Enhanced catalytic activity of monodispersed AgPd alloy nanoparticles assembled on mesoporous graphitic carbon nitride for the hydrolytic dehydrogenation of ammonia borane under sunlight

We address the composition-controlled synthesis of monodispersed AgPd alloy nanoparticles (NPs),their assembly for the first time on mesoporous graphitic carbon nitride (mpg-C3N4),and the unprecedented catalysis of mpg-C3N4@AgPd in the hydrolytic dehydrogenation of ammonia borane (AB) at room temperature.Monodispersed AgPd alloy NPs were synthesized using a high-temperature organic-phase surfactant-assisted protocol comprising the co-reduction of silver(Ⅰ) acetate and palladium(Ⅱ) acetylacetonate in the presence of oleylamine,oleic acid,and 1-octadecene.This protocol allowed the synthesis of four different compositions of AgPd alloy NPs.The AgPd alloy NPs were then assembled on mpg-C3N4,reduced graphene oxide,and Ketjenblack using a liquid-phase self-assembly method.Among the three supports tested,the mpg-C3N4@AgPd catalysts provided the best activity because of the Mott-Schottky effect,which was driven by the favorable work function difference between mpg-C3N4 and the metal NPs.Moreover,the activity of the mpg-C3N4@AgPd catalyst was further enhanced by an acetic acid treatment (AAt),and a record initial turnover frequency of 94.1 mol(hydrogen)·mol(catalyst)-1·min-1 was obtained.Furthermore,the mpg-C3N4@Ag42Pd58-AAt catalyst also showed moderate durability for the hydrolysis of AB.This study also includes a wealth of kinetic data for the mpg-C3N4@AgPd-catalyzed hydrolysis of AB.     

Synthesis of boron carbon nitride oxide (BCNO) from urea and boric acid

A solid state synthesis of boron carbon nitride oxide (BCNO) material was carried out starting from urea and boric acid treated at 600°C. The X-ray diffraction pattern corresponded to amorphous BCNO with an interlayer distance of 3.49 Å. The material had a layered structure similar to that of graphite and hexagonal boron nitride (h-BN). Infrared spectroscopy (IR) showed bands which were similar to those typical of BN and carbon nitride. The presence of boron was also confirmed by energy dispersive spectroscopy in an amount compatible with the IR spectrum. The spectra obtained by X-ray photoelectron spectroscopy (XPS) corresponded to those of a BCNO family with a considerable content of oxygen too. The optical band gap was estimated to be 3.22 eV, typical of a wide band-gap semiconductor. The particle size was very dispersed from micro to nanosize. The material dispersed in polar solvents formed stable suspensions due to the presence of hydroxyl groups.     

中空纤维膜接触器分离CO2/N2混合气体的研究

以氢氧化钠(NaOH)、单乙醇胺(MEA)、二乙醇胺(DEA)为吸收剂,采用疏水性聚丙烯中空纤维微孔膜接触器技术进行了从CO2/N2混合气中分离CO2的研究.从机理上简要探讨了影响CO2吸收传质的因素.结果表明3种吸收剂分离CO2的效率依次为MEA＞NaOH＞DEA,CO2的分离效率随吸收剂浓度和流速的提高而增大,随混合气流速及其中CO2浓度的增大而减小;在壳流程与腔流程的对比中腔流程对CO2的吸收效率要明显好于壳流程.     

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g‐C₃N₄) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g‐C₃N₄. The resultant boron‐doped and nitrogen‐deficient g‐C₃N₄ exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h^?1 g^?1, much higher than previously reported g‐C₃N₄. It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g‐C₃N₄, the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C–N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g‐C₃N₄ with simultaneous introduction of dopants and defects for high‐performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.     

Argon+carbon dioxide gaseous mixture viscosities and anisotropic pair potential energy functions

The viscosities of pure gaseous carbon dioxide and argon+carbon dioxide mixtures have been measured with a capillary flow viscometer. The viscosities are relative to those of argon, in the temperature range 213 to 353 K, and considered accurate to ±0.7%. The pure-component viscosities agree closely with previous measurements. The mixture viscosities are used to calculate interaction viscosities and binary diffusion coefficients, which are compared with previous measurements. Interaction viscosities have been calculated, by use of the Mason-Monchick approximation, from the anisotropic pair potential energy functions for the unlike interaction proposed by Pack and his co-workers and by Hough and Howard. Comparison of these calculated interaction viscosities with those derived from our experiments and the higher-temperature measurements of Hobley, Matthews, and Townsend proves to be a powerful discriminant for the proposed anisotropic potential functions.Paper dedicated to Professor Joseph Kestin.     

氨硼烷水解制氢催化剂载体的研究进展

氢由于具有高效率和高功率密度而被认为是一种出色的清洁能源。化学储氢材料要求具有高的氢储存量。氨硼烷具有高氢含量(19.6%),且在普通贮存条件下稳定,被认为是有吸引力的储氢材料之一。由于氨硼烷在常温下不易放氢,故放氢催化剂成为氨硼烷放氢研究的核心技术和主要方向。金属催化剂可以显著提高水解放氢速度,是影响氨硼烷水解放氢的关键因素,但是金属颗粒催化剂一般都存在颗粒粒径生长过快、易团聚等缺点。为了解决这一问题,研究者选择不同的载体来分散催化剂,使催化剂金属分散在载体表面,防止团聚和过快增长,从而暴露更多活性位点,使催化氨硼烷放氢速率更快。文章将针对不同催化剂载体对氨硼烷水解的催化效果进行阐述。     

无机酸刻蚀多孔氮化碳的合成及光催化性能

通过合理的形貌调控使石墨相氮化碳(g-C_3N_4)低维化和多孔化,是提高其光催化活性的有效途径.采用高温煅烧方法制备了HCl、HNO_3和H_2SO_4刻蚀的g-C_3N_4,并对它们进行了结构形貌表征、形成机理探究和光催化降解罗丹明B测试,还给出了活性增强机理.结果显示:酸刻蚀g-C_3N_4具有和g-C_3N_4相同的基本晶体结构,但是呈薄片状,且表面出现了大量纳米孔,这些孔是由无机酸阻碍前驱体中N—H键参与热缩聚反应所致,按照HCl、HNO_3、H_2SO_4的顺序阻碍作用依次增强,对应的孔径依次增大,结构边缘(C)_2—N—H基团的XPS特征峰强度也依次增加;经过40 min光反应,g-C_3N_4和HCl、HNO_3、H_2SO_4刻蚀的g-C_3N_4对罗丹明B的降解率分别为45%、 56%、 52%和95%,H_2SO_4刻蚀的g-C_3N_4光催化活性最高;酸刻蚀引起的薄片和多孔结构不仅增加了g-C_3N_4的比表面积,促进了暗条件下对罗丹明B的吸附,还通过量子限域效应提高了其光吸收能力,拓宽了禁带宽度,有效促进了光生电荷的分离.因此,酸刻蚀克服了g-C_3N_4的缺点,为探寻其光催化活性的提高方法提供了有价值的启发.     

Application of carbon nanotube in wireless sensor network to monitor carbon dioxide

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Over the years, new discoveries have led to new applications, often taking advantage of their unique electrical properties, extraordinary strength and efficiency in heat conduction. Since industrialisation, human activities have resulted in steadily increasing concentrations of the greenhouse gases. Excess amount of carbon dioxide (CO₂) in living environment is toxic and unsuitable for human consumption. Thus, a need exists for accurate, inexpensive, long-term monitoring of environmental contaminants using sensors that can be operated on site. Over the past decade, many wireless sensor network (WSN)-based monitoring applications have been proposed. This article reviews the developments of sensing elements to monitor CO₂ in the environment. The cylindrical carbon molecules have novel properties that make them potentially useful in many applications in nanotechnology, electronics, optics and other fields of materials science, as well as potential sensing element in wireless sensor technology. They exhibit extraordinary strength and unique electrical properties, and are efficient thermal conductors. The unique properties of CNT makes it a potential sensing element in the WSN technology.     

The viscosity of liquid carbon dioxide

The paper reports new masurements of the viscosity of liquid carbon dioxide along three isotherms at 260, 280, and 300 K for pressures up to 100 MPa. The measurements have been carried out in a vibrating-wire viscometer and have an estimated accuracy of ±0.5%. The results are employed to distinguish between conflicting data sets that already exist in the literature and that have inhibited accurate representations of the viscosity of this important fluid. It is shown that the experimental results can be represented with a high precision by means of procedures founded on the hard-sphere theory of liquids, although the observed density dependence of the viscosity is different from that characteristic of hydrocarbons.     

Orientation controlled preparation of nanoporous carbon nitride fibers and related composite for gas sensing under ambient conditions

Creating pores in suprastructures of two-dimensional (2D) materials while controlling the orientation of the 2D building blocks is important in achieving large specific surface areas and tuning the anisotropic properties of the obtained functional hierarchical structures.In this contribution,we report that arranging graphitic carbon nitride (g-C3N4) nanosheets into one-dimensional (1D) architectures with controlled orientation has been achieved by using 1D oriented melem hydrate fibers as the synthetic precursor via a polycondensation process,during which the removal of water molecules and release of ammonia gas led to the creation of pores without destroying the 1D morphology of the oriented structures.The resulting porous g-C3N4 fibers with both meso-and micro-sized pores and largely exposed edges exhibited good sensing sensitivity and selectivity towards NO2.The sensing performance was further improved by hybridization of the porous fibers with Au nanoparticles (Au NPs),leading to a detection limit of 60 ppb under ambient conditions.Our results suggest that the highly porous g-C3N4 fibers and the related hybrid structures with largely exposed graphitic layer edges are excellent sensing platforms and may also show promise in other electronic and electrochemical applications.     

Chilling hot boned meat with solid carbon dioxide

This Paper describes the development of a method to chill meat at mobile abattoirs in remote areas and compares its feasibility with conventional chilling. Hot boned meat and solid CO₂ pellets (5 kg of CO₂ per 25 kg of meat) were packed in boxes which were then stacked tightly in insulated containers. This process was simple to use, produced meat of good bacterial quality and reduced the capital cost of a complete mobile abattoir by 43%. Tests with two carcasses indicated that the yield of meat was increased by 3% which more than offset the cost of the CO₂.     

脱除与浓缩二氧化碳的膜分离技术

综述了液膜、聚合物膜、无机膜及膜基气体吸收等膜与膜过程在ＣＯ２的脱除与浓缩中的研究进展，并讨论了这几种与膜过程在民用方面如发电厂燃料废气（ＣＯ２／Ｎ２分离）、天然气中ＣＯ２的脱除（ＣＯ２／ＣＨ４分离）及军用方面如潜艇、空间站等密封环境中ＣＯ２的脱除与浓缩（ＣＯ２／Ｏ２、ＣＯ２／Ｎ２分离）的可能应用。     

Ammonia Thermal Treatment toward Topological Defects in Porous Carbon for Enhanced Carbon Dioxide Electroreduction

Topological defects, with an asymmetric local electronic redistribution, are expected to locally tune the intrinsic catalytic activity of carbon materials. However, it is still challenging to deliberately create high-density homogeneous topological defects in carbon networks due to the high formation energy. Toward this end, an efficient NH₃ thermal-treatment strategy is presented for thoroughly removing pyrrolic-N and pyridinic-N dopants from N-enriched porous carbon particles, to create high-density topological defects. The resultant topological defects are systematically investigated by near-edge X-ray absorption fine structure measurements and local density of states analysis, and the defect formation mechanism is revealed by reactive molecular dynamics simulations. Notably, the as-prepared porous carbon materials possess an enhanced electrocatalytic CO₂ reduction performance, yielding a current density of 2.84 mA cm⁻² with Faradaic efficiency of 95.2% for CO generation. Such a result is among the best performances reported for metal-free CO₂ reduction electrocatalysts. Density functional theory calculations suggest that the edge pentagonal sites are the dominating active centers with the lowest free energy (ΔG) for CO₂ reduction. This work not only presents deep insights for the defect engineering of carbon-based materials but also improves the understanding of electrocatalytic CO₂ reduction on carbon defects.     

Double-Heterostructured Nickel Phosphate-Phosphides as High-Activity Electrocatalyst for Ammonia Borane Electrooxidation

The direct electrooxidation reaction of ammonia borane (ABOR) as the anodic reaction of direct ammonia borane fuel cells (DABFCs) is greatly dependent on the properties of electrocatalysts. Both the active sites and charge/mass transfer characteristics are the key to promoting the processes of kinetics and thermodynamics, which can further improve the electrocatalytic activity. Hence, the catalyst double-heterostructured Ni₂P/Ni₂P₂O₇/Ni₁₂P₅ (d-NPO/NP) with the optimistic redistribution of electrons and active sites is prepared for the first time. The d-NPO/NP-750 catalyst obtained after pyrolysis at 750 °C shows the outstanding electrocatalytic activity toward ABOR with an onset potential of −0.329 V vs RHE which is better than all the published catalysts. The density functional theory (DFT) computations illustrate that the Ni₂P₂O₇/Ni₂P acts as the activity enhancement heterostructure with a high d-band center (−1.60 eV) and the low activation energy barrier, while the Ni₂P₂O₇/Ni₁₂P₅ acts as the conductivity enhancement heterostructure with the highest density of valence electrons.     

新型CO2捕获材料研究进展

高效、经济、环境友好的CO2捕获技术的开发与应用将是未来发展的趋势.本文概括了对CO2的吸附分离技术以及捕获机理,总结了传统CO2捕获材料的研究与不足,重点讨论了新型CO2捕获材料的发展状况和研究进展,新型CO2捕获材料的研发与应用将大大缓解全球气候变暖.     

聚乙烯亚胺型吸附纤维的制备及其对二氧化碳的吸附性能

以玻璃纤维作为基质复合聚乙撑亚胺（PEI），制得含多胺基的复合型吸附纤维。表征了该吸附纤维的化学结构，评价了不同PEUEP比例、涂布质量以及吸附气体中CO2浓度对CO2吸附容量的影响。研究表明，在饱和水蒸汽环境中，CO2吸附量随PEUEP比例的增加而增加，对二氧化碳的吸附量最高可达89．11mgCO2／g-吸附纤维，相当于276．96mg CO2／g-PEI，但CO2吸附量随涂布质量的增加而降低。吸附气中CO2含量对CO2吸附容量的影响较大，随吸附气中CO2含量的增加，吸附纤维对CO2的吸附容量也增加。     

可降解聚碳酸亚丙酯马来酸酐的合成与表征

在负载双金属PBM型催化剂下,以二氧化碳(CO2),环氧丙烷(PO)和马来酸酐(MA)为原料,三元共聚反应合成了聚碳酸亚丙酯马来酸酐(PPCMA).采用FTIR、1H-NMR、13C-NMR、DSC等对PPCMA进行了表征.结果表明,产物中引入了马来酸酐单元且共聚过程中不发生双键交联和构型转化;同时,马来酸酐单元的引入有效地提高了聚合物的特性粘数[η],玻璃化转变温度T g以及热稳定性;且增强了材料的降解性;不同的聚合反应时间对PPCMA的特性粘数和粘均分子量有着明显的影响.     

Unravelling charge carrier dynamics in protonated g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> interfaced with carbon nanodots as co-catalysts toward enhanced photocatalytic CO<Subscript>2</Subscript> reduction: A combined experimental and first-principles DFT study

In this work,we demonstrated the successful construction of metal-free zerodimensional/two-dimensional carbon nanodot (CND)-hybridized protonated g-C3N4 (pCN) (CND/pCN) heterojunction photocatalysts by means of electrostatic attraction.We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis.The CND/pCN-3 sample with a CND content of 3 wt.％ showed the highest catalytic activity in the CO2 photoreduction process under visible and simulated solar light.Thisprocess results in the evolution of CH4 and CO.The total amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 μmol·gcatalyst-1,respectively.These values were 3.6 and 2.28 times higher,respectively,than the amounts generated when using pCN alone.The corresponding apparent quantum efficiency (AQE) was calculated to be 0.076％.Furthermore,the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles,with no significant decrease in the catalytic activity.The significant improvement in the photoactivity using CND/pCN-3 was attributed to the synergistic interaction between pCN and CNDs.This synergy allows the effective migration of photoexcited electrons from pCN to CNDs via wellcontacted heterojunction interfaces,which retards the charge recombination.This was confirmed by photoelectrochemical measurements,and steady-state and time-resolved photoluminescence analyses.The first-principles density functional theory (DFT) calculations were consistent with our experimental results,and showed that the work function of CNDs (5.56 eV) was larger than that of pCN (4.66 eV).This suggests that the efficient shuttling of electrons from the conduction band of pCN to CNDs hampers the recombination of electron-hole pairs.This significantly increased the probability of free charge carriers reducing CO2 to CH4 and CO.Overall,this study underlines the importance of understanding the charge carrier dynamics of the CND/pCN hybrid nanocomposites,in order to enhance solar energy conversion.     

Removal of nitrophenols from water using cellulose derived nitrogen doped graphitic carbon material containing titanium dioxide

Nitrophenols (NPs) and their derivatives are highly toxic, mutagenic and bio-refractory pollutants commonly present in natural water resources and industrial wastewater. To remove NPs from water, N-doped graphitic carbon (NGC) and NGC adsorbent containing titanium dioxide (NGC–TiO₂) were synthesized by pyrolysis of microcrystalline cellulose and dopamine mixture, and the mixture along with TiO₂ at 500°C, respectively. NCG-TiO₂ was thoroughly characterized using various analytical techniques. NP adsorption on the NGC–TiO₂ adsorbent surface was studied by varying the pH, initial concentration of NP, and adsorbent dose. The results showed that the most efficient adsorption was achieved at pH 3. After 4?h sonication at pH 3, 80% 4-NP adsorption was achieved using NGC–TiO₂ compared to 74% with NGC adsorbent. The percentage removal of 4-NP was higher than 3-NP which was also higher than 2,4-DNP using NGC–TiO₂. 4-NP adsorption best fitted to the Langmuir isotherm plot with R² value of 0.9981 and adsorption capacity of 52.91?mg?g^?1. The adsorption process of NP was found to follow a pseudo-second-order kinetic model. The rate constant value for the adsorption of 10^?4?M 4-NP at pH 3 using 10?mg of NGC–TiO₂ adsorbent was found to be 3.76?×?10^?5?g.mg^?1.min^?1