Co4+ in porous ZIF-67-derives intercalating-bridging adsorption of 2-reaction sites for simultaneous 2-electron transfer toward sensitive detection of uric acid.

Metal-organic frameworks (MOFs) have been used to detect uric acid (UA), but still very challenging to achieve a low detection limit due to the low inferior conductivity of MOFs. Herein, three different N-doped ZIF-67-derived carbons were synthesized for the first time by one-step co-pyrolysis of 2-methylimidazole with cobalt nitrate (CN), cobalt acetate (CA) or cobalt chloride (CC) toward UA sensing. Afterwards, the cobalt nitrate-derived Co particle (Co/CN) supported by N-doped ZIF-67-derived carbon displays extremely low detection limit and high sensitivity for UA, outperformed all reported MOFs-based UA sensors. More interestingly, it was discovered that the high valence Co4+ within the Co/CN sample produced in high-acidic environment can intercalate in the frame for a bridge adsorption between two reaction sites, which boosted simultaneous 2-electron transfer, while Co3+ only allows an end-adsorption structure for one-electron transfer being the rate determining step. Furthermore, the bridge adsorption mode of UA on Co4+ -based catalyst was also verified by theoretical DFT calculations and XPS experiment. This work holds great promise for a selective and sensitive UA sensor for practical bioscience and clinic diagnostic applications while shedding lights in fundamental research for innovative designs and developments of high-sensitive electrochemical sensors.

Atomically Dispersed Co to an End-Adsorbing Molecule for Excellent Biomimetically and Prime Sensitively Detecting O2•- Released from Living Cells.

Single-atom catalysis efficiently exposes the catalytic sites to reactant molecules while rendering opportunity to investigate the catalysis mechanisms at atomic levels for scientific insights. Here, for the first time, atomically dispersed Co atoms are synthesized as biomimetic "enzymes" to monitor superoxide anions (O2•-), delivering ultraordinary high sensitivity (710.03 µA·µM-1·cm-2), low detection limit (1.5 nM), and rapid response time (1.2 s), ranking the best among all the reported either bioenzymatic or biomimetic O2•- biosensors. The sensor is further successfully employed to real-time monitor O2•- released from living cells. Moreover, theoretical calculation and analysis associated with experimental results discover that a mode of end adsorption of the negatively charged O2•- on the Co3+ atom rather than a bridge or/and side adsorption of the two atoms of O2•- on two Co3+ atoms, respectively, plays an important role in the single-atomic catalysis toward O2•- oxidation, which not only facilitates faster electron transfer but also offers better selectivity. This work holds great promise for an inexpensive and sensitive atomic biomimetic O2•- sensor for bioresearch and clinic diagnosis, while revealing that the adsorption mode plays a critical role in single-atom catalysis for a fundamental insight.

Tailoring of pore structure in mesoporous carbon for favourable flavin mediated interfacial electron transfer in microbial fuel cells.

Mesoporous carbon (MC) is supposed to be a good candidate for microbial fuel cell (MFC) anodes as it possesses a large specific area for the redox reaction of the electron shuttles and should deliver high power density. However, the power generation performance of MC anodes is often un-satisfying. It seems that a large portion of the pore surface is not available for anodic redox reaction but the reason is not clear. Here, three MCs with different pore sizes and pore shapes were fabricated and used to explore the effect of the pore structure on the bioelectrocatalysis in Shewanella putrefaciens CN32 MFCs. It is interesting that MC with 40-60 nm spheric pores (MC-III) possesses superior bio-electrocatalytic performance to the CMK-3 (MC-I with 3 nm channel like pores) and the one with 14 nm spheric pores (MC-II) although the specific surface area of MC-III is lower than MC-II and MC-I. The reason might be that the MC-III provides a more favorable pore structure than the other two MCs for flavin based redox reaction at the interface between the biofilm and the electrode. As a result, the MC-III anode delivered the highest power density at around 1700 mW m-2, which is 1.6 fold higher than that of the MC-I anode. A possible mechanism for the pore shape/size dependent interfacial electron transfer process has also been proposed. This work reveals that spheric mesopores with large pore width could be more favorable than the narrow channel-like pores for flavin based interfacial electron transfer in biofilm anodes, which will provide some insights for the design of the mesoporous anode in MFCs.

Biofilm promoted current generation of Pseudomonas aeruginosa microbial fuel cell via improving the interfacial redox reaction of phenazines.

Bacteria biofilm plays a key role in current generation of microbial fuel cells (MFCs), especially for the start-up stage. However, the detailed mechanism of the biofilm promoting the power generation is not very clear so far, especially for those exoelectrogens who rely on the self-excreted electron mediators for extracellular electron transfer. In this work, a biofilm formation inhibitor-sodium houttuyfonate (SH) is used to build a "non-biofilm" anode of Pseudomonas aeruginosa (P. aeruginosa) without affecting the bacteria growth during the MFC operation. According to the comparison results of the "non-biofilm" anode and biofilm-covered anode on current generation, phenazines concentration variation and anodic electrocatalysis, the biofilm on the anode not only provides plenty of bacterial cells for catalysis but also promotes the interfacial phenazine redox reaction through accumulating the self-generated mediators on anode for fast interfacial electron transfer. This work proves that the biofilm assisted electron mediator accumulation will benefit such kind of exoelectrogens to sustain sufficient electron mediators for extracellular electron transfer.

Imidazolium Ionic Liquid Functionalized Carbon Nanotubes for Improved Interfacial Charge Transfer and Simultaneous Determination of Dihydroxybenzene Isomers.

In this paper; an imidazolium ionic liquid (IL) is used to functionalize multi-walled carbon nanotubes (MWNTs) by covalent bonding on the MWNT surface. The functionalization not only provides a hydrophilic surface for ion accessibility but also prevents the aggregation of MWNTs. The IL-functionalized MWNTs were then applied for the electrochemical determination of the dihydroxybenzene isomers hydroquinone (HQ); catechol (CC); and resorcinol (RC), exhibiting excellent recognition ability towards the three compounds. The linear calibration ranges for HQ; CC and RC are 0.9-150 µM; 0.9-150 µM and 1.9-145 µM and the detection limits are found to be 0.15 µM for HQ; 0.10 µM for CC and 0.38 µM for RC based on S/N of 3. The proposed electrochemical sensor was also found to be useful for the determination of the dihydroxybenzene isomers in Yellow River water with reliable recovery.