High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalystWeibin Qiu, Xiaoying Xie, Jian‐Ding Qiu et al.|Nature Communications|2018 Abstract Conversion of naturally abundant nitrogen to ammonia is a key (bio)chemical process to sustain life and represents a major challenge in chemistry and biology. Electrochemical reduction is emerging as a sustainable strategy for artificial nitrogen fixation at ambient conditions by tackling the hydrogen- and energy-intensive operations of the Haber–Bosch process. However, it is severely challenged by nitrogen activation and requires efficient catalysts for the nitrogen reduction reaction. Here we report that a boron carbide nanosheet acts as a metal-free catalyst for high-performance electrochemical nitrogen-to-ammonia fixation at ambient conditions. The catalyst can achieve a high ammonia yield of 26.57 μg h –1 mg –1 cat. and a fairly high Faradaic efficiency of 15.95% at –0.75 V versus reversible hydrogen electrode, placing it among the most active aqueous-based nitrogen reduction reaction electrocatalysts. Notably, it also shows high electrochemical stability and excellent selectivity. The catalytic mechanism is assessed using density functional theory calculations.
Regenerable and stable sp2 carbon-conjugated covalent organic frameworks for selective detection and extraction of uraniumWei‐Rong Cui, Cheng-Rong Zhang, Wei Jiang et al.|Nature Communications|2020 Abstract Uranium is a key element in the nuclear industry, but its unintended leakage has caused health and environmental concerns. Here we report a sp 2 carbon-conjugated fluorescent covalent organic framework (COF) named TFPT-BTAN-AO with excellent chemical, thermal and radiation stability is synthesized by integrating triazine-based building blocks with amidoxime-substituted linkers. TFPT-BTAN-AO shows an exceptional UO 2 2+ adsorption capacity of 427 mg g −1 attributable to the abundant selective uranium-binding groups on the highly accessible pore walls of open 1D channels. In addition, it has an ultra-fast response time (2 s) and an ultra-low detection limit of 6.7 nM UO 2 2+ suitable for on-site and real-time monitoring of UO 2 2+ , allowing not only extraction but also monitoring the quality of the extracted water. This study demonstrates great potential of fluorescent COFs for radionuclide detection and extraction. By rational designing target ligands, this strategy can be extended to the detection and extraction of other contaminants.
Regenerable Covalent Organic Frameworks for Photo‐enhanced Uranium Adsorption from SeawaterWei‐Rong Cui, Fangfang Li, Rui‐Han Xu et al.|Angewandte Chemie International Edition|2020 Abstract Uranium is a key resource for the development of the nuclear industry, and extracting uranium from the natural seawater is one of the most promising ways to address the shortage of uranium resources. Herein, a semiconducting covalent organic framework (named NDA‐TN‐AO) with excellent photocatalytic and photoelectric activities was synthesized. The excellent photocatalytic effect endowed NDA‐TN‐AO with a high anti‐biofouling activity by generating biotoxic reactive oxygen species and promoting photoelectrons to reduce the adsorbed U VI to insoluble U IV , thereby increasing the uranium extraction capacity. Owing to the photoinduced effect, the adsorption capacity of NDA‐TN‐AO to uranium in seawater reaches 6.07 mg g −1 , which is 1.33 times of that in dark. The NDA‐TN‐AO with enhanced adsorption capacity is a promising material for extracting uranium from the natural seawater.
Boron-Doped Graphene Quantum Dots for Selective Glucose Sensing Based on the “Abnormal” Aggregation-Induced Photoluminescence EnhancementLi Zhang, Zhiyi Zhang, Ru‐Ping Liang et al.|Analytical Chemistry|2014 A hydrothermal approach for the cutting of boron-doped graphene (BG) into boron-doped graphene quantum dots (BGQDs) has been proposed. Various characterizations reveal that the boron atoms have been successfully doped into graphene structures with the atomic percentage of 3.45%. The generation of boronic acid groups on the BGQDs surfaces facilitates their application as a new photoluminescence (PL) probe for label free glucose sensing. It is postulated that the reaction of the two cis-diol units in glucose with the two boronic acid groups on the BGQDs surfaces creates structurally rigid BGQDs-glucose aggregates, restricting the intramolecular rotations and thus resulting in a great boost in the PL intensity. The present unusual "aggregation-induced PL increasing" sensing process excludes any saccharide with only one cis-diol unit, as manifested by the high specificity of BGQDs for glucose over its close isomeric cousins fructose, galactose, and mannose. It is believed that the doping of boron can introduce the GQDs to a new kind of surface state and offer great scientific insights to the PL enhancement mechanism with treatment of glucose.
Controllable Deposition of Platinum Nanoparticles on Graphene As an Electrocatalyst for Direct Methanol Fuel CellsJian‐Ding Qiu, Guo‐Chong Wang, Ru‐Ping Liang et al.|The Journal of Physical Chemistry C|2011 Platinum nanoparticles (Pt NPs) with uniform size and high dispersion have been successfully assembled on poly(diallyldimethylammonium chloride) functionalized graphene oxide via a sodium borohydride reduction process. The loading concentration of Pt NPs on graphene can be adjusted in the range of 18–78 wt %. The obtained Pt/graphene nanocomposites are characterized by transmission electron microscopy, high resolution transmission electron microscopy, energy dispersive spectrometry, X-ray diffraction, and thermogravimetric analysis. The results show that the Pt NPs with sizes of approximate 4.6 nm uniformly disperse on graphene surface for all Pt loading densities. Electrochemical studies reveal that the Pt/graphene nanocomposites with electrochemically active surface area of 141.6 m2/g show excellent electrocatalytic activity toward methanol oxidation and oxygen reduction. The present method is promising for the synthesis of high performance catalysts for fuel cells, gas phase catalysis, and sensors.