自掺杂SnO2微球的水热合成及其可见光催化性能

本研究采用水热法,以柠檬酸为螯合剂,通过控制n(Sn⁴⁺)/n(Sn²⁺)的数值,合成了由具有丰富氧空位的SnO₂纳米晶体组装成的微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)及UV-Vis漫反射光谱对SnO₂纳米微球进行表征分析,结果表明:在酸性水热条件和柠檬酸的螯合作用下,二氧化锡纳米晶体聚集形成微球;在Sn⁴⁺/Sn²⁺摩尔比例为3:7时,其微球尺寸最小,整体分散性较好;同时适量二价锡离子的掺杂使得该样品氧空位浓度达到最佳,氧空位的存在将使得样品光吸收范围拓展至可见光,因而该样品显示出较强的可见光催化效率,在8 min内完全降解甲基橙。     

Effect of oxygen on regulation of properties of moderately boron-doped diamond films

Regulation of oxygen on properties of moderately boron-doped diamond films is fully investigated. Results show that, with adding a small amount of oxygen (oxygen-to-carbon ratio < 5.0%), the crystal quality of diamond is improved, and a suppression effect of residual nitrogen is observed. With increasing ratio of O/C from 2.5% to 20.0%, the hole concentration is firstly increased then reduced. This change of hole concentration is also explained. Moreover, the results of Hall effect measurement with temperatures from 300 K to 825 K show that, with adding a small amount of oxygen, boron and oxygen complex structures (especially B₃O and B₄O) are formed and exhibit as shallow donor in diamond, which results in increase of donor concentration. With further increase of ratio of O/C, the inhibitory behaviors of oxygen on boron leads to decrease of acceptor concentration (the optical emission spectroscopy has shown that it is decreased with ratio of O/C more than 10.0%). This work demonstrates that oxygen-doping induced increasement of the crystalline and surface quality could be restored by the co-doping with oxygen. The technique could achieve boron-doped diamond films with both high quality and acceptable hole concentration, which is applicable to electronic level of usage.     

射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

Copper-based metal–organic framework decorated by CuO hair-like nanostructures: Electrocatalyst for oxygen evolution reaction

We report a Cu-based metal–organic framework (MOF) decorated by CuO nanostructures as an efficient catalyst for the oxygen evolution reaction (OER). MIL-53(Cu) was synthesized by a hydrothermal approach using 1,4-bezenedicarboxylic acid as organic precursor and further annealed at 300°C to form CuO nanostructures on its surface. The produced electrocatalyst, CuO@MIL-53(Cu), was characterized using various techniques. Under alkaline conditions, the developed electrocatalyst exhibited an overpotential of 801 and 336 mV versus RHE at 10 and 1 mA cm⁻², respectively. The reproducibility of the catalytic performance was validated using several electrodes. It was confirmed that the CuO hair-like nanostructures grown on MIL-53(Cu) using thermal treatment exhibit high OER activity, good kinetics and durability. CuO@MIL-53(Cu) is an economic noble-metal-free OER electrocatalyst. It has potential for application as anode material for sustainable energy technologies like batteries, fuel cells and water electrolysis.     

Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen

A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals.     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

BiVO4/TiO2 heterojunction with rich oxygen vacancies for enhanced electrocatalytic nitrogen reduction reaction

The large-scale production of ammonia mainly depends on the Haber–Bosch process, which will lead to the problems of high energy consumption and carbon dioxide emission. Electrochemical nitrogen fixation is considered to be an environmental friendly and sustainable process, but its efficiency largely depends on the activity and stability of the catalyst. Therefore, it is imperative to develop highefficient electrocatalysts in the field of nitrogen reduction reaction (NRR). In this paper, we developed a BiVO₄/TiO₂ nanotube (BiVO₄/TNT) heterojunction composite with rich oxygen vacancies as an electrocatalytic NRR catalyst. The heterojunction interface and oxygen vacancy of BiVO₄/TNT can be the active site of N₂ dynamic activation and proton transition. The synergistic effect of TiO₂ and BiVO₄ shortens the proton transport path and reduces the over potential of chemical reaction. BiVO₄/TNT has high ammonia yield of 8.54 μg·h⁻¹·cm⁻² and high Faraday efficiency of 7.70% in −0.8 V vs. RHE in 0.1 M Na₂SO₄ solution.     

Research progress of Pt and Pt-based cathode electrocatalysts for proton-exchange membrane fuel cells

Proton-exchange membrane fuel cells (PEMFCs) have been widely used commercially to solve the energy crisis and environmental pollution. The oxygen reduction reaction (ORR) at the cathode is the rate-determining step in PEMFCs. Platinum (Pt) catalysts are used to accelerate the ORR kinetics. Pt's scarcity, high cost, and instability in an acidic environment at high potentials seriously hinder the commercialization of PEMFCs. Therefore, studies should explore electrocatalysts with high catalytic activity, enhanced stability, and low-Pt loading. This review briefly introduces the research progress on Pt and Pt-based ORR electrocatalysts for PEMFCs, including anticorrosion catalyst supports, Pt, and Pt-based alloy electrocatalysts. Advanced preparation technology and material characterization of Pt-based ORR electrocatalysts are necessary to improve the performance and corresponding reaction mechanisms.     

PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

EAST上由垂直不稳定性引发破裂的分析与预测

从EAST 装置2016 年的放电实验中，选取了119 次等离子体破裂放电数据，分析诱发等离子体破裂的原因，发现约60%的破裂是由垂直不稳定性直接引起的，其破裂后将会产生更大的晕电流，从而产生更大的电磁应力损坏装置。对由垂直不稳定性引起的破裂(简称为VID)(72 次放电)进行了研究，建立了分别基于单变量(垂直位移)和两维变量(垂直位移、垂直位移增长率)的预测模型用于对VID 破裂的预测。离线测试表明，基于两维变量的预测模型可以在破裂发生前20ms 给出破裂预警信号，预测成功率达93%。