Systematic Engineering on Ni-Based Nanocatalysts Effectively Promote Hydrogen Evolution Reaction.

Designing a synthesis of ultra-small Ni-based nanomaterials with high intrinsic activity and stability in alkaline hydrogen evolution reaction (HER) is a major challenge. Herein, a series of noble metal doped ultra-small size (4 nm) M-Ni/NiO nanoparticles supported on CNT are rationally designed by a solvent-free microwave reduction method that is fast (60 s), simple, includes no surfactants, extensive (>1 g), and has high yield (82.7%). The Ir-Ni/NiO@CNT has superior performance with a low overpotential of 24.6 mV at 10 mA cm-2 . In addition, the turnover frequency (TOF) value up to 2.51 s-1 and the exchange current density reaches 4.34 mA cm-2 , indicating that the catalyst has better intrinsic catalytic activity. It is further proved by density functional theory (DFT) that the NiO surface is conducive to the adsorption of OH* in the Volmer step while the Ni is inclined to adsorb H*, which synergistically promotes the water-splitting reaction, thereby increasing the catalytic rate of HER. It is believed that this work will provide valuable contributions and inspirations toward the large-scale production of high-performance Ni-based electrocatalysts for HER.

Noble Metal (Pt, Rh, Pd, Ir) Doped Ru/CNT Ultra-Small Alloy for Acidic Hydrogen Evolution at High Current Density.

There are still great challenges to prepare high-efficiency Ru-based catalysts that are superior to Pt/C under acidic conditions, especially under high current conditions. In this work, a series of surfactant-free noble metal doped Ru/CNT (M-Ru/CNT, M = Pt, Rh, Pd, Ir, CNT stands for carbon nanotube) are prepared by microwave reduction method in 1 minute with ≈3-3.5 nm in size for the first time. In 0.5 m H2 SO4 , the overpotential of Pt-Ru/CNT (Pt: 4.94 at %) is only 12 mV. What's more, it also has much larger electrochemical surface area and intrinsic activity than Pt/C. Pt-Ru/CNT still has an ultra-small overpotential under high current density (113 mV at 500 mA cm-2 , 155 mV at 1000 mA cm-2 ). At the same time, it possesses excellent stability regardless of high current or low current after the durability test of 100 h. Theoretical calculation also deeply reveals that Ru is the main adsorption site of H+ . The comparison of the electronic structure of a series of noble metals adjusted by Ru shows that Pt has the most excellent Gibbs free energy of the adsorbed hydrogen and promotes the desorption of the product.

High Valence M-Incorporated PdCu Nanoparticles (M = Ir, Rh, Ru) for Water Electrolysis in Alkaline Solution.

The high-valence metal catalysts show extraordinary talent in various electrochemical reactions. However, there is no facile method to synthesize high-valence noble metal-based materials. Herein, we synthesized the different high valence noble metal M-incorporated PdCu nanoparticles (M = Ir, Ru, Rh) by the assistant of Fe3+ and exhibit excellent performance for water electrolysis. In 0.1 M KOH, the OER and HER mass activities of Ir16-PdCu/C were 50.5 and 16.5 times as much as PdCu/C, and achieved a current density of 10 mA cm-2 at 1.63 V when worked for overall water splitting. DFT calculation revealed that the incorporating of high valence Ir could optimize the binding energy of the intermediate products, and promote the evolution of oxygen and hydrogen. Ex situ XPS shows that the huge amount of oxidized Ir (V) formed in OER could promote the formation of O-O bonds.

Ordered Vacancies on the Body-Centered Cubic PdCu Nanocatalysts.

Defect engineering has become one of the important considerations in today's electrocatalyst design. However, the vacancies in the ordered crystal structure (especially body-centered cubic (bcc) and the effect of ordered vacancies (OVs) on the electronic fabric have not been researched yet. In this work, we report the inaugural time of the generation of OVs in the bcc architecture and discuss the insight of the modulation system of the material and its part in the electrochemical N2 reduction reaction (NRR). OV-PdCu-2 achieves the highest Faradaic efficiency value of 21.5% at 0.05 V versus RHE. When the potential increases to 0 V versus RHE, the highest ammonia yield is 55.54 µg h-1 mgcat-1, which is significantly better than the unetched PdCu nanoparticles (12.83 µg h-1 mgcat-1). It is the latest reported catalyst to date in the NRR process at 0 V versus RHE (see Supporting Information).

Superfast Synthesis of Densely Packed and Ultrafine Pt-Lanthanide@KB via Solvent-Free Microwave as Efficient Hydrogen Evolution Electrocatalysts.

At present, it is still a great challenge to synthesize refractory Pt-based electrocatalysts with excellent active specific surface area, specific activity, and stability by a simple method. Here, a superfast and solvent-free microwave strategy is reported to synthesize refractory ultrafine (≈3 nm) Pt-lanthanide@Ketjen Black (PtM@KB, M = La, Gd, Tb, Er, Tm, and Yb) alloy with densely packed as efficient hydrogen evolution electrocatalysts in a domestic microwave oven for the first time. The optimized Pt61 La39 @KB delivers excellent hydrogen evolution reaction (HER) activity with a low overpotential of 38 mV (10 mA cm-2 ) and a high TOF value of 44.13 s-1  (100 mV) in 0.5 m H2 SO4 , and performs well in 1.0 m KOH. This method can also be used to grow catalysts on carbon cloth (CC) directly. PtLa@CC shows an overpotential of 99 mV (1000 mA cm-2 ) in 0.5 m H2 SO4 and can maintain activity after 500 h. Theoretical calculations reveal the enhanced stability and activity owing to the higher vacancy formation energy of Pt atoms and the optimized value of ΔGH* . Solvent-free microwave strategy constitutes a significant insight into the development of refractory electrocatalyst with ultrafine size and highly dense, which can also work well at high current densities.

Free radicals promote electrocatalytic nitrogen oxidation.

In this work, we introduce hydroxyl radicals into the electrocatalytic nitrogen oxidation reaction (NOR) for the first time. Cobalt tetroxide (Co3O4) acts not only as an electrocatalyst, but also as a nanozyme (in combination with hydrogen peroxide producing ˙OH), and can be used as a high-efficiency nitrogen oxidation reaction (NOR) electrocatalyst for environmental nitrate synthesis. Co3O4 + ˙OH shows an excellent nitrogen oxidation reaction (NOR) performance among Co3O4 catalysts in 0.1 M Na2SO4 solution. At an applied potential of 1.7 V vs. RHE, the HNO3 yield of Co3O4 + ˙OH reaches 89.35 µg h-1 mgcat -1, which is up to 7 times higher than that of Co3O4 (12.8 µg h-1 mgcat -1) and the corresponding FE is 20.4%. The TOF of Co3O4 + ˙OH at 1.7 V vs. RHE reaches 0.58 h-1, which is higher than that of Co3O4 (0.083 h-1), demonstrating that free radicals greatly enhance the intrinsic activity. Density functional theory (DFT) demonstrates that ˙OH not only can drive nitrogen adsorption, but also can decrease the energy barrier (rate-determining step) of N2 to N2OH*, thus producing great NOR activity.

Porous PdWM (M = Nb, Mo and Ta) Trimetallene for High C1 Selectivity in Alkaline Ethanol Oxidation Reaction.

Direct ethanol fuel cells are among the most efficient and environmentally friendly energy-conversion devices and have been widely focused. The ethanol oxidation reaction (EOR) is a multielectron process with slow kinetics. The large amount of by-product generated by incomplete oxidation greatly reduces the efficiency of energy conversion through the EOR. In this study, a novel type of trimetallene called porous PdWM (M = Nb, Mo and Ta) is synthesized by a facile method. The mass activity (15.6 A mgPd -1 ) and C1 selectivity (55.5%) of Pd50 W27 Nb23 /C trimetallene, obtained after optimizing the compositions and proportions of porous PdWM, outperform those of commercial Pt/C (1.3 A mgPt -1 , 5.9%), Pd/C (5.0 A mgPd -1 , 7.2%), and Pd97 W3 /C bimetallene (9.5 A mgPd -1 , 14.1%). The mechanism by which Pd50 W27 Nb23 /C enhances the EOR performance is evaluated by in situ Fourier transform infrared spectroscopy and density functional theory calculations. It is found that W and Nb enhance the adsorption of CH3 CH2 OH and oxophilic high-valence Nb accelerates the subsequent oxidation of CO and CHx species. Moreover, Nb promotes the cleavage of CC bonds and increases the C1 selectivity. Pd60 W28 Mo12 /C and Pd64 W27 Ta9 /C trimetallene synthesized by the same method also exhibit excellent EOR performance.

Correction: High-efficiency methanol oxidation electrocatalysts realized by ultrathin PtRuM-O (M = Ni, Fe, Co) nanosheets.

Correction for 'High-efficiency methanol oxidation electrocatalysts realized by ultrathin PtRuM-O (M = Ni, Fe, Co) nanosheets' by Yue Pan et al., Chem. Commun., 2020, 56, 9028-9031, DOI: .

Solvent-free microwave synthesis of ultra-small Ru-Mo2C@CNT with strong metal-support interaction for industrial hydrogen evolution.

Exploring a simple, fast, solvent-free synthetic method for large-scale preparation of cheap, highly active electrocatalysts for industrial hydrogen evolution reaction is one of the most promising work today. In this work, a simple, fast and solvent-free microwave pyrolysis method is used to synthesize ultra-small (3.5 nm) Ru-Mo2C@CNT catalyst with heterogeneous structure and strong metal-support interaction in one step. The Ru-Mo2C@CNT catalyst only exhibits an overpotential of 15 mV at a current density of 10 mA cm-2, and exhibits a large turnover frequency value up to 21.9 s-1 under an overpotential of 100 mV in 1.0 M KOH. In addition, this catalyst can reach high current densities of 500 mA cm-2 and 1000 mA cm-2 at low overpotentials of 56 mV and 78 mV respectively, and it displays high stability of 1000 h. This work provides a feasible way for the reasonable design of other large-scale production catalysts.

Optimizing Energy Transfer in Nanostructures Enables In Vivo Cancer Lesion Tracking via Near-Infrared Excited Hypoxia Imaging.

To explore highly sensitive and low-toxicity techniques for tracking and evaluation of non-small-cell lung cancer (NSCLC), one of the most mortal tumors in the world, it is utterly imperative for doctors to select the appropriate treatment strategies. Herein, developing near-infrared (NIR) excited nanosensors, in which the donor and acceptor pairs within a biological metal-organic framework (bio-MOF) matrix are precisely controlled to rationalize upconversion Förster resonance energy transfer (FRET), is suggested for detecting the O2 concentration inside tumors with reduced signal disturbance and health detriment. Under NIR excitation, as-fabricated core/satellite nanosensors exhibit much improved FRET efficiency and reversible hypoxic response with high sensitivity, which are effective both in vitro and in vivo (zebrafish) for cycling normoxia-hypoxia imaging. Significantly, combined with a reliable preclinical genetically engineered murine model, such nanosensors successfully realize tracking of in vivo NSCLC lesions upon clear and gradient hypoxia signals without apparent long-term biotoxicity, illustrating their exciting potential for efficient NSCLC evaluation and prognosis.

High-efficiency methanol oxidation electrocatalysts realized by ultrathin PtRuM-O (M = Ni, Fe, Co) nanosheets.

A general method for controlling the synthesis of a class of ultrathin PtRuM-O (M = Ni, Fe, Co) NSs is reported for the first time. By optimizing the metal ratio, the Pt7RuNi2-O NS catalyst is found to have the highest electrocatalytic activity (mass activity, 3.57 A mgPt-1) for the MOR among PtRuM-O NSs and PtRu-O NSs, which is 10.5 times higher than that of commercial Pt/C (0.34 A mgPt-1). And the Pt7RuNi2-O NSs also have better stability and CO anti-poisoning properties in the prepared materials. In addition, the ultrathin Pt7RuNi2-O NS catalyst also shows the highest performance among reported Pt-based catalysts for the MOR in acidic medium.

Advanced Ultrathin RuPdM (M = Ni, Co, Fe) Nanosheets Electrocatalyst Boosts Hydrogen Evolution.

The hydrogen evolution reaction (HER) is one of the most significant reactions in the electrolysis water process, and electrocatalysts which possess high mass activity and excellent stability are the most important driving factors to improve the efficiency of HER. As for the efficient commercially electrocatalyst, Pt/C is limited in development because of its high cost. Therefore, the study of non-Pt high-efficiency catalysts is particularly important at this moment. Here, we creatively report for the first time a kind of RuPdM (M= Ni, Co, Fe) ultrathin nanosheets (NSs), which exhibit extraordinary electrochemical properties for HER under alkaline conditions. The overpotential of optimized trimetallic Ru38Pd34Ni28 ultrathin NSs is only 20 mV (10 mA cm-2), and the mass activity reaches 6.15 A mg-1 noble metal at -0.07 V vs RHE. It can be compared to Pt-based electrocatalysts, which have the highest mass activity currently reported. The durability tests also prove that the stability of the electrocatalyst is outstanding. DFT calculations disclose that the flexible modulation of electronic structures of RuPd ultrathin NSs is achieved by utilizing the additional 3d transition metals Fe, Co, and Ni. In particular, the Ni-3d bands act as the continuous electron-supply center for Ru to ensure an efficient electron transfer toward the adsorbates. Meanwhile, the stable Pd sites are critical for coupling the O-2pπ orbital in the initial H2O splitting with a facile barrier. This work will open up a new era of non-Pt materials for alkaline hydrogen evolution toward practical application.