Alloying cobalt with ruthenium in nitrogen doped graphene layers for developing highly active hydrogen evolution electrocatalysts in alkaline media

Subject Code:B01With the support by the National Natural Science Foundation of China,a creative study by the research group led by Prof.Chen Qianwang(陈乾旺)from the University of Science and Technology of China and High Magnetic Field Laboratory,Hefei Institutes of Physical Science,Chinese Academy of

Highly Active and Stable Ni_2P/SiO_2 Catalyst for Hydrogenation of C_9 Petroleum Resin

Catalytic hydrogenation is an appropriate method for the improvement of C9 petroleum resin（C9PR） quality. In this study, the Ni2P/SiO2（containing 10% of Ni） catalyst prepared by the temperature-programmed reduction（TPR） method was used for hydrogenation of C9 petroleum resins. The effect of reaction conditions on catalytic performance was studied, and the results showed that the optimum reaction temperature, pressure and liquid hourly space velocity（LHSV） was 250 ℃, 6.0 MPa, and 1.0 h-1, respectively. The bromine numbers of hydrogenated products were maintained at low values（250 mg Br/100g） within 300h, showing the high activity and stability of Ni2P/SiO2 catalyst. The fresh and spent catalysts were characterized by X-ray diffraction（XRD）, BET surface area（BET） analysis, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, Fourier transform infrared（FTIR） pyridine adsorption, and X-ray photoelectron spectroscopy（XPS）. Compared with the traditional sulfurated-Ni W catalysts, Ni2P possessed globe-like structure instead of layered structure like the active phase of Ni WS, thereof exposing more active sites, which were responsible for the high activity of Ni2P/SiO2 catalyst. The stability of Ni2P/SiO2 catalyst was probably attributed to its high sulfur tolerance, antisintering, anti-coking and carbon-resistance ability. These properties might be further ascribed to the special Ni-P-S surface phase, high thermal stability of Ni2P nanoparticles and weak surface acidity for the Ni2P/SiO2 catalyst.

Bicarbonate activation of hydrogen peroxide: A new emerging technology for wastewater treatment

The serious limitations of available technologies for decontamination of wastewater have compelled researchers to search for alternative solutions. Catalytic treatment with hydrogen peroxide, which appears to be one of the most efficient treatment systems, is able to degrade various organics with the help of powerful ·OH radicals. This review focuses on recent progress in the use of bicarbonate activated hydrogen peroxide for wastewater treatment. The introduction of bicarbonate to pollutant treatment has led to appreciable improvements, not only in process efficiency, but also in process stability. This review describes in detail the applications of this process in homogeneous and heterogeneous systems. The enhanced degradation, limited or lack of leaching during heterogeneous degradation, and prolonged catalysts stability during degradation are salient features of this system. This review provides readers with new knowledge regarding bicarbonate, including the fact that it does not always harm pollutant degradation, and can significantly benefit degradation under some conditions.

Catalytic Performance of Carbon Materials Supported Pd Nanoparticles in Selective Hydrogenation of Acetylene

Pd/C catalysts were prepared by deposited Pd nanoparticles （NPs） on different carbon supports including activated carbon （AC）, graphite oxide （GO）, and reduced graphite oxide （rGO） using sol-immobilization method. Through transmission electron microscopy, powder X-ray di raction, and X-ray photoelectron spectroscopy, the role of the carbon supports for the catalytic performances of Pd/C catalysts was examined in selective hydrogenation of acetylene. The results indicate that Pd/AC exhibited higher activity and selectivity than Pd/GO and Pd/rGO in the gas phase selective hydrogenation of acetylene. Thermal and chemical treatment of AC supports also have some effect on the catalytic performance of Pd/AC catalysts. The differences in the activity and selectivity of various Pd/C catalysts were partly attributed to the metal-support interaction.

Acetylene hydrochlorination over supported ionic liquid phase(SILP)gold-based catalyst:Stabilization of cationic Au species via chemical activation of hydrogen chloride and corresponding mechanisms

The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based supported ionic liquid phase(Au–SILP)technology with the[N(CN)2^–]anion.This strategy enables HCl to accept electrons from[N(CN)2^–]anions in Au–[N(CN)2^–]complexes rather than from pure[Bmim][N(CN)2],leading to notable improvement in both the reaction path and the stability of the catalyst without changing the reaction triggered by acetylene adsorption.Furthermore,the induction period of the Au–SILP catalyst was shown to be absent in the reaction process due to the high Au(III)content in the Au(Ⅲ)/Au(Ⅰ)site and the high substrate diffusion rate in the ionic liquid layer.This work provides a facile method to improve the stability of Au-based catalysts for acetylene hydrochlorination.

Determination of reactive oxygen generated from natural medicines and their antibacterial activity

Extracts of 16 natural medicine powders {Galla chinensis,Malloti cortex,Cassiae semen,Sophorae radix,Myricae cortex,Crataegi fructus,Gambit,Mume fructus,Geranii herba,Phellodendri cortex,Coptidis rhizoma,Swertiae herba,and Cinnamomi cortex） were assayed for reactive oxygen concentrations using the peroxyoxalate chemiluminescent detection system.High luminescence intensity was observed in Galla chinensis,Geranii herba,Malloti cortex,Myricae cortex,and Cinnamomi cortex.Additional experiments identified the reactive oxygen species as hydrogen peroxide.Galla chinensis generated 2.4 × 10^（-4） mol/L hydrogen peroxide from a 1 mg/mL solution.In bacterial growth tests,Galla chinensis extract had antibacterial activity against Escherichia coli.Staphylococcus aureus,Bacteroides thetaiotaomicron,Campylobacter sputorum biovar sputorum.Streptococcus salivarius thermophilus,Lactobacillus casei,and Bifidobacterium longum infantis.This antibacterial activity was decreased by the addition of catalase.It revealed that hydrogen peroxide which Galla chinensis produced participated in antibacterial activity.

Taming Electrons in Pt/C Catalysts to Boost the Mesokinetics of Hydrogen Production

Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties.Herein,we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is,for the electron-withdrawing/donating oxygencontaining groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles.Taking the ammonia borane hydrolysis as an example,a combination of density functional theory(DFT)calculations,advanced characterizations,and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry,Pt charge state and binding energy,activation entropy/enthalpy,and resultant catalytic activity.After decoupling the influences of other factors,the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site,contributing to a 15-fold increment in the hydrogen generation rate.Further incorporating the Pt charge with the number of Pt active sites,a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance.Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

Cobalt nanoparticles encapsulated in nitrogen-doped carbon for room-temperature selective hydrogenation of nitroarenes

Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized by pyrolyzing a mixture of a cobalt salt,an inexpensive organic molecule,and carbon nitride.Using the Co@NC catalyst,a turnover frequency of^12.3 h?1 and selectivity for 4‐aminophenol of>99.9%were achieved for hydrogenation of 4‐nitrophenol at room temperature and 10 bar H2 pressure.The excellent catalytic performance can be attributed to the cooperative effect of hydrogen activation by electron‐deficient Co nanoparticles and energetically preferred adsorption of the nitro group of nitroarenes to electron‐rich N‐doped carbon.In addition,there is electron transfer from the Co nanoparticles to N‐doped carbon,which further enhances the functionality of the metal center and carbon support.The catalyst also exhibits stable recycling performance and high activity for nitroaromatics with various substituents.

THE SYNTHESIS,HYDROGENATION ACTIVITY AND STRUCTURAL CHARACTERIZATION OF POLY-γ- (L-GLYCYLALANINE) PROPYL SILOXANE PALLADIUM CATALYSTS

This paper describes the synthesis of poly-γ-(L-glycylalanine) propylsiloxane palladium catalysts withdifferent N/Pd molar ratios and their catalytic activity. XPS data of the title catalyst indicated that the active center may be complex compound composed of the -COOH and -NH2 of amino acid ligand and PdCl2. The hydrogenation activity of the title catalysts is very high for acrylonitrile,propenol and acrylic acid,but inactive for a-methyl acrylic acid and 1-decene. The influence of solvents,N/Pd molar tatio,and reaction temperature on catalytic hydrogenation of acrylonitrile was studied respectively.

Solution-based Synthesis of Ni Sb Nanoparticles for Electrochemical Activity in Hydrogen Evolution Reaction

A cost-effective,facile solution-based hot-injection synthetic route has been developed to synthesize NiSb nanoparticles in oleylamine(OAm)using commercially available inexpensive precursor with reducing toxicity at a relatively low temperature of 160℃.Especially,an organic reductant of borane-tert-butylamine complex is intentionally involved in the reaction system to promote a fast reduction of metallic Ni and Sb for the formation of the NiSb nanoparticles.Structural characterizations reveal that the NiSb nanoparticles are hexagonal phase with space group P63/mmc and they are composed of small granules with size about 10 nm that tend to form agglomerates with porous-like geometries.This is the first report on the generation of transition metal antimonide via solution-based strategy,and the asfabricated nanoparticles possess actively electrocatalytic hydrogen evolution reaction(HER)property in acidic electrolytes when the long-chain ligand of OAm adhered on the surface of the nanoparticles is exchanged by ligand-removal and exchange procedure.It is found that the NiSb nanoparticles as a new kind of non-noble-metal HER electrocatalysts only require overpotentials of 437 and 531 mV to achieve high current densities of 10 and 50 mA/cm^2 respectively,as well as exhibit low charge transfer resistance and excellent HER stability.

Experimental Design Technique on Removal of Hydrogen Sulfide using CaO-eggshells Dispersed onto Palm Kernel Shell Activated Carbon：Experiment,Optimization,Equilibrium and Kinetic Studies

This study presents the use of chicken eggshells waste utilizing palm kernel shell based activated carbon（PKSAC） through the modification of their surface to enhance the adsorption capacity of H2S. Response surface methodology technique was used to optimize the process conditions and they were found to be： 500 mg/L for H2S initial concentration, 540 min for contact time and 1 g for adsorbent mass. The impacts of three arrangement factors（calcination temperature of impregnated activated carbon（IAC）, the calcium solution concentration and contact time of calcination） on the H2S removal efficiency and impregnated AC yield were investigated. Both responses IAC yield（IACY, %） and removal efficiency（RE, %） were maximized to optimize the IAC preparation conditions. The optimum preparation conditions for IACY and RE were found as follows： calcination temperature of IAC of 880 ℃, calcium solution concentration of 49.3% and calcination contact time of 57.6 min, which resulted in 35.8% of IACY and 98.2% RE. In addition, the equilibrium and kinetics of the process were investigated. The adsorbent was characterized using TGA, XRD, FTIR, SEM/EDX, and BET. The maximum monolayer adsorption capacity was found to be 543.47 mg/g. The results recommended that the composite of PKSAC and Ca O could be a useful material for H2S containing wastewater treatment.

Sequential reactant water management by complementary multisite catalysts for surpassing platinum hydrogen evolution activity

Alkaline hydrogen evolution reaction(HER)offers a near-zero-emission approach to advance hydrogen energy.However,the activity limited by the multiple reaction steps involving H_(2)O molecules transfer,absorption,and activation still unqualified the thresholds of economic viability.Herein,we proposed a multisite complementary strategy that incorporates hydrophilic Mo and electrophilic V into Ni-based catalysts to divide the distinct steps on atomically dispersive sites and thus realize sequential regulation of the HER process.The Isotopic labeled in situ Raman spectroscopy describes 4-coordinated hydrogen bonded H_(2)O to be free H_(2)O passing the inner Helmholtz plane in the vicinity of the catalysts under the action of hydrophilic Mo sites.Furthermore,potential-dependent electrochemical impedance spectroscopy(EIS)reveals that electrophilic V sites with abundant 3d empty orbitals could activate the lone-pair electrons in the free H_(2)O molecules to produce more protic hydrogen,and dimerize into H_(2) at the Ni sites.By the sequential management of reactive H_(2)O molecules,NiMoV oxides multisite catalysts surpass Pt/C hydrogen evolution activity(49 mV@10 mA∙cm^(-2) over 140 h).Profoundly,this study provides a tangible model to deepen the comprehension of the catalyst–electrolyte interface and create efficient catalysts for diverse reactions.

A Pincer Cobalt Complex as Catalyst with Dual Hydrogenation Activities for Hydrodeoxygenation of Ketones with H2

Reductive deoxygenation of ketones using H_(2) is a highly desirable but also challenging transformation in both chemical synthesis,industrial-scale petroleum and biomass feedstock reforming processes.Herein,we report a cooperative cobalt/Lewis acid (LA)-catalyzed hydrodeoxygenation of ketones using H_(2) as the reductant.In particular,the newly developed pincer cobalt catalyst possesses dual hydrogenation activities for both ketones and alkenes under the same reaction conditions.This reaction features a broad substrate scope,excellent functional-group compatibility,and potential applicability.

An Integrated Carbon Dioxide Capture and Methanation Process

Reducing the ever-growing level of CO_(2)in the atmosphere is critical for the sustainable development of human society in the context of global warming.Integration of the capture and upgrading of CO_(2)is,therefore,highly desirable since each process step is costly,both energetically and economically.Here,we report a CO_(2)direct air capture(DAC)and fixation process that produces methane.Low concentrations of CO_(2)(∼400 ppm)in the air are captured by an aqueous solution of sodium hydroxide to form carbonate.The carbonate is subsequently hydrogenated to methane,which is easily separated from the reaction system,catalyzed by TiO2-supported Ru in the aqueous phase with a selectivity of 99.9%among gas-phase products.The concurrent regenerated hydroxide,in turn,increases the alkalinity of the aqueous solution for further CO_(2)capture,thereby enabling this one-ofits-kind continuous CO_(2)capture and methanation process.Engineering simulations demonstrate the energy feasibility of this CO_(2)DAC and methanation process,highlighting its promise for potential largescale applications.

Hydrogen evolution activity enhancement by tuning the oxygen vacancies in self-supported mesoporous spinel oxide nanowire arrays

The development of facile strategies to tune the oxygen vacancy （OV） content in transition metal oxides （TMOs） is paramount to obtain low-cost and stable electrocatalysts, but still highly challenging. Taking NiC0204 as a model system, we have experimentally established a facile calcination and electrochemical activation （EA） methodology to dramatically increase the concentration of OVs and provide theoretical insight into how the concentration of OVs affects the performance of spinel TMOs towards the electrochemical hydrogen evolution reaction （HER）. A self-supported cathode of OV-rich NiC0204 nanowire arrays was found to exhibit higher HER activity and better stability in alkaline media than its counterparts with fewer OVs. The electrocatalytic HER activity was in good agreement with the increasing concentration of OVs in the studied samples. A large current density of 360 mA.cm-2 was reached with an overpotential of only 317 mV. Additionally, such a facile strategy was able to efficiently generate OVs in other TMOs （e.g., CoFe204 and NiFe204） for enhanced HER performance. In addition, our theoretical results suggest that the increasing OV concentration reduces the adsorption energy of water molecules and their dissociation energy barrier on the surface of the catalyst, thus leading to performance improvement of spinel TMOs toward the electrochemical HER. This work may open a new avenue to increase the concentration of OVs in TMOs in a controlled manner for promising applications in a variety of fields.

Cu_(2)O-SupportedAtomicallyDispersed Pd Catalysts for Semihydrogenation of Terminal Alkynes: Critical Role of Oxide Supports

Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations.However,limited success has been achieved in applying oxide-supported atomically dis-persed catalysts to semihydrogenation of alkynes under mild conditions.

Hydrogen Storage Kinetics of Nanocrystalline and Amorphous LaMg_(12)-Type Alloy–Ni Composites Synthesized by Mechanical Milling

The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systematically investigated, The results indicate that the as-milled composites exhibit excellent hydrogen storage kinetic performances, and increasing Ni content significantly facilitates the improvement of the hydrogen storage kinetics properties of the composites. The gaseous and electrochemical hydrogen storage kinetics of the composites reaches a maximum value with the variation of milling time. Increasing Ni content and milling time both make the hydrogen desorption activation energy lower, which are responsible for the enhancement in the hydrogen storage kinetics properties of the composites. The diffusion coefficient of hydrogen atom and activation enthalpy of charge transfer on the surface of the as-milled composites were also calculated, which are considered to be the dominated factors for the electrochemical high rate discharge ability.

Hydrogen storage thermodynamic and kinetic characteristics of PrMg12-type alloys synthesized by mechanical milling

To improve the hydrogen storage performance of PrMg12-type alloys, Ni was adopted to replace partially Mg in the alloys. The PrMgllNi＋x wt.% Ni （x=100, 200） alloys were prepared via mechanical milling. The phase structures and morphology of the experimental alloys were in vestigated by X-ray diffraction and transmission electron microscopy. The results show that increasing milling time and Ni content accelerate the formation of nanocrystalline and amorphous structure. The gaseous hydrogen storage properties of the experimental alloys were determined by differential scanning calorimetry （DSC） and Sievert apparatus. In addition, increasing milling time makes the hydrogenation rates of the alloys augment firstly and decline subsequently and the dehydrogenation rate always increases. The maximum capacity is 5. 572 wt. % for the x = 100 alloy and 5. 829 wt. % for the x = 200 alloy, respectively. The enthalpy change （ △H ）, entropy change （△S） and the dehydrogenation activation energy （Exde） markedly lower with increasing the milling time and the Ni content due to the generation of nanocrystalline and amorphous structure.

Hydrogen Storage Thermodynamics and Dynamics of Nd–Mg–NiBased Nd Mg_(12^-)Type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H_2 detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore,varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio（R^a_（10）; a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity） of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio（R^d_（20）, a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity） of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.