Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia

Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH₃) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi⁰/Bi³⁺ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900  ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH₃ yield rate and remarkable Faradaic efficiency of 15.10  ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis.     

Hydrogen carriers: Production,transmission, decomposition,and storage

Recognizing the potential role of liquid hydrogen carriers in overcoming the inherent limitations in transporting and storing gaseous and liquid hydrogen, a complete production and use scenario is postulated and analyzed for perspective one-way and two-way carriers. The carriers, methanol, ammonia and toluene/MCH (methylcyclohexane), are produced at commercially viable scales in a central location, transmitted by rail or pipelines for 2000 miles, and decomposed near city gates to generate fuel-cell quality hydrogen for distribution to refueling stations. In terms of the levelized cost of H₂ distributed to the stations, methanol is less expensive to produce ($1.22/kg-H₂) than MCH ($1.35/kg-H₂) or ammonia ($2.20/kg-H₂). Levelized train transmission cost is smaller for methanol ($0.63/kg-H₂) than ammonia ($1.29/kg-H₂) or toluene/MCH system ($2.07/kg-H₂). Levelized decomposition cost is smaller for ammonia ($0.30–1.06/kg-H₂) than MCH ($0.54–1.22/kg-H₂) or methanol ($0.43–1.12/kg-H₂). Over the complete range of demand investigated, 10–350 tpd-H₂, the levelized cost of H₂ distributed to stations is aligned as methanol « ammonia ~ MCH. With pipelines at much larger scale, 6000 tpd-H₂, the levelized cost decreases by ~1 $/kg-H₂ for ammonia and MCH and much less for methanol. Methanol is a particularly attractive low-risk carrier in the transition phase with lower than 50-tpd H₂ demand.     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

铋精矿加压氧化氨浸高效分离铜、硫和铋

针对湖南柿竹园铋精矿火法冶炼过程中存在的成本高、低浓度SO₂和散烟排放污染环境、有价金属综合回收率低等问题, 以柿竹园铋精矿为原料, 提出了加压氧化氨浸分离铋与铜、硫的新工艺, 研究了氨水加入量、浸出温度、浸出时间、浸出压力及浸出液固比等因素对铜、硫、铋浸出率的影响。在氨水用量1.8 mL/g_铋精矿、液固比4∶1、釜压2.8 MPa、浸出温度160 ℃、浸出时间5 h、搅拌速度600 r/min的优化工艺条件下, 铜、硫浸出率分别达93.57%和92.87%, 铋不浸出并以氧化铋形态全部入渣, 实现了铜、硫与铋的高效分离。     

液氮/液氨速冻鮰鱼片理化性质与组织结构变化

研究分析液氮与液氨速冻对斑点叉尾鮰鱼肉品质的影响。新鲜斑点叉尾鮰分割鱼片后分别进行工业隧道式液氮喷淋速冻（－90 ℃、35 min）、隧道式液氨速冻（－35 ℃、90 min），速冻样品置于－18 ℃下贮藏90 d。分析比较新鲜鱼肉以及速冻鱼肉在不同冻藏时间解冻损失率、蒸煮损失率、加压失水率、剪切力、pH值、K值、挥发性盐基氮（total volatile basic nitrogen，TVB-N）含量、三甲胺（trimethylamine，TMA）含量与硫代巴比妥酸反应物（thiobarbituric acid reactive substance，TBARs）值，应用荧光显微镜观察鱼肉组织微观结构变化。结果表明：与新鲜鱼肉相比，速冻鱼肉蒸煮损失率增加，加压失水率、剪切力、pH值降低，K值、TVB-N含量、TMA含量、TBARs值均呈上升趋势；随着冻藏时间延长，速冻鱼肉理化性质发生劣变；鱼肉速冻后肌肉细胞面积减小，细胞间隙增大；相比液氨速冻，液氮速冻更有利于保持鱼肉持水性、新鲜度以及组织结构完整性，可有效抑制鱼肉冻藏期间的品质劣变。综上，液氮速冻可以有效保持冷冻鱼肉品质，冻藏30 d内，液氮速冻鱼肉品质特性更接近于新鲜鱼肉。     

电催化氮气还原合成氨催化材料研究进展

氨是纺织、制药、化肥等领域重要的化工原料，也是一种清洁的能源载体，需求量大。目前氨的工业生产主要为Haber-Bosch法，反应条件严苛，能源消耗大且碳排放较高。电催化氮气还原(NRR)合成氨是一种在常温常压下进行的反应，工作电位低，且电能可通过清洁能源提供，是一种很有潜力的合成氨新工艺。但目前电催化NRR材料的产氨速率和法拉第效率低、工作稳定性不够高、溶液中痕量氨的定量检测困难及检测标准不统一等都为其发展带来了巨大挑战。本文首先介绍了电催化NRR的反应机理和常用研究方法，然后重点梳理了2019年以来NRR催化材料的最新研究进展，最后对该领域研究面临的挑战和机遇进行了展望。     

Carbon supported bimetallic Ru‐Co catalysts for H2 production through NaBH4 and NH3BH3 hydrolysis

This work investigates the effect of the addition of small amounts of Ru (0.5‐1 wt%) to carbon supported Co (10 wt%) catalysts towards both NaBH₄ and NH₃BH₃ hydrolysis for H₂ production. In the sodium borohydride hydrolysis, the activity of Ru‐Co/carbon catalysts was sensibly higher than the sum of the activities of corresponding monometallic samples, whereas for the ammonia borane hydrolysis, the positive effect of Ru‐Co systems with regard to catalytic activity was less evident. The performances of Ru‐Co bimetallic catalysts correlated with the occurrence of an interaction between Ru and Co species resulting in the formation of smaller ruthenium and cobalt oxide particles with a more homogeneous dispersion on the carbon support. It was proposed that Ru^°, formed during the reduction step of the Ru‐Co catalysts, favors the H₂ activation, thus enhancing the reduction degree of the cobalt precursor and the number of Co nucleation centers. A subsequent reduction of cobalt and ruthenium species also occurs in the hydride reaction medium, and therefore the state of the catalyst before the catalytic experiment determines the state of the active phase formed in situ. The different relative reactivity of the Ru and Co active species towards the two investigated reactions accounted for the different behavior towards NaBH₄ and NH₃BH₃ hydrolysis.     

氨浸-草酸盐沉淀法回收废弃线路板中金属铜的工艺研究

采用氨浸-草酸盐沉淀法回收废弃线路板中的金属铜,考察了氨水浓度、NH₄Cl溶液浓度、液固比、反应温度和时间对铜浸出率的影响。结果表明,最佳工艺条件为:氨水浓度10%、NH₄Cl溶液浓度1.5 mol/L、液固比10∶1、反应温度60 ℃、反应时间3 h,在此工艺条件下,铜浸出率高达99.25%。在铜的富集过程中,调节溶液pH值至1.5,60 ℃下反应30 min,铜沉淀率达到了98.15%。     

Dynamic Passivation in Perovskite Quantum Dots for Specific Ammonia Detection at Room Temperature

Perovskite structured CsPbX₃ (X = Cl, Br, or I) quantum dots (QDs) have attracted considerable interest in the past few years due to their excellent optoelectronic properties. Surface passivation is one of the main pathways to optimize the optoelectrical performance of perovskite QDs, in which the amino group plays an important role for the corresponding interaction between lead and halide. In this work, it is found that ammonia gas could dramatically increase photoluminescence of purified QDs and effectively passivate surface defects of perovskite QDs introduced during purification, which is a reversible process. This phenomenon makes perovskite QDs a kind of ideal candidate for detection of ammonia gas at room temperature. This QD film sensor displays specific recognition behavior toward ammonia gas due to its significant fluorescence enhancement, while depressed luminescence in case of other gases. The sensor, in turn‐on mode, shows a wide detection range from 25 to 350 ppm with a limit of detection as low as 8.85 ppm. Meanwhile, a fast response time of ≈10 s is achieved, and the recovery time is ≈30 s. The fully reversible, high sensitivity and selectivity characteristics make CsPbBr₃ QDs ideal active materials for room‐temperature ammonia sensing.     

温度对生物净化滤柱中氨氮、铁、锰去除效果的影响

温度是生物净化滤柱运行的一个重要参数，采用生物净化滤柱处理模拟含氨氮、铁、锰地下水，考察水温从约25℃降到约6℃过程中氨氮、铁、锰的去除效果。结果表明，出水氨氮、总铁、锰的浓度分别低于0.15mg/L、0.1mg/L、0.05mg/L，均低于国家标准。出水总铁、锰均未受到水温下降的影响，但是出水氨氮浓度逐渐从约0.02mg/L升高到约0.12mg/L。进一步分析发现，铁主要在滤层的0~0.4m段去除，去除效果没有受到水温变化的影响。氨氮、锰主要在滤层的0~0.8m段去除，其沿程浓度均随水温降低而明显升高。氨氮、锰的生物去除符合一级动力学反应，水温为24.6℃、15.3℃、6.7℃时，两者的动力学常数k分别为0.154min^-1、0.186min^-1，0.143min^-1、0.175min^-1，0.103min^-1、0.163min^-1；半反应时间t_1/2分别为4.51min、3.72min，4.83min、3.96min，6.72min、4.24min。随着试验水温的降低，氨氮、锰的去除效果明显受到影响。