Amendment of palladium nanocubes with iron oxide nanowires for boosted formic acid electro−oxidation

To quickly move the formic acid (FA) fuel cells closer to a real commercialization, an inexpensive, efficient, and durable electrocatalyst for the direct FA electro-oxidation (FAEO) was developed. This involved a sequential modification of a glassy carbon (GC) substrate with palladium nanocubes (ca. 70 nm, nano-Pd) and iron oxide nanowires (nano-FeO_x, ca. 40 nm and 150 nm in average diameter and length, respectively). The deposition sequence and loading level of nano-FeO_x in the catalyst were optimized to minimize the catalyst's poisoning with CO that might probably release from a parallel dehydration of FA or from CO₂ reduction. Surprisingly, the FeO_x/Pd/GC catalyst exhibited a high (21.6 mA cm^?2) specific activity for FAEO, which denoted ca. 7 times that of the “pristine” Pd/GC catalyst. This was synchronized with a better (up to fivefold increase in turnover frequency) “long-termed” stability that extended for 90 min of continuous electrolysis at room temperature. A successful effort was dedicated to improving more the catalyst's stability by activating the catalyst electrochemically at –0.5 V vs Ag/AgCl/KCl (sat.) in 0.2 mol L^?1 NaOH. The CO stripping agreed perfectly with the impedance analysis in appending the observed enhancement in the catalytic efficiency of FAEO to a favorable electronic modulation at the Pd surface that boosted the oxidative desorption of poisoning CO species at a lower potential.     

Dynamic Open Coordination Cage from Nonsymmetrical Imidazole–Pyridine Ditopic Ligands for Turn‐On/Off Anion Binding

This work demonstrates a new nonconventional ligand design, imidazole/pyridine‐based nonsymmetrical ditopic ligands ( 1 and 1 ^S ), to construct a dynamic open coordination cage from nonsymmetrical building blocks. Upon complex formation with Pd²⁺ at a 1:4 molar ratio, 1 and 1 ^S initially form mononuclear PdL₄ complexes (Pd²⁺( 1 )₄ and Pd²⁺( 1 ^S )₄) without formation of a cage. The PdL₄ complexes undergo a stoichiometrically controlled structural transition to Pd₂L₄ open cages ((Pd²⁺)₂( 1 )₄ and (Pd²⁺)₂( 1 ^S )₄) capable of anion binding, leading to turn‐on anion binding. The structural transitions between the Pd₂L₄ open cage and the PdL₄ complex are reversible. Thus, stoichiometric addition (2 equiv) of free 1 ^S to the (Pd²⁺)₂( 1 ^S )₄ open cage holding a guest anion ((Pd²⁺)₂( 1 ^S )₄?G^?) enables the structural transition to the Pd²⁺( 1 ^S )₄ complex, which does not have a cage and thus causes the release of the guest anion (Pd²⁺( 1 ^S )₄+G^?).     

碳纳米管负载的Pd-Ag-Sn催化剂对甲酸的电氧化

采用硼氢化钠还原的方法合成了碳纳米管负载的钯基纳米催化剂（Pd/CNT,Pd₇Ag₃/CNT,Pd₇Sn₂/CNT,Pd₇Ag₁Sn₂/CNT,Pd₇Ag₂Sn₂/CNT和Pd₇Ag₃Sn₂/CNT）。通过XRD,TEM和XPS对其进行了表征,结果表明,相比Pd/CNT和Pd-Ag（或Pd-Sn）催化剂的纳米颗粒,Pd-Ag-Sn催化剂展现出了更小的平均颗粒尺寸（2.3 nm）。此外,还通过循环伏安（CV）和计时电流法（CA）测试了这些催化剂对甲酸氧化的电活性,在酸碱介质中,Pd-Ag-Sn/CNT对甲酸氧化都表现出了更高的电流密度。其中,Pd₇Ag₂Sn₂/CNT催化剂在酸碱介质中的电流密度分别是108.8和211.3 mA·cm^-2,相应的Pd质量电流密度高达1 364和2 640 mA·mg^-1,远远高于商业Pd/C,表明Pd-Ag-Sn/CNT催化剂对甲酸氧化表现出了极好的电催化活性。     

Dendrimer Templated Synthesis of Carbon Nanotube Supported PdAu Catalyst and its Application as Hydrogen Peroxide Sensor

At present, CNT supported catalysts were prepared by two different methods as NaBH₄ reduction and dendrimer templated NaBH₄ reduction method to observe the effect of preparation method on the sensitivity and activity of H₂O₂ reduction. Then, CNT supported Pd_xAu_y bimetallic nanocatalysts having various atomic ratio were synthesized via novel dendrimer templated NaBH₄ reduction method. The resulting materials were characterized employing XRD and TEM. Crystallite size of 10 %Pd_0.7Au_0.3/CNT_dendrimer was obtained from XRD 17.1 nm and mean particle size obtained from TEM is about 15 nm. Moreover, the electrochemical behavior of these catalysts was characterized by cyclic voltammetry (CV) and chronoamperometry (CA) techniques. Pd_xAu_y bimetallic nanocatalysts have excellent electrocatalytic properties and great potential for applications in electrochemical detection. The sensitivity and the limit of detection values for the prepared sensor with monometallic 10 % Pd/CNT_dendrimer catalysts are 219.78 μA mM^?1cm^?2 and 2.6 μM, respectively. However, the sensor constructed with 10 %Pd_0.7Au_0.3/CNT_dendrimer modified electrode has a very high sensitivity of 316.89 μA mM^?1 cm^?2 with a quick response time of 2 s and a wide linear range of 0.001–19.0 mM. In addition, the interference experiment indicated that the 10 % Pd_0.7Au_0.3/CNT_dendrimer nanoparticles have good selectivity toward H₂O₂.     

Imine Gels Based on Ferrocene and Porphyrin and Their Electrocatalytic Property

A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H₂TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H₂, Ni²⁺, Co²⁺, Pd²⁺ and Zn²⁺) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm^?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade^?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm^?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (E_p) of 0.95 V and half‐wave potential (E_1/2) of 0.84 V in 1.0 mol L^?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.     

The preparation of ionic liquid based iron phosphate/CNTs composite via microwave radiation for hydrogen evolution reaction and oxygen evolution reaction

Water electrolysis is a promising method for hydrogen production, so the preparation of low-cost and efficient electrocatalysts with a quick and simple procedure is crucial. Herein, iron phosphate (Fe₇(PO₄)₆) was prepared via microwave radiation using ionic liquid (IL) as iron and phosphorus dual-source. This method is simple and rapid, and the product can be directly used as electrocatalysts without further treatment. The experimental results show that the IL can influence the morphology and electrocatalytic performance. Moreover, the addition of carbon nanotubes (CNTs) is favorable for formation of iron phosphate nanoparticles to improve the catalytic activities. As hydrogen evolution reaction (HER) catalyst, this iron phosphate/CNTs exhibits an onset overpotential of 120 mV, Tafel slope of 32.9 mV dec^-1, and current densities of 10 mA cm⁻² at overpotential of 185 mV. Then, it obtains a good activity for oxygen evolution reaction (OER) with a low onset potential of 1.48 V, Tafel slope of 73.3 mV dec^-1, and it only needs an overpotential of 300 mV to drive the 10 mA cm⁻². This bifunctional catalyst also shows good durability for HER and OER. This microwave-assisted method provides an outstanding strategy to prepare iron phosphate in a simple and fast process with good catalytic performance for water splitting.     

Synergistic enhancement of formic acid electro-oxidation on PtxCuy co-electrodeposited binary catalysts

A propitious binary catalyst composed of Pt and Cu which were electrodeposited simultaneously onto a glassy carbon (GC) substrate was recommended for the formic acid (FA) electro-oxidation reaction (FAOR); the principal anodic reaction in the direct FA fuel cells (DFAFCs). The simultaneous co-electrodeposition of Pt and Cu in the catalyst provided an opportunity to tune the geometric functionality of the catalyst to resist the adsorption of poisoning CO at the Pt surface that represented the major impediment for DFAFCs marketing. The catalytic activity of the catalyst toward FAOR was significantly influenced by the (Pt⁴⁺/Cu²⁺) molar ratio of the electrolyte during electrodeposition, which also affected the surface coverage of Pt and Cu in the catalyst. Interestingly, with a molar (Pt⁴⁺/Cu²⁺) ratio of (1:4), the catalyst sustained superior (3.58 compared to 0.65 obtained at the pristine Pt/GC catalyst) activity for FAOR, concurrently with up to four-times (0.73 compared to 0.18 obtained at the pristine Pt/GC catalyst) improvement in the catalytic tolerance against CO poisoning. This associated, surprisingly, a negative shift of ca. 336 mV in the onset potential of FAOR, in an indication for the competitiveness of the catalyst to minimize superfluous polarizations in DFAFCs. Furthermore, it offered a better (ended up with 20% loss in the activity) stability for continuous (1 h) electrolysis than pristine Pt/GC catalyst (the loss reached 35%). The impedance and CO stripping measurements together excluded the electronic element but confirmed the geometrical influence in the catalytic enhancement.     

Tetrazole-functionalized two-dimensional covalent organic frameworks coordinated with metal ions for electrocatalytic oxygen evolution reaction

The search for functionalized covalent organic framework (COF) materials is significant on account of their great promise for frontline applications in various fields. Herein, a novel and convenient tactic is developed to design and fabricate the tetrazole-functionalized COF materials with abundant nitrogen atoms, which can provide active sites, facilitating the incorporation of COFs with metal ions. In particular, a β-ketoenamine-linked COF named COF-TpDb is selected as precursor for postsynthetic modification to introduce the tetrazole moieties to coordinate with metal ions cobalt (Co²⁺) and palladium (Pd²⁺), giving two functional metal-coordinated COFs complexes COF-TpDb-TZ-Co and COF-TpDb-TZ-Pd. The resultant COF-TpDb-TZ-Co displays a higher oxygen evolution reaction activity with a lower overpotential of 390 mV at a current density of 10 mA cm^?2, which is much enhanced compared with COF-TpDb-TZ. The tactic for the fabrication of tetrazole-functionalized COFs with abundant nitrogen atoms implements rational design for the construction of functional COFs and expands the promising application of metal-coordinated COF materials in electrocatalysis.     

Facile fabrication of hydrangea-like NiSe/FeSe2 nanostructures towards efficient water oxidation

A facile one-pot hydrothermal method has been demonstrated for the fabrication of an innovative hydrangea-like NiSe/FeSe₂ nanocatalyst for boosting oxygen evolution reaction (OER). Benefitting from the advantages of the porous architecture, high specific surface area, facilitated electron transfer rate, an ultralow overpotential of merely 210 mV is required for the optimized NiSe/FeSe_2(1:1.5) to drive the electrocatalytic water oxidation to reach to 10 mA cm^?2. Moreover, by equipping NiSe/FeSe_2(1:1.5) with Pt/C for electrochemical water splitting, a cell potential of merely 1.60 V is demanded to attain 10 mA cm^?2, even outperforming the IrO₂ 6 Pt/C couple. More importantly, the structure and morphology of NiSe/FeSe_2(1:1.5) are still well maintained after a long-term chronopotentiometry test. This work opens a new avenue for constructing effective and durable non-precious electrocatalysts for OER.     

Hexanoyl chitosan/ENR25 blend polymer electrolyte system for electrical double layer capacitor

Single salt polymer electrolytes based on hexanoyl chitosan‐ENR25 were prepared by employing LiN (CF₃SO₂)₂ or LiCF₃SO₃ as the doping salt. Elastic property of hexanoyl chitosan was enhanced with the incorporation of ENR25. DSC studies revealed immiscibility of hexanoyl chitosan and ENR25, and dissolution of salt was favored in ENR25 phase. Conductivity enhancement was observed in the blends as compared with the neat hexanoyl chitosan. The maximum conductivities achieved for LiCF₃SO₃‐ and LiN (CF₃SO₂)₂‐comprising electrolyte systems were 1.6 × 10^?8 and 5.0 × 10^?7 S cm^?1, respectively. Deconvolution of spectra bands in the v_as (SO₂^?) mode of LiN (CF₃SO₂)₂ and v_s (SO₃^?) mode of LiCF₃SO₃ has been carried out to estimate the relative percentage of free ions and associated ions. The findings were in good agreement with conductivity results. Electrical double layer capacitor (EDLC) was fabricated with hexanoyl chitosan/ENR25 (90:10)‐LiN (CF₃SO₂)₂‐EmImTFSI electrolyte and activated carbon‐based electrodes. The conductivity and electrochemical stability window of hexanoyl chitosan/ENR25‐LiN (CF₃SO₂)₂‐EmImTFSI were ~10^?6 S cm^?1 and 2.7 V, respectively. The performance of the EDLC was analyzed by cyclic voltammetry (CV) and galvanostatic charge‐discharge (GCD). From GCD, the specific capacitance of EDLC was 58.0 F g^?1 at 0.6 mA cm^?2. The specific capacitance was found to decrease with increasing current density.     

Introduction of high valent Mo6+ in Prussian blue analog derived Co-layered double hydroxide nanosheets for improved water splitting

Herein, we report a facile method for synthesizing MoCo-layered double hydroxide (LDH) nanosheets employing Prussian blue analog (PBA) as the precursor. The introduction of Mo in Co-LDH modulates the electronic structure, increases the number of active sites and electrochemical surface area to improve the hydrogen evolution, oxygen evolution, and overall water splitting activity. As a result, PBA-derived Mo_0.25Co_0.75-LDH nanosheets demonstrated 10 mA cm^?2 current density at only 220 mV and 115 mV overpotentials for OER and HER, respectively. The overall water splitting was attained at 1.52 V cell voltage for 10 mA cm^?2 current density.     

Theory-enforced Re-investigation of the Origin of the Large Metal–Carbon Bond Strength in PdCH2I+ and its reactions with unsaturated hydrocarbons

State-of-the-art ab initio studies demonstrate that the reaction Pd⁺ + CH₃I → PdCH₂I⁺ + H^. is endothermic by ca. 20 kcal/mol, which translates into a bond dissociation energy (BDE) of ca. 83 kcal/mol for the Pd⁺? CH₂I bond. This figure is in agreement with an experimental bracket of 68 kcal/mol < BDE(Pd⁺? CH₂I) < 92 kcal/mol. Based on these findings, the previously studied Pd⁺/CH₃I system was re-investigated, and double-resonance experiments demonstrate that the formation of PdCH₂I⁺ occurs stepwise via PdCH as a reactive intermediate. Further, ion/molecule reactions of PdCH₂I⁺ with unsaturated hydrocarbons are studied, which reveal the formation of carbon–carbon bonds in the gas phase.     

Photoelectrochemical studies on gold electrodes with surface oxide layers: Part I. Photocurrent measurement in the visible region

By illumination with visible light at wavelengths of 340–730 nm, anodic photocurrents were observed at a gold electrode in contact with a 0.2 M NaClO₄ aqueous solution (pH 6.0) in the potential range from +1.0 to +2.1 V vs. RHE. Based on the results of potentiodynamic and photocurrent measurements, the following three characteristic potential ranges have been distinguished: (1) +1.0–+1.4 V, where possibly low-coverage surface oxides (or chemisorbed OH) other than Au₂O₃ are present; (2) +1.5–+1.8V where the predominant surface oxide is Au₂O₃ up to ca. 1 nm in thickness; and (3) above +1.9 V, where a thicker surface layer, absorbing mainly in the UV wavelength range, is formed on the Au₂O₃ under-layer. The photocurrent quantum yield at the Au₂O₃ layer 0.3–0.8 nm thick was estimated to be on the order of 20% at 490 nm, assuming an absorption coefficient of 10⁵ cm^?1.     

Evolution of microstructure and crack pattern in NiO thin films under 200 MeV Au ion irradiation

NiO thin films grown on Si (100) substrate by electron beam evaporation method and sintered at 700 °C were irradiated with 200 MeV Au¹⁵⁺ ions. The fcc structure of the sintered films was retained up to the highest fluence (1×10¹³ ions cm^?2) of irradiation. However the microstructure of the pristine film underwent a considerable modification with increasing ion fluence. 200 MeV Au ion irradiation led to compressive stress generation in NiO medium. The diameter of the stressed region created by 200 MeV Au ions along the ion path was estimated from the variation of stress with ion fluence and found to be ～11.6 nm. The film surface started cracking when irradiated at and above the fluence of 3×10¹² ions cm^?2. Ratio of the fractal dimension of the cracked surface obtained at 200 MeV and 120 MeV (Mallick et al., 2010a) Au ions was compared with the ratio of the radii of ion tracks calculated based on Coulomb explosion and thermal spike models. This comparison indicated applicability of thermal spike model for crack formation.     

A hexanuclear gold carbonyl cluster

The hexanuclear gold carbonyl cluster [PPh₄]₂[Au₆(CF₃)₆Br₂(CO)₂] (4) has been obtained by spontaneous self-assembly of the following independent units: CF₃AuCO (1) and [PPh₄][Br(AuCF₃)₂] (3). The cyclo-Au₆ aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm^–1 in the separate component 1 to 2171 cm^–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh₄][CF₃AuBr] (2) are also reported.     

A highly uniform CuO@SiO2 porous sphere with improved electrochemical sensing performance for the accurate determination of vanillin in food samples

A porous sphere of CuO@SiO₂ was obtained by simple calcination of the copper silicate (CuSiO₃) sphere. The formation of the porous sphere was studied in detail with the support of various physical characterization techniques. The CuO@SiO₂ was coated on an electrode surface where it demonstrates high catalytic activity for the electro-oxidation of vanillin in phosphate buffer solution (PBS; pH 7.0). The modified electrode has good surface adsorption (1.861 × 10^?10 mol cm^?2) and rate constant (2.866 × 10⁵ cm³ mol^?1 s^?1) characteristics for vanillin detection. The CuO@SiO₂-modified surface exhibited good linear range (0.05 μM–1.2 μM and 6.2 to 111.2 μM), detection limit (53 nM), sensitivity (2.88 μA μM^?1 cm^?2), selectivity, stability, and reproducibility. The CuO@SiO₂-modified electrode was further examined for the determination of vanillin in real samples including biscuits and chocolates with satisfactory recoveries.     

Enhanced frequency upconversion of Sm3+ ions by elliptical Au nanoparticles in dichroic Sm3+: Au-antimony glass nanocomposites

Dichroic Sm³⁺: Au-antimony glass nanocomposites are synthesized in a new reducing glass (dielectric) matrix (mol%) K₂O–B₂O₃–Sb₂O₃ (KBS) by a single-step melt-quench technique involving selective thermochemical reduction. X-ray diffraction (XRD) and selected area electron diffraction (SAED) results indicate that Au⁰ nanoparticles are grown along the (2 0 0) plane direction. The transmission electron microscopic (TEM) image reveals the elliptical Au⁰ nanoparticles having major axis range 12–17 nm. Dichroic behavior is due to elliptical shape of Au⁰ nanoparticles of aspect ratio ～1.2. Au⁰ NPs of concentration of 0.03 wt% (4.1 × 10¹⁸ atoms/cm³) drastically enhances the intensity (～7-folds) of electric dipole ⁴G_5/2 → ⁶H_9/2 red transition (636 nm) of Sm³⁺ ions and then attenuates with further increase in Au⁰ concentration. The magnetic dipole ⁴G_5/2 → ⁶H_5/2 green (566 nm) and ⁴G_5/2 → ⁶H_7/2 orange (602 nm) transitions remain almost unaffected by presence of nano Au⁰. Local field enhancement (LFE) induced by Au⁰ SPR and energy transfer (ET) from fluorescent Au⁰ → Sm³⁺ ions are found to be responsible for the enhancement while reverse ET from Sm³⁺ → Au⁰ and optical re-absorption due to Au⁰ SPR for attenuation.     

Solid-state synthesis of nitrogen-doped graphitic nanotubes with outstanding electrochemical properties

Synthesis of new anodes is crucial for commercialization of rechargeable potassium-ion batteries (PIBs). In this work, the nitrogen-doped graphitic nanotubes (NGTs) were synthesized by solid-state reaction method. The microstructural characterization of synthesized NGTs revealed the presence of many active sites (provided by N-doping i.e. N_p and N_g) and tubular channels for the K⁺ ion transport. The NGTs electrode was tested against potassium metal in the presence of carbonate based electrolytes. The NGTs revealed the maximum reversible capacity of 220 mA h g^?1 at 20 mA g^?1 current density. Furthermore, the cycle stability of NGTs was confirmed by cycling it for 200 times at the current density of 100 mA g^?1, where specific capacity of 81.2 mA h g^?1 was retained. The excellent electrochemical properties (rate capability) and fast synthesis of NGTs highlights its possibility to be used against post-lithium metal anodes in near future.     

Chemical deposition and exfoliation from liquid crystal template: Nickel/nickel (II) hydroxide nanoflakes electrocatalyst for a non-enzymatic glucose oxidation reaction

This work reports the synthesis of nickel/nickel hydroxides nanoflakes (Ni/Ni(OH)₂-NFs) at room temperature via a novel chemical deposition and exfoliation from a liquid crystal template mixture. The nickel ions dissolved in the interstitial aqueous domain of the Brij®78 hexagonal liquid crystal template were deposited by a reducing agent of sodium borohydride that concurrently reduces the nickel ions and generates extreme hydrogen gas bubbles, that exfoliated the nickel/nickel hydroxide layers. The Ni/Ni(OH)₂-NFs crystal structure, morphology, and surface area characterizations revealed the formation of semi-crystalline α-Ni(OH)₂ nanoflakes with a thickness of approximately 10 nm and a specific surface area of about 135 m²/g. The electrochemical measurements of cyclic voltammetry, chronoamperometry, and impedance analysis showed that the Ni/Ni(OH)₂-NFs exhibited significant performance for the glucose non-enzymatic oxidation in an alkaline solution in comparison to the bare-nickel hydroxide (bare-Ni(OH)₂) deposited without surfactant. The Ni/Ni(OH)₂-NFs electrode showed superior glucose oxidation activity over the bare-Ni(OH)₂ catalyst with a sensitivity of 1.078 mA mM^?1 cm^?2 with a linear concentration dependency range from 0.2 to 60 mM and a detection limit of 0.2 mM (S/N = 3). The enhanced electrochemical active surface area and mesoporosity of the 2D nanoflakes make the Ni/Ni(OH)₂-NFs a promising catalyst in the application of glucose non-enzymatic sensing.     

Superabsorbent polymer binder for achieving MnO2 supercapacitors of greatly enhanced capacitance density

One common dilemma encountered in designing a supercapacitor electrode is that the specific capacitance (C_s) of the active material decreases significantly as the active-material loading (mass area^? 1) increases. As a result, the geometric capacitance density (GCD; Farad area^? 1) of the electrode does not scale up linearly but gradually levels off with increasing loading. For MnO₂ supercapacitors, this problem has been solved to a great extent by introducing a superabsorbent polymer (SAP) binder, namely polyacrylic acid (PAA), to form composite particles with MnO₂. Other than acting as a binder to bound together MnO₂ particles, the SAP is believed to facilitate distribution of electrolyte throughout the active layer owing to its electrolyte-absorbing and swelling behaviors. The C_s of MnO₂ remains almost unchanged as the oxide loading varies over a wide range (1.5–6.5 mg cm^? 2) of heavy active-material loading. In addition, putting PAA throughout the entire active layer helps to magnify the specific interaction between PAA and MnO₂ that is known to enhance the capacitance of individual MnO₂ particles. The success in combining both high C_s and high active-material loading results in GCD of ca. 1.8–1.4 F cm^? 2 even under very high current densities (ca. 35–260 mA cm^? 2 or 5–40 A g^? 1-MnO₂).