Noble-Metal-Metalloid Alloy Architectures: Mesoporous Amorphous Iridium-Tellurium Alloy for Electrochemical N2 Reduction.

Amorphous noble metals with high surface areas have attracted significant interest as heterogeneous catalysts due to the numerous dangling bonds and abundant unsaturated surface atoms created by the amorphous phase. However, synthesizing amorphous noble metals with high surface areas remains a significant challenge due to strong isotropic metallic bonds. This paper describes the first example of a mesoporous amorphous noble metal alloy [iridium-tellurium (IrTe)] obtained using a micelle-directed synthesis method. The resulting mesoporous amorphous IrTe electrocatalyst exhibits excellent performance in the electrochemical N2 reduction reaction. The ammonia yield rate is 34.6 µg mg-1 h-1 with a Faradaic efficiency of 11.2% at -0.15 V versus reversible hydrogen electrode in 0.1 M HCl solution, outperforming comparable crystalline and Ir metal counterparts. The interconnected porous scaffold and amorphous nature of the alloy create a complementary effect that simultaneously enhances N2 absorption and suppresses the hydrogen evolution reaction. According to theoretical simulations, incorporating Te in the IrTe alloy effectively strengthens the adsorption of N2 and lowers the Gibbs free energy for the rate-limiting step of the electrocatalytic N2 reduction reaction. Mesoporous chemistry enables a new route to achieve high-performance amorphous metalloid alloys with properties that facilitate the selective electrocatalytic reduction of N2.

Porous and Partially Dehydrogenated Fe2+ -Containing Iron Oxyhydroxide Nanosheets for Efficient Electrochemical Nitrogen Reduction Reaction (ENRR).

The design and development of efficient catalysts for electrochemical nitrogen reduction reaction (ENRR) under ambient conditions are critical for the alternative ammonia (NH3 ) synthesis from N2 and H2 O, wherein iron-based electrocatalysts exhibit outstanding NH3 formation rate and Faradaic efficiency (FE). Here, the synthesis of porous and positively charged iron oxyhydroxide nanosheets by using layered ferrous hydroxide as a starting precursor, which undergoes topochemical oxidation, partial dehydrogenated reaction, and final delamination, is reported. As the electrocatalyst of ENRR, the obtained nanosheets with a monolayer thickness and 10-nm mesopores display exceptional NH3 yield rate (28.5 µg h-1 mgcat. -1 ) and FE (13.2%) at a potential of -0.4 V versus RHE in a phosphate buffered saline (PBS) electrolyte. The values are much higher than those of the undelaminated bulk iron oxyhydroxide. The larger specific surface area and positive charge of the nanosheets are beneficial for providing more exposed reactive sites as well as retarding hydrogen evolution reaction. This study highlights the rational control on the electronic structure and morphology of porous iron oxyhydroxide nanosheets, expanding the scope of developing non-precious iron-based highly efficient ENRR electrocatalysts.

The Core/Shell Structure P Doped MoS2 @Ni3 S2 Nanorods Array for High Current Density Hydrogen Evolution in Alkaline and Acidic Electrolyte.

Electrocatalysis is the most promising strategy to generate clean energy H2 , and the development of catalysts with excellent hydrogen evolution reaction (HER) performance at high current density that can resist strong alkaline and acidic electrolyte environment is of great significance for practical industrial application. Therefore, a P doped MoS2 @Ni3 S2 nanorods array (named P-NiMoS) was successfully synthesized through successive sulfuration and phosphorization. P-NiMoS presents a core/shell structure with a heterojunction between MoS2 (shell) and Ni3 S2 (core). Furthermore, the doping of P modulates the electronic structure of the P-NiMoS; the electrons transfer from the t2g orbital of Ni element to the eg empty orbital of Mo element through the Ni-S-Mo bond at the Ni3 S2 and MoS2 heterojunction, facilitating the hydrogen evolution reaction. As a result, P-NiMoS exhibits excellent HER activity; the overpotential is 290 mV at high current density of 250 mA cm-2 in alkaline electrolyte, which is close to Pt/C (282 mV@250 mA cm-2 ), and P-NiMoS can stably evolve hydrogen for 48 h.

Aprotic Lithium-Carbon Dioxide Batteries: Reaction Mechanism and Catalyst Design.

In recent years, the combustion of fossil fuels leads to the release of a large amount of CO2 gas, which induces the greenhouse effect and the energy crisis. To solve these problems, researchers have turned their focus to a novel Li-CO2 battery (LCB). LCB has received much attention because of its high theoretical energy density and reversible CO2 reduction/evolution process. So far, the emerging LCB still faces many challenges derived from the slow reaction kinetics of discharge products. In this review, the latest status and progress of LCB, especially the influence of the structure design of cathode catalysts on the battery performance, are systematically elaborated. This review summarizes in detail the existing issues and possible solutions of LCB, which is of high research value for further promoting the development of Li-Air battery.

Electrochemical Fabrication of Porous Au Film on Ni Foam for Nitrogen Reduction to Ammonia.

Electrochemical reduction of N2 to NH3 provides an alternative strategy to replace the industrial Haber-Bosch process for facile and sustainable production of NH3 . The development of efficient electrocatalysts for the nitrogen reduction reaction (NRR) is highly desired. Herein, a micelle-assisted electrodeposition method is presented for the direct fabrication of porous Au film on Ni foam (pAu/NF). Benefiting from its interconnected porous architectonics, the pAu/NF exhibits superior NRR performance with a high NH3 yield rate of 9.42 µg h-1 cm-2 and a superior Faradaic efficiency of 13.36% at -0.2 V versus reversible hydrogen electrode under the neutral electrolyte (0.1 m Na2 SO4 ). The proposed micelle-assisted electrodeposition strategy is highly valuable for future design of active NRR catalysts with desired compositions toward various electrocatalysis fields.

Ultralong Ternary PtRuTe Mesoporous Nanotubes Fabricated by Micelle Assembly with a Self-Sacrificial Template.

High surface area and fast mass transport rate are important to enhance the activity and stability of catalysts. In this work, tellurium nanowires and F127 triblock copolymer are used as self-sacrificial and soft templates, respectively, to synthesize PtRuTe mesoporous nanotubes (MNTs). The designed PtRuTe MNTs show uniformly distributed mesopores and an internally hollow structure, which can effectively improve Pt utilization, the catalytic activity and durability, and CO tolerance for the methanol oxidation reaction. Very different from previous 1D metallic catalysts with solid interiors and smooth surfaces, PtRuTe MNTs are unique, with a mesoporous exterior and hollow interior. The facile route presented herein is very feasible for fabricating 1D mesoporous metallic catalysts.

PtPdRh Mesoporous Nanospheres: An Efficient Catalyst for Methanol Electro-Oxidation.

Porous multimetallic alloyed nanostructures possess unique physical and chemical properties to generate promising potential in fuel cells. However, the controllable synthesis of this kind of materials still remains challenging. Herein, we report a facile method for the one-pot, high-yield synthesis of trimetallic PtPdRh mesoporous nanospheres (PtPdRh MNs) under mild conditions. The resultant PtPdRh MNs possess the features of uniform shape, a narrow size distribution, plenty of well-defined mesopores, highly open structure, and multicomponent effects, which impart advantages such as large surface area, favorable mass diffusion, high utilization of electrocatalysts, and synergy among the various metal components. Benefitting from the synergetic effects originating from the multimetallic composition and unique mesoporous structure, the as-prepared PtPdRh MNs exhibit remarkably enhanced electrocatalytic performance for methanol oxidation reaction relative to bimetallic PtPd MNs and commercial Pt/C catalyst.

All-metallic nanorattles consisting of a Pt core and a mesoporous PtPd shell for enhanced electrocatalysis.

The fabrication of nanorattles with controllable compositions and structures is very important for catalytic applications. Herein, we propose a facile method for synthesis of very unique all-metallic nanorattle consisting of a Pt core and a mesoporous PtPd shell (named Pt@mPtPd). Owing to its spatially and locally separated active inner Pt core and mesoporous PtPd shell, the Pt@mPtPd nanorattle shows the enhanced performance for oxygen reduction reaction. The newly designed Pt@mPtPd nanorattle is quite different from traditional nanorattles with porous carbon and silica shell in its catalytically functional mesoporous metallic shell. The proposed facile method is highly valuable for the design of all-metallic nanorattle with controllable compositions and desired functions.

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution.

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy-carbon core-shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10-30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2-6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction.

The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

Spatially-controlled NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 cores and MnO2 flake shells: an efficient catalyst for oxygen evolution reaction.

Control of structures and components of the nanoarray catalysts is very important for electrochemical energy conversion. Herein, unique NiCo2O4@MnO2 core-shell nanoarray with hollow NiCo2O4 Cores and MnO2 flake shells is in situ fabricated on carbon textile via a two-step hydrothermal treatment followed by a subsequent annealing. The as-made nanoarray is highly active and durable catalyst for oxygen evolution reaction in alkaline media attribute to the synergetic effect derived from spatially separated nanoarray with favorable NiCo2O4 and MnO2 compositions.

Tri-metallic PtPdAu mesoporous nanoelectrocatalysts.

The design of mesoporous materials with multi-metallic compositions is highly important for various electrocatalytic applications. In this paper, we demonstrate an efficient method to directly fabricate tri-metallic PtPdAu mesoporous nanoparticles (PtPdAu MNs) in a high yield, which is simply performed by heating treatment of the reaction mixture aqueous solution at 40 °C for 4 h. Profiting from its mesoporous structure and multi-metallic components, the as-prepared PtPdAu MNs exhibit enhanced electrocatalytic activities toward both methanol oxidation reaction and oxygen reduction reaction in comparison with bi-metallic PtPd MNs and commercial Pt/C catalyst.

Functional Species Encapsulated in Nitrogen-Doped Porous Carbon as a Highly Efficient Catalyst for the Oxygen Reduction Reaction.

The scarcity, high cost, and poor stability of precious metal-based electrocatalysts have stimulated the development of novel non-precious metal catalysts for the oxygen reduction reaction (ORR) for use in fuel cells and metal-air batteries. Here, we fabricated in situ a hybrid material (Co-W-C/N) with functional species (tungsten carbide and cobalt nanoparticles) encapsulated in an N-doped porous carbon framework, through a facile multi-constituent co-assembly method combined with subsequent annealing treatment. The unique structure favors the anchoring active nanoparticles and facilitates mass transfer steps. The homogenously distributed carbide nanoparticles and adjacent Co-N-C sites lead to the electrocatalytic synergism for the ORR. The existence of Co and W can promote the graphitization of the carbon matrix. Benefiting from its structural and material superiority, the Co-W-C/N electrocatalyst exhibits excellent electrocatalytic activity (with a half-wave potential of 0.774 V vs. reversible hydrogen electrode (RHE)), high stability (96.3 % of the initial current remaining after 9000 s of continuous operation), and good immunity against methanol in alkaline media.

High-Loading Nano-SnO2 Encapsulated in situ in Three-Dimensional Rigid Porous Carbon for Superior Lithium-Ion Batteries.

Tin oxide nanoparticles (SnO2 NPs) have been encapsulated in situ in a three-dimensional ordered space structure. Within this composite, ordered mesoporous carbon (OMC) acts as a carbon framework showing a desirable ordered mesoporous structure with an average pore size (≈6 nm) and a high surface area (470.3 m(2) g(-1)), and the SnO2 NPs (≈10 nm) are highly loaded (up to 80 wt %) and homogeneously distributed within the OMC matrix. As an anode material for lithium-ion batteries, a SnO2 @OMC composite material can deliver an initial charge capacity of 943 mAh g(-1) and retain 68.9 % of the initial capacity after 50 cycles at a current density of 50 mA g(-1), even exhibit a capacity of 503 mA h g(-1) after 100 cycles at 160 mA g(-1). In situ encapsulation of the SnO2 NPs within an OMC framework contributes to a higher capacity and a better cycling stability and rate capability in comparison with bare OMC and OMC ex situ loaded with SnO2 particles (SnO2/OMC). The significantly improved electrochemical performance of the SnO2@OMC composite can be attributed to the multifunctional OMC matrix, which can facilitate electrolyte infiltration, accelerate charge transfer, and lithium-ion diffusion, and act as a favorable buffer to release reaction strains for lithiation/delithiation of the SnO2 NPs.

Preparation of the TiO2/Graphic Carbon Nitride Core-Shell Array as a Photoanode for Efficient Photoelectrochemical Water Splitting.

The photoelectrochemical (PEC) oxygen evolution reaction over a photoanode is a promising process for renewable energy. The fascinating properties of graphic carbon nitride (g-CN) in water splitting make the photoelectrode engineering of it for PEC use quite meaningful. In this work, we report the fabrication of the core-shell-structured TiO2/g-CN composite film by hydrothermal growth for TiO2 nanorod arrays and solvothermal growth for the g-CN layer. Herein, TiO2 is used as an effective electron-transfer layer, and g-CN is used as a visible light absorption layer. Different reaction conditions were investigated in order to obtain the uniform TiO2/g-CN nanorod core-shell structure. Outstanding photoelectrochemical performances of the optimized composites were obtained compared to that of pristine TiO2 or g-CN because the high-quality heterojunction between g-CN and TiO2 turned out to effectively reduce the recombination of charge carriers and improve the photoelectric conversion ability. Thus, the photocurrent density under visible light of TiO2/g-CN reached 80.9 µA cm-2, which is 21 times that of g-CN under 0.6 V (vs SCE). Finally, a systematic photoelectrocatalytic mechanism of charge carrier migration and the recombination path in the TiO2/g-CN nanorod core-shell heterojunction was proposed, which can be considered to be a probable explanation of efficient PEC performance.

Treatment of anastomotic stricture after rectal cancer operation by magnetic compression technique: A case report.

BACKGROUND: The treatment of postoperative anastomotic stenosis (AS) after resection of colorectal cancer is challenging. Endoscopic balloon dilation is used to treat stenosis in such cases, but some patients do not show improvement even after multiple balloon dilations. Magnetic compression technique (MCT) has been used for gastrointestinal anastomosis, but its use for the treatment of postoperative AS after colorectal cancer surgery has rarely been reported. CASE SUMMARY: We report a 72-year-old man who underwent radical resection of colorectal cancer and ileostomy one year ago. An ileostomy closure was prepared six months ago, but colonoscopy revealed a narrowing of the rectal anastomosis. Endoscopic balloon dilation was performed three times, but colonoscopy showed no significant improvement in stenosis. The AS was successfully treated using MCT. CONCLUSION: MCT is a minimally invasive method that can be used for the treatment of postoperative AS after colorectal cancer surgery.

Novel magnetic compression technique for the treatment of postoperative anastomotic stenosis in rectal cancer: A case report.

BACKGROUND: The treatment of postoperative anastomotic stenosis after excision of rectal cancer is challenging. Endoscopic balloon dilation and radial incision are not effective in all patients. We present a new endoscopy-assisted magnetic compression technique (MCT) for the treatment of rectal anastomotic stenosis. We successfully applied this MCT to a patient who developed an anastomotic stricture after radical resection of rectal cancer. CASE SUMMARY: A 50-year-old man had undergone laparoscopic radical rectal cancer surgery at a local hospital 5 months ago. A colonoscopy performed 2 months ago indicated that the rectal anastomosis was narrow due to which ileostomy closure could not be performed. The patient came to the Magnetic Surgery Clinic of the First Affiliated Hospital of Xi'an Jiaotong University after learning that we had successfully treated patients with colorectal stenosis using MCT. We performed endoscopy-assisted magnetic compression surgery for rectal stenosis. The magnets were removed 16 d later. A follow-up colonoscopy performed after 4 months showed good anastomotic patency, following which, ileostomy closure surgery was performed. CONCLUSION: MCT is a simple, non-invasive technique for the treatment of anastomotic stricture after radical resection of rectal cancer. The technique can be widely used in clinical settings.

Constructing Fast Transmembrane Pathways in a Layered Double Hydroxide Nanosheets/Nanoparticles Composite Film for an Inorganic Anion-Exchange Membrane.

Anion-exchange membranes (AEMs) with high conductivity are crucial for realizing next-generation energy storage and conversion systems in an alkaline environment, promising a huge advantage in cost reduction without using precious platinum group metal catalysts. Layered double hydroxide (LDH) nanosheets, exhibiting a remarkably high hydroxide ion (OH-) conductivity approaching 10-1 S cm-1 along the in-plane direction, may be regarded as an ideal candidate material for the fabrication of inorganic solid AEMs. However, two-dimensional anisotropy results in a substantially low conductivity of 10-6 S cm-1 along the cross-plane direction, which poses a hurdle to achieve fast ion conduction across the membrane comprising restacked nanosheets. In the present work, a composite membrane was prepared based on mixing/assembling micron-sized LDH nanosheets with nanosized LDH platelets (nanoparticles) via a facile vacuum filtration process. The hybridization with nanoparticles could alter the orientation of LDH nanosheets and reduce the restacking order, forming diversified fast ion-conducting pathways and networks in the composite membrane. As a result, the transmembrane conductivity significantly improved up to 1000-fold higher than that composed of restacked nanosheets only, achieving a high conductivity of 10-2 to 10-1 S cm-1 in both in-plane and cross-plane directions.