like reaction. By definition, the conversion rate of Fe3+ to Fe2+ in the proposed Fenton-like reaction can be significantly accelerated through a specific DA-mediated electron transfer process which further promotes the reaction activity in the Fenton-like reaction to generate more ˙OH and ˙O2- radicals. As a result, the produced ˙OH and ˙O2- radicals in such a reaction system can significantly oxidize TMB indicator into its oxidation product (TMBox) and therefore indicate the corresponding target-dependent color and photothermal signal readout, enabling the successful fabrication of a more sensitive and stable colorimetric and photothermometric DA sensor. More significantly, this strategy can greatly advance the practical application of Fenton-like reactions in the fields of colorimetric and photothermometric bioassays.

Photothermometric analysis of bismuth ions using aggregation-induced nanozyme system with a target-triggered surface cleaning effect.

The development of nanozyme-based photothermometric sensing for point-of-care testing (POCT) heavy metal ions is of great significance for disease diagnosis and health management. Considering the low catalytic activity of most nanozymes at physiological pH, we found bismuth ions (Bi3+) could effectively enhance the peroxidase (POX)-like activity of cetyltrimethylammonium bromide and citrate-capped octahedral gold nanoparticle (CTAB/Cit-AuNP) nanozymes. It is mainly based on Bi3+ ions being able to trigger the surface cleaning effect of CTAB/Cit-AuNPs. Because the more active Bi3+ ions could effectively bind with citrate on the gold surface and competitively destroy the electrostatic interaction between citrate and CTAB, resulting in the removal of CTAB ligands from the gold surface. Without the ligand protection, CTAB/Cit-AuNPs aggregated immediately, and further resulted in a significant activation of the POX-like activity of AuNP nanozymes. Based on this principle, we introduced the enzyme substrate 3,3',5,5'-tetramethylbenzidine (TMB) into this aggregation-induced nanozyme system, and rationally designed a photothermometric platform to quickly and sensitively detect Bi3+ ions by using the good photothermal effect of the oxidation product of TMB (oxTMB). The developed photothermometric method only using a common thermometer has a limit of detection (LOD) as low as 45.7 nM for POCT analysis of Bi3+ ions. This study not only provides a more accurate understanding of the aggregation-induced nanozymes based on the surface cleaning principle, but also shows the potential applications of aggregation-induced nanozymes in the POCT field.

A sensitive photothermometric biosensor based on redox reaction-controlled nanoprobe conversion from Prussian blue to Prussian white.

As a new low-cost photothermal nanoprobe, Prussian blue nanoparticles (PB NPs) have been demonstrated to have more potential in photothermometric-based point-of-care testing (POCT) application. However, most of the existing PB NP-based photothermometric sensors were constructed mainly relying on in situ generation of PB NPs or their combination with antigens and antibodies, therefore usually suffering from the inherent defects like complicated preparation and cumbersome surface process as well as high-cost modification. To break this limitation of PB NP-based photothermometric POCT, we proposed an ingenious redox reaction-controlled nanoprobe conversion strategy and successfully applied to photothermometric detection of ascorbate oxidase (AAO). In this design, the heat of PB NP photothermal system under 808-nm laser irradiation dramatically decreased with the addition of AA, due to a unique AA-induced Prussian blue to Prussian white (PB-to-PW) conversion. Upon AAO addition, the heat of reaction system increased because of the enzymatic catalytic reaction between AAO and AA, which led to a significant reduction of AA and resultantly inhibited PB-to-PW conversion. Such target-mediated nanoprobe conversion resulted in an obvious temperature change that could be easily detected by a common thermometer and exhibited good linear ranges from 0.25 to 14 mU/mL with a detection limit as low as 0.21 mU/mL for POCT analysis of AAO. This facile, convenient, and portable photothermometric sensing platform provides an innovative route for the design of PB NP nanoprobe-based photothermometric detection methods. A sensitive photothermometric AAO sensor based on a redox reaction-controlled nanoprobe conversion strategy from Prussian blue to Prussian white.

Schottky Barrier-Induced Surface Electric Field Boosts Universal Reduction of NOx - in Water to Ammonia.

NOx - reduction acts a pivotal part in sustaining globally balanced nitrogen cycle and restoring ecological environment, ammonia (NH3 ) is an excellent energy carrier and the most valuable product among all the products of NOx - reduction reaction, the selectivity of which is far from satisfaction due to the intrinsic complexity of multiple-electron NOx - -to-NH3 process. Here, we utilize the Schottky barrier-induced surface electric field, by the construction of high density of electron-deficient Ni nanoparticles inside nitrogen-rich carbons, to facilitate the enrichment and fixation of all NOx - anions on the electrode surface, including NO3 - and NO2 - , and thus ensure the final selectivity to NH3 . Both theoretical and experimental results demonstrate that NOx - anions were continuously captured by the electrode with largely enhanced surface electric field, providing excellent Faradaic efficiency of 99 % from both electrocatalytic NO3 - and NO2 - reduction. Remarkably, the NH3 yield rate could reach the maximum of 25.1 mg h-1 cm-2 in electrocatalytic NO2 - reduction reaction, outperforming the maximum in the literature by a factor of 6.3 in neutral solution. With the universality of our electrocatalyst, all sorts of available electrolytes containing NOx - pollutants, including seawater or wastewater, could be directly used for ammonia production in potential through sustainable electrochemical technology.

Heterojunction-Based Electron Donators to Stabilize and Activate Ultrafine Pt Nanoparticles for Efficient Hydrogen Atom Dissociation and Gas Evolution.

Platinum (Pt) is the most effective bench-marked catalyst for producing renewable and clean hydrogen energy by electrochemical water splitting. There is demand for high HER catalytic activity to achieve efficient utilization and minimize the loading of Pt in catalysts. In this work, we significantly boost the HER mass activity of Pt nanoparticles in Ptx /Co to 8.3 times higher than that of commercial Pt/C by using Co/NC heterojunctions as a heterogeneous version of electron donors. The highly coupled interfaces between Co/NC and Pt metal enrich the electron density of Pt nanoparticles to facilitate the adsorption of H+ , the dissociation of Pt-H bonds and H2 release, giving the lowest HER overpotential of 6.9 mV vs. RHE at 10 mA cm-2 in acid among reported HER electrocatalysts. Given the easy scale-up synthesis due to the stabilization of ultrafine Pt nanoparticles by Co/NC solid ligands, Ptx /Co can even be a promising substitute for commercial Pt/C for practical applications.

Enhanced Thermometric Sensor for Arsenate Analysis Based on Dual Temperature Readout Signaling Strategy.

New methods for portable detection of arsenate are still in urgent need. Herein, we explored a simple but sensitive thermometric strategy for arsenate determination without complex instruments and skilled technicians. Cobalt oxyhydroxide (CoOOH) nanoflakes, can ingeniously decompose hydrogen peroxide into oxygen in a sealed reaction vessel, accompanied by marked pressure and significant temperature increase due to the exothermic reaction effect (ΔH = -98.2 kJ/mol). The increased pressure then compelled a certain amount of H2O overflowing from the drainage device into another vessel, leading to a significant temperature decrease due to the preloaded ammonium nitrate (NH4NO3) and its good dissolution endothermic effect (ΔH = 25.4 kJ/mol). In the presence of arsenate, the catalytic activity of CoOOH nanoflakes for H2O2 decomposition was inhibited dramatically, resulting in an obvious decrease of the pressure, weighting water and temperature response. The two temperature responses with increasing and decreasing feature were easily measured through a common thermometer, and exhibited an effective signaling amplification via coupling both "signal-on" and "signal-off" temperature readout elements. The obtained dual superimposing temperature readout exhibits a good linear with the concentration of arsenate with a lower detection limit (51 nM, 3.8 ppb). Compared to the inductively coupled plasma mass spectrometry, this enhanced thermometric strategy provides a simple, rapid, convenient, low cost, and portable platform for sensing arsenate in real environmental water.

Molecule-gated surface chemistry of Pt nanoparticles for constructing activity-controllable nanozymes and a three-in-one sensor.

Herein, a simple strategy for constructing activity-controllable nanozymes is proposed based on the glutathione (GSH)-gated surface chemistry of citrate-capped Pt nanoparticles (PtNPs). PtNPs have been shown to have oxidase-like activity that can effectively catalyze the oxidation of 3,3',5,5'-tertamethylbenzidine (TMB) by O2, resulting in a typical color reaction from colorless to blue. We found that GSH can inhibit the oxidase-like activity of PtNPs as a molecule-gated surface chemistry element, resulting in a dramatic decrease of the oxidation of TMB. The addition of copper ions (Cu2+) could oxidize GSH into glutathione disulfide (GSSG), resulting in the distinct suppression of GSH-modulated PtNP surface chemistry and oxidase-like activity inhibition, which further results in a significant acceleration of TMB oxidation and the obvious recovery of intense blue color. Furthermore, the color-based detection signal associated with the redox of TMB indicator here was found to show good fluorescence and a photothermal effect and exhibit sensitive and selective response toward the proposed molecule-gated surface chemistry and Cu2+ target. On the basis of this phenomenon, we successfully constructed a three-in-one sensor for Cu2+ with a triple signal readout, colorimetric, photothermal (temperature), and fluorescence, depending on the proposed in situ modulation method for PtNP catalysis. The applicability of the three-in-one sensor was also demonstrated by measuring Cu2+ in human serum with a standard addition method, and the results are of satisfactory accuracy as confirmed by ICP-MS measurements.

Electrochemical Reduction of N2 into NH3 by Donor-Acceptor Couples of Ni and Au Nanoparticles with a 67.8% Faradaic Efficiency.

The traditional NH3 production method (Haber-Bosch process) is currently complemented by electrochemical synthesis at ambient conditions, but the rather low selectivity (as indicated by the Faradaic efficiency) for the electrochemical reduction of molecular N2 into NH3 impedes the progress. Here, we present a powerful method to significantly boost the Faradaic efficiency of Au electrocatalysts to 67.8% for the nitrogen reduction reaction (NRR) by increasing their electron density through the construction of inorganic donor-acceptor couples of Ni and Au nanoparticles. The unique role of the electron-rich Au centers in facilitating the fixation and activation of N2 was also investigated via theoretical simulation methods and then confirmed by experimental results. The highly coupled Au and Ni nanoparticles supported on nitrogen-doped carbon are stable for reuse and long-term performance of the NRR, making the electrochemical process more sustainable for practical application.

Schottky Barrier Induced Coupled Interface of Electron-Rich N-Doped Carbon and Electron-Deficient Cu: In-Built Lewis Acid-Base Pairs for Highly Efficient CO2 Fixation.

Highly efficient fixation of CO2 for the synthesis of useful organic carbonates has drawn much attention. The design of sustainable Lewis acid-base pairs, which has mainly relied on expensive organic ligands, is the key challenge in the activation of the substrate and CO2 molecule. Here, we report the application of Mott-Schottky type nanohybrids composed of electron-deficient Cu and electron-rich N-doped carbon for CO2 fixation. A ligand-free and additive-free method was used to boost the basicity of the carbon supports and the acidity of Cu by increasing the Schottky barrier at their boundary, mimicking the beneficial function of organic ligands acting as the Lewis acid and base in metal-organic frameworks (MOFs) or polymers and simultaneously avoiding the possible deactivation associated with the necessary stability of a heterogeneous catalyst. The optimal Cu/NC-0.5 catalyst exhibited a remarkably high turnover frequency (TOF) value of 615 h-1 at 80 °C, which is 10 times higher than that of the state-of-the-art metal-based heterogeneous catalysts in the literature.

Synthesis of three-dimensional Au-graphene quantum dots@Pt core-shell dendritic nanoparticles for enhanced methanol electro-oxidation.

Au-graphene quantum dots (GQDs)@Pt core-shell nanodendrites are synthesized through a two-step reduction approach, in which Au forms the core, GQDs form an intermediate layer and dendritic Pt forms the shell. Among the above synthesized catalysts, the GQDs can manipulate the binding of reaction intermediates on the Pt surface as well as assemble π-π * conjugate bonds, thus forming a dendritic Pt shell instead of a compact Pt shell. The obtained core-shell structure was characterized by transmission electron microscopy, energy-dispersive x-ray and x-ray photoelectron spectroscopy. The methanol electro-oxidation was investigated in alkaline media on the Au-GQDs@Pt modified electrode via cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy analysis. In particular, we discovered that Au-Pt assembled with GQDs could dramatically improve the activity and stability of the catalysts, owing to the synergistic effect raised by the GQDs, which exhibit prominent electron conductivity and great chemical/physical stability. It was also found that the Pt/Au mole ratios could control the Pt shell thickness, which significantly affected the catalytic methanol oxidation activity of the Au-GQDs@Pt nanodendrites. The Au-GQDs@Pt nanodendrites with optimum Pt/Au mole ratios of 1.0 exhibited a 2.5 times increase in electrocatalytic activity toward methanol oxidation compared with the commercial catalyst (Pt/C), and its CO tolerance was also greatly improved. The above results show that the Au-GQDs@Pt nanocatalysts have potential application prospects in direct methanol fuel cells.

New Insight into Procedure of Interface Electron Transfer through Cascade System with Enhanced Photocatalytic Activity.

Recombination of photogenerated electron-hole pairs is extremely limited in the practical application of photocatalysis toward solving the energy crisis and environmental pollution. A rational design of the cascade system (i.e., rGO/Bi2 WO6 /Au, and ternary composites) with highly efficient charge carrier separation is successfully constructed. As expected, the integrated system (rGO/Bi2 WO6 /Au) shows enhanced photocatalytic activity compared to bare Bi2 WO6 and other binary composites, and it is proved in multiple electron transfer (MET) behavior, namely a cooperative electron transfer (ET) cascade effect. Simultaneously, UV-vis/scanning electrochemical microscopy is used to directly identify MET kinetic information through an in situ probe scanning technique, where the "fast" and "slow" heterogeneous ET rate constants (Keff ) of corresponding photocatalysts on the different interfaces are found, which further reveals that the MET behavior is the prime source for enhanced photocatalytic activity. This work not only offers a new insight to study catalytic performance during photocatalysis and electrocatalysis systems, but also opens up a new avenue to design highly efficient catalysts in photocatalytic CO2 conversion to useful chemicals and photovoltaic devices.

Tuning the Adsorption Energy of Methanol Molecules Along Ni-N-Doped Carbon Phase Boundaries by the Mott-Schottky Effect for Gas-Phase Methanol Dehydrogenation.

Engineering the adsorption of molecules on active sites is an integral and challenging part for the design of highly efficient transition-metal-based catalysts for methanol dehydrogenation. A Mott-Schottky catalyst composed of Ni nanoparticles and tailorable nitrogen-doped carbon-foam (Ni/NCF) and thus tunable adsorption energy is presented for highly efficient and selective dehydrogenation of gas-phase methanol to hydrogen and CO even under relatively high weight hourly space velocities (WHSV). Both theoretical and experimental results reveal the key role of the rectifying contact at the Ni/NCF boundaries in tailoring the electron density of Ni species and enhancing the absorption energies of methanol molecules, which leads to a remarkably high turnover frequency (TOF) value (356 mol methanol mol-1 Ni h-1 at 350 °C), outpacing previously reported bench-marked transition-metal catalysts 10-fold.

A Polyimide Nanolayer as a Metal-Free and Durable Organic Electrode Toward Highly Efficient Oxygen Evolution.

The exploitation of metal-free organic polymers as electrodes for water splitting reactions is limited by their presumably low activity and poor stability, especially for the oxygen evolution reaction (OER) under more critical conditions. Now, the thickness of a cheap and robust polymer, poly(p-phenylene pyromellitimide) (PPPI) was rationally engineered by an in situ polymerization method to make the metal-free polymer available for the first time as flexible, tailorable, efficient, and ultra-stable electrodes for water oxidation over a wide pH range. The PPPI electrode with an optimized thickness of about 200 nm provided a current density of 32.8 mA cm-2 at an overpotential of 510 mV in 0.1 mol L-1 KOH, which is even higher than that (31.5 mA cm-2 ) of commercial IrO2 OER catalyst. The PPPI electrodes are scalable and stable, maintaining 92 % of its activity after a 48-h chronoamperometric stability test.

Ultratrace Naked-Eye Colorimetric Detection of Hg2+ in Wastewater and Serum Utilizing Mercury-Stimulated Peroxidase Mimetic Activity of Reduced Graphene Oxide-PEI-Pd Nanohybrids.

Herein, we developed a general strategy for rapid, highly selective, and ultratrace naked-eye colorimetric detection of Hg2+ in aqueous solutions. Two dimensional rGO/PEI/Pd nanohybrids, where rGO, PEI, and Pd were referred to as reduced graphene oxide, polyethylenimine, and Pd nanoparticles, respectively, were synthesized and used as mimetic peroxidase for selective and ultrasensitive detection of Hg2+ in water and human serum samples. In the presence of mercury ions, the peroxidase mimetic activity of rGO/PEI/Pd nanohybrids was found to be stimulated and enhanced significantly, which promoted the effective oxidation and color change of 3,3',5,5'-tetramethylbenzidine (TMB) in solution to dark blue that was detected by the naked-eye and the absorption spectroscopic method. The proposed sensing strategy coupled with spectroscopic detection method showed an ultralow detection limit of 0.39 nM for Hg2+ in ddH2O and ∼1 nM in wastewater as well as serum samples, respectively. On the basis of the colorimetric assay, a minimum concentration of ∼10 nM for Hg2+ in wastewater and human serum can be detected with the naked-eye. The naked-eye-based colorimetric assay for sensitive and selective detection of mercury is expected to hold huge potentials in applications such as environmental monitoring, clinical diagnosis, and pharmaceutical analysis.

A colorimetric sensor of cysteine based on self-assembly nanostructures of Fe3+-H2O2/Tetramethylbenzidine system with "On-Off" switching function.

Many strategies have been explored for selectively and sensitively detecting cysteine in different samples. Here, a novel colorimetric sensor based on self-assembly nanostructures of Fe3+-H2O2/Tetramethylbenzidine system with dual-level logic gate function and colorimetric determination of cysteine were firstly explored. The proposed Fe3+-H2O2-TMB system provides a sensitive optical signal due to the selectively reductive ability of cysteine to the oxidized TMB and thus could be successfully applied to the construction of instant on-site visual detection method with a paper based test strip for cysteine determination in a sample solution as well as for a dual-level logic gate fabrication.

Plasmonic and nanozyme dual-channel-based logic judgment for enhancing gold nanoparticle based colorimetric Hg2+ ion sensing performance.

An AND logic gate-based Hg2+ ion colorimetric assay was constructed using the plasmonic and nanozyme dual signal channels of gold nanoparticles (AuNPs). This assay increased the judgment criteria for the identification of Hg2+ ions and effectively improved the accuracy of Hg2+ ion detection.

Ultra-rapid and highly selective colorimetric detection of hydrochloric acid via an aggregation to dispersion change of gold nanoparticles.

A rapid and highly selective naked-eye detection of hydrochloric acid (HCl) in an aqueous medium was established using HCl-triggered redispersion of gold nanoparticle aggregates.

Response of cardiovascular environment to sulfonated hyaluronic acid with higher sulfur content.

Sulfonated hyaluronic acid (S-HA) has been shown to promote endothelialization in the treatment of cardiovascular diseases according to amounts of investigations. In this study, two kinds of S-HA with higher sulfur content were obtained successfully. Through a series of cell experiments, it was found that the S-HA with higher sulfur content not only possessed stronger ability of promoting the growth and migration of endothelial cells, regulating the phenotype of smooth muscle cells, but also had stronger anti-inflammatory function. Furthermore, all the S-HA molecules are very compatible with blood.