Self-Powered Electrochemical CO2 Conversion Enabled by a Multifunctional Carbon-Based Electrocatalyst and a Rechargeable Zn-Air Battery.

Multifunctional electrocatalysts are required for diverse clean energy-related technologies (e.g., electrochemical CO2 reduction reaction (CO2RR) and metal-air batteries). Herein, a nitrogen and fluorine co-doped carbon nanotube (NFCNT) is reported to simultaneously achieve multifunctional catalytic activities for CO2RR, oxygen reduction reaction (ORR), and oxygen evolution reaction (OER). Theoretical calculations reveal that the superior multifunctional catalytic activities of NFCNT are attributed to the synergistic effect of nitrogen and fluorine co-doping to induce charge redistribution and decrease the energy barrier of rate-determining step for different electrocatalytic reactions. Furthermore, the rechargeable Zn-air battery (ZAB) with NFCNT electrode delivers a high peak power density of 230 mW cm-2 and superior durability over 100 cycles, outperforming the ZAB with Pt/C+RuO2 based electrodes. More importantly, a self-driven CO2 electrolysis unit powered by the as-assembled ZABs is developed, which achieves 80% CO Faraday efficiency and 60% total energy efficiency. This work provides a new insight into the exploration of highly efficient multifunctional carbon-based electrocatalysts for novel energy-related applications.

Lattice Oxygen Activation through Deep Oxidation of Co4N by Jahn-Teller-active Dopants for Improved Electrocatalytic Oxygen Evolution.

Triggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the directly formation of oxygen-oxygen bond. High-valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre-catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn-Teller (J-T) distortion induced structural instability, we incorporate high-spin Mn3+ (t2g3eg1) dopant into Co4N. Mn dopants enable a surface structural transformation from Co4N to CoOOH, and finally to CoO2, as observed by various in-situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn doped Co4N triggers the lattice oxygen activation, as evidenced experimentally by pH-dependent OER, tetramethylammonium cation adsorption and on-line electrochemical mass spectrometry measurements of 18O-labelled catalysts. In general, this work not only offers the introducing J-T effect approach to regulate the structural transition, but also provides an understanding about the influence of catalyst's electronic configuration on determining the reaction route, which may inspire the design of more efficient catalysts with activated lattice oxygen.

Spin-state Conversion by Asymmetrical Orbital Hybridization in Ni-doped Co3 O4 to Boost Singlet Oxygen Generation for Microbial Disinfection.

Singlet oxygen (1 O2 ) plays a significant role in environmental and biomedical disinfection fields. Electrocatalytic processes hold great potential for 1 O2 generation, but remain challenging. Herein, a facile Ni doping converted spin-state transition approach is reported for boosting 1 O2 production. Magnetic analysis and theoretical calculations reveal that Ni occupied at the octahedral site of Co3 O4 can effectively induce a low-to-high spin-state transition. The high-spin Ni-Co3 O4 generate appropriate binding strength and enhance electron transfer between the Co centers with oxygen intermediates, thereby improving the catalytic activity of Ni-Co3 O4 for effective generating 1 O2 . In neutral conditions, 1×106  CFU mL-1 Gram-negative ESBL-producing Escherichia coli (E. coli) could be inactivated by Ni-Co3 O4 system within 5 min. Further antibacterial mechanisms indicate that 1 O2 can lead to cell membrane damage and DNA degradation so as to irreversible cell death. Additionally, the developed Ni-Co3 O4 system can effectively inactivate bacteria from wastewater and bioaerosols. This work provides an effective strategy for designing high-spin electrocatalysis to boost 1 O2 generation for disinfection process.

Physicochemical Dual Cross-Linking Conductive Polymeric Networks Combining High Strength and High Toughness Enable Stable Operation of Silicon Microparticle Anodes.

The poor interfacial stability and insufficient cycling performance caused by undesirable stress hinder the commercial application of silicon microparticles (µSi) as next-generation anode materials for high-energy-density lithium-ion batteries. Herein, a conceptionally novel physicochemical dual cross-linking conductive polymeric network is designed combining high strength and high toughness by coupling the stiffness of poly(acrylic acid) and the softness of carboxyl nitrile rubber, which includes multiple H-bonds, by introducing highly branched tannic acid as a physical cross-linker. Such a design enables effective stress dissipation by folded molecular chains slipping and sequential cleavage of H-bonds, thus stabilizing the electrode interface and enhancing cycle stability. As expected, the resultant electrode (µSi/PTBR) delivers an unprecedented high capacity retention of ≈97% from 2027.9 mAh g-1 at the 19th to 1968.0 mAh g-1 at the 200th cycle at 2 A g-1 . Meanwhile, this unique stress dissipation strategy is also suitable for stabilizing SiOx anodes with a much lower capacity loss of ≈0.012% per cycle over 1000 cycles at 1.5 A g-1 . Atomic force microscopy analysis and finite element simulations reveal the excellent stress-distribution ability of the physicochemical dual cross-linking conductive polymeric network. This work provides an efficient energy-dissipation strategy toward practical high-capacity anodes for energy-dense batteries.

Oxygen-regulated carbon quantum dots as an efficient metal-free electrocatalyst for nitrogen reduction.

An electrocatalytic nitrogen reduction reaction under ambient conditions provides a wonderful blueprint for the conversion of nitrogen to ammonia. However, current research on ammonia synthesis is mainly focused on metal-based catalysts. It is still a great challenge to realize the effective activation of N2 on non-metallic catalysts. Herein, carbon quantum dots are reported to reduce dinitrogen to ammonia under ambient conditions. Benefiting from its numerous defect sites, this metal-free catalyst shows excellent catalytic performance in 0.1 M HCl with a faradaic efficiency of 17.59%. In addition, both experimental and theoretical results confirm that the catalytic performance of the catalyst can be improved by appropriately controlling the oxygen content of samples at different temperatures, and the utmost ammonia yield is 134.08 µg h-1 mg-1cat., which is almost three times higher than that of a reported metal-free material. The proposed oxygen regulation provides a new method to optimize the surface properties of metal-free catalysts for ammonia synthesis.

Construction of a Hierarchical Structure of Bimetallic Oxide Derived from Metal-Organic Frameworks.

Bimetallic oxides are a class of promising advanced functional metal nanomaterials, especially in terms of the sophisticated hierarchical structure of bimetallic oxide, which not only is in favor of enhancing their intrinsic physiochemical properties because of more accessible actives sites but also is capable of integrating the synergistic effect between two metals. Herein, we report a novel strategy to controllably construct bimetallic CuO/ZnO nanomaterials with sophisticated hierarchical structure through a pseudomorphic transformation and subsequent calcination process. The resulting unique hierarchical structure of ZnO/CuO is primarily constituted of a nanosphere and a rod grafted in a microscale cube with multidimensional size, which thus results in excellent dispersion, superior charge-transport capability, and abundant accessible active sites. Impressively, the optimized hierarchical structure product of CuO/ZnO (4:1) demonstrates an excellent glucose detection performance with a rapid response time, a wide linear range, a low detection limit, and strong antiinterference ability, realizing more advantages than commercial CuO or ZnO materials and shedding light on the positive correlation of the structure and performance. This study provides a new strategy for the controllable fabrication of the sophisticated hierarchical structure of bimetallic oxide nanomaterials.

Fabrication of Hierarchical Quaternary Architectures of Metal-Organic Frameworks through Programmed Transformation.

A new method to construct hierarchical architectures has been developed by programmed transformation of metal-organic frameworks (MOFs). A MOF precursor was fabricated by reaction of Cu(OAC)2 and 2,5-dihydroxyterephthalic acid (H4DOBDC), which could perform transformation in pure methanol solvent and the sodium dodecyl benzene sulfonate (SDBS) solution of methanol, respectively. Interestingly, two kinds of immersion solutions could induce the transformation of the MOF precursor into MOF-74, which resulted in different morphologies: nanoneedles for the methanol and nanosheets for the SDBS. Herein, nanosheets-mesorods-microcuboid hierarchical quaternary architectures of MOF have been successfully achieved by sequential immersion of the precursor in two kinds of transformation solutions, which demonstrates well-defined hierarchy from the nanoscale to mesoscale to microscale. A unique hierarchical architecture could be recognized as quaternary structures, taking the MOF unit cell as the primary structure, the nanosheets as the secondary structure, the mesorods as the tertiary structure, and the microcuboid as the quaternary structure. Our study indicated the potential of programmed transformation between MOFs in the construction of hierarchical architectures, offering a new approach to sophisticated materials.

Boride-derived oxygen-evolution catalysts.

Metal borides/borates have been considered promising as oxygen evolution reaction catalysts; however, to date, there is a dearth of evidence of long-term stability at practical current densities. Here we report a phase composition modulation approach to fabricate effective borides/borates-based catalysts. We find that metal borides in-situ formed metal borates are responsible for their high activity. This knowledge prompts us to synthesize NiFe-Boride, and to use it as a templating precursor to form an active NiFe-Borate catalyst. This boride-derived oxide catalyzes oxygen evolution with an overpotential of 167 mV at 10 mA/cm2 in 1 M KOH electrolyte and requires a record-low overpotential of 460 mV to maintain water splitting performance for over 400 h at current density of 1 A/cm2. We couple the catalyst with CO reduction in an alkaline membrane electrode assembly electrolyser, reporting stable C2H4 electrosynthesis at current density 200 mA/cm2 for over 80 h.

Synthesis of amorphous FeNiCo trimetallic hybrid electrode from ZIF precursors for efficient oxygen evolution reaction.

Development of non-noble multi-metallic electrocatalyst with high oxygen evolution reaction (OER) activity via a simple and low-cost method is of great importance for improving the efficiency of water electro-chemical splitting. Herein, a solution impregnation strategy was proposed to synthesize novel FeNi-doped Co-ZIF-L trimetallic hybrid electrocatalyst using Co-ZIF-L as sacrificial templates and Fe and Ni ions as etchants and dopants. This synthetic strategy could be realized via the etching-coprecipitation mechanism to obtain an amorphous hybrid containing multi-metal hydroxides. The as-prepared electrocatalyst loaded on Ni foam displays a low overpotential of 245 mV at 10 mA·cm-2, a small Tafel slope of 54.9 mV·dec-1, and excellent stability at least 12 h in the OER process. The facile and efficient synthetic strategy presents a new entry for the fabrication of ZIFs-derived multi-metallic electrocatalysts for OER electrocatalysis.

Fe-doped CoP nanosheet arrays: an efficient bifunctional catalyst for zinc-air batteries.

It is highly desired to design and develop low-cost and efficient bifunctional electrocatalysts for zinc-air batteries (ZABs). In this communication, we report that Fe-doped CoP nanosheet arrays on nickel foam (Fe0.33-CoP/NF) act as a highly active bifunctional electrocatalyst for both the oxygen reduction reaction and the oxygen evolution reaction in alkaline media. We further demonstrate the use of Fe0.33-CoP/NF as the cathode to construct rechargeable ZABs with superior performance to that of the CoP/NF counterpart. In concentrated alkaline electrolytes, such ZABs exhibit a higher power density of 63 mW cm-2 than that of CoP/NF (23 mW cm-2) with a long cycle life (up to 200 h).

Photoelectrochemical biosensor for microRNA detection based on multiple amplification strategies.

A photoelectrochemical biosensor is described for sensitive detection of microRNA-162a. A multiple amplification strategy is employed that involves (a) isothermal strand displacement polymerase reaction; (b) terminal deoxynucleotidyl transferase-mediated extension, (c) amplification of streptavidin-coated gold nanoparticles, and (d) biotin functionalized alkaline phosphatase. Graphite-like C3N4 (g-C3N4) nanosheets were used as photoactive material. By using these amplification strategies, the detection limit is as low as 0.18 fM of microRNA, and the photocurrent increases linearly with the concentration of microRNA-162a in the range from 0.5 fM to 1 pM. The method was successfully applied to quantify the expression level of microRNA-162a in total RNA extracted from the leaves of maize seedlings after incubation with the chemical mutagen ethyl methanesulfonate. The results confirmed the applicability of the method to the analysis of practical biological samples. Graphical Abstract Schematic of a photoelectrochemical microRNA assay based on a multiple amplification strategy involving (a) isothermal strand displacement polymerase reaction; (b) terminal deoxynucleotidyl transferase-mediated extension,

In situ development of amorphous Mn-Co-P shell on MnCo2O4 nanowire array for superior oxygen evolution electrocatalysis in alkaline media.

Exploitation of efficient and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is of great importance. Herein, we report that the formation of an amorphous Mn-Co-P shell on MnCo2O4 can boost its OER activity in alkaline media. The core-shell Mn-Co-P@MnCo2O4 nanowire array on Ti mesh (Mn-Co-P@MnCo2O4/Ti) shows excellent electrochemical catalytic activity and requires an overpotential of 269 mV to drive 10 mA cm-2 in 1.0 M KOH, which is 93 mV less than that for the MnCo2O4 nanoarray. Notably, this catalyst also shows strong long-term electrochemical durability with its activity being maintained for at least 100 h and achieves a high turnover frequency of 1.06 s-1 at an overpotential of 450 mV.