Surface-Plasmonic-Field-Induced Photoredox Catalysis and Mediated Electron Transfer for Washing-Free DNA Detection

Distance-dependent electromagnetic radiation and electron transfer have been commonly employed in washing-free fluorescence and electrochemical bioassays, respectively. In this study, we combined the two distance-dependent phenomena for sensitive washing-free DNA detection. A distance-dependent surface plasmonic field induces rapid photoredox catalysis of surface-bound catalytic labels, and distance-dependent mediated electron transfer allows for rapid electron transfer from the surface-bound labels to the electrode. An optimal system consists of a chemically reversible acceptor (Ru(NH₃)₆³⁺), a chemically reversible photoredox catalyst (eosin Y), and a chemically irreversible donor (triethanolamine). Side reactions with O₂ do not significantly decrease the efficiency of photoredox catalysis. Energy transfer quenching between the electrode and the label can be lowered by increasing the distance between them. Washing-free DNA detection had a detection limit of approximately 0.3 nm in buffer and 0.4 nm in serum without a washing step.     

A Universal Graphene Quantum Dot Tethering Design Strategy to Synthesize Single-Atom Catalysts

A general graphene quantum dot-tethering design strategy to synthesize single-atom catalysts (SACs) is presented. The strategy is applicable to different metals (Cr, Mn, Fe, Co, Ni, Cu, and Zn) and supports (0D carbon nanosphere, 1D carbon nanotube, 2D graphene nanosheet, and 3D graphite foam) with the metal loading of 3.0–4.5 wt %. The direct transmission electron microscopy imaging and X-ray absorption spectra analyses confirm the atomic dispersed metal in carbon supports. Our study reveals that the abundant oxygenated groups for complexing metal ions and the rich defective sites for incorporating nitrogen are essential to realize the synthesis of SACs. Furthermore, the carbon nanotube supported Ni SACs exhibits high electrocatalytic activity for CO₂ reduction with nearly 100 % CO selectivity. This universal strategy is expected to open up new research avenues to produce SACs for diverse electrocatalytic applications.     

Unveiling the Promotion of Surface-Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction

Transition metal chalcogenides (TMCs) are efficient oxygen evolution reaction (OER) pre-electrocatalysts, and will in situ transform into metal (oxy)hydroxides under OER condition. However, the role of chalcogen is not fully elucidated after oxidation and severe leaching. Here we present the vital promotion of surface-adsorbed chalcogenates on the OER activity. Taking NiSe₂ as an example, in situ Raman spectroscopy revealed the oxidation of Se-Se to selenites (SeO₃²⁻) then to selenates (SeO₄²⁻). Combining the severe Se leaching and the strong signal of selenates, it is assumed that the selenates are rich on the surface and play significant roles. As expected, adding selenites to the electrolyte of Ni(OH)₂ dramatically enhance its OER activity. And sulfates also exhibit the similar effect, suggesting the promotion of surface-adsorbed chalcogenates on OER is universal. Our findings offer unique insight into the transformation mechanism of materials during electrolysis.     

高碳铬铁在氢氧化钠水溶液中电化学氧化过程

铬铁电化学氧化法是一种新的制备铬酸钠的方法,然而高碳铬铁在NaOH水溶液中的电化学氧化过程尚不明确。 采用循环伏安法(CV)、稳态极化法(LSV)等电化学测试方法对金属铬、高碳铬铁在NaOH水溶液中的电化学氧化过程进行研究,通过扫描电子显微镜(SEM)、能量散射谱(EDS)和X射线光电子能谱(XPS)对高碳铬铁电解后固相产物表征,判断固相产物的组成。 结果表明,高碳铬铁不同于金属铬的电氧化过程,它在NaOH溶液中通过Cr(0)→Cr(Ⅵ)的电氧化方式生成铬酸钠,中间产物Cr(OH)₃和Fe(0)发生电化学反应生成稳定的FeCr₂O₄。 随着NaOH浓度的增加,电势较低时,受高碳铬铁中Fe(0)的影响,高碳铬铁容易在NaOH水溶液中发生钝化;当电势足够正时,钝化膜溶解,生成铬酸钠、氢氧化铁和亚铬酸亚铁,同时,阳极表面有氧气析出。 高碳铬铁电化学氧化制备铬酸钠的适宜条件:碱浓度≥2 mol/L,阳极电势≥1.6 V(vs.SCE)。     

金属硫化物在可充电电池中的研究进展

低成本、长寿命、高安全性、高性能且易于大规模生产的锂/钠离子电池已被证实为重要的二次储能设备。 电极材料对锂/钠电池性能与循环寿命影响极大,金属硫化物由于具有高比容量和低电势而极具潜力成为锂/钠离子电池负极材料。 在电化学循环过程中,由于金属硫化物容易产生穿梭效应和体积变化,从而电极材料结构被破坏,进一步导致电池容量衰退、稳定性降低。 本文总结了多种金属硫化物的微观结构调控策略,从三维空间构建到与其它材料的复合,增强了电极的导电性和减缓体积变化带来的负面影响,进而获得性能优异的金属硫化物负极材料。 通过对金属硫化物的结构与性能的讨论,对其研究前景进行了积极的展望。     

无电沉积法AuNPs-MWCNTs的制备及其对黄酮类化合物的电化学催化性能研究

利用多壁碳纳米管具有较低的还原电位,以多壁碳纳米管作为还原剂和负载基底,通过无电沉积法制备了负载纳米金粒子的碳纳米管催化剂。此种材料具有更多的活性位点,避免了纳米金粒子表面保护剂的存在造成其催化活性降低的缺陷,发现其对典型黄酮类化合物-芦丁和黄芩苷具有良好的电化学催化性能和较高的灵敏度,并将其应用于电化学分析检测黄酮类化合物。     

普鲁士蓝正极材料的离子交换法制备及电化学储钾性能

采用氯化钾(KCl)和钠基普鲁士蓝(NPB)材料Na2-xMn[Fe(CN)6]z·yH2O为原料,通过离子交换法制备了掺钠钾基普鲁士蓝(NKPB)材料K1.9Na0.1Mn[Fe(CN)6]·0.4H2O。电化学测试表明,与用传统共沉淀法制备的钾基普鲁士蓝(KPB)材料K1.85Mn[Fe(CN)6]0.98□0.02·0.7H2O(□代表[Fe(CN)6]空位)相比,采用离子交换法制备的NKPB具有更高的容量(0.1C首次放电容量达136.3 mAh·g^-1)、较好的循环稳定性(0.5C经过100次循环,容量保持率为96.1%)和优异的倍率性能(5C和10C容量分别为87.6和68.4 mAh·g^-1)。NKPB优异的电化学性能与其高的钾含量、完整的晶体结构、钠离子掺杂、纳米级的颗粒尺寸,以及独特的开放框架结构有关。     

对苯二胺缩对苯二甲醛席夫碱及其配合物的制备和电化学性能

以对苯二胺和对苯二甲醛为原料缩合制备出对苯二胺缩对苯二甲醛席夫碱聚合物（PT）,研究了采用不同物质的量之比的单体所制备的聚合物的电化学性能。利用席夫碱聚合物中N原子上的孤对电子与不同金属离子配位形成席夫碱配位聚合物（PT-M）,并对所形成聚合物的电化学性能进行了研究。采用X射线衍射（XRD）、红外（IR）、热重-差示扫描量热法（TG-DSC）、扫描电子显微镜（SEM）和能谱（EDS）对产物进行了表征,PT-M的XRD峰强度相比于PT明显降低,表明金属离子配位进入分子链骨架中引起的空间位阻减少了分子链排列的有序性。采用循环伏安、恒电流充放电和交流阻抗评价了所制备的配位聚合物材料的电化学性能。研究发现,聚席夫碱铝配合物（PT-Al）表现出较优的电化学性能,在0.5 A·g^-1的电流密度下其电容值为649.6 F·g^-1,并且具有较好的循环稳定性,在8 A·g^-1的电流密度下循环1 000次后仍有80.9%的电容保持率。     

高指数晶面纳米催化剂的电化学制备及应用

催化剂的性能与其表面结构及组成密切相关,高指数晶面纳米晶的表面含有高密度的台阶原子等活性位点而表现出较高的催化活性. 本文综述了电化学方波电位方法用于Pt、Pd、Rh等贵金属高指数晶面结构纳米晶催化剂的制备、形成机理及其电催化性能的研究. 针对贵金属利用率问题,还着重介绍了具有较高质量活性的小粒径Pt二十四面体的制备. 在此基础上,还介绍了电化学方波电位方法用于低共熔溶剂中制备高指数晶面纳米晶,以及高指数晶面纳米催化剂的表面修饰及应用;最后对高指数晶面纳米催化剂的发展做出了展望.     

Electrochemical CO2 reduction reaction on cost-effective oxide-derived copper and transition metal–nitrogen–carbon catalysts

The electrochemical CO₂ reduction reaction (CO₂RR) either to generate multicarbon (C₂₊) or single carbon (C₁) value-added products provides an effective and promising approach to mitigate the high CO₂ concentration in the atmosphere and promote energy storage. However, cost-effectiveness of catalytic materials limits practical application of this technology in the short term. Herein, we summarize and discuss recent and advanced works on cost-effective oxide-derived copper catalysts for the generation of C₂₊ products (hydrocarbons and alcohols) and transition metal–nitrogen–doped carbon electrocatalytic materials for C₁ compounds production from CO₂RR. We think they represent suitable electrocatalyst candidates for scaling up electrochemical CO₂ conversion. This short review may provide inspiration for the future design and development of innovative active, cost-effective, selective and stable electrocatalysts with improved properties for either the production of C₂₊ (alcohols, hydrocarbons) or carbon monoxide from CO₂RR.