Pyrolysis of furfural residues: Property and applications of the biochar.

Furfural residue (FR) is a solid waste generated during the production of furfural from corn cobs. The chemical energy and material potential of FR can be potentially recovered via pyrolysis. In this study, the pyrolysis of FR at the temperature ranging from 350 to 650 °C at the varied heating rate was investigated, aiming to understand the characteristics of the pyrolysis products. The results indicate that the organic components of FR tend to be cracked to form biochar and gases as the dominate products, due to the high ash content of FR. The FR-derived bio-oil also contained abundant organics derived from cellulose and lignin. Increasing pyrolysis temperature favored formation of the organics with fused ring structures. Lower heating rate in pyrolysis also formed biochar with higher thermal stability and higher fixed carbon content by enhancing the extent of deoxygenation. Additionally, the transformation of -OH via dehydration, -C-H into = C-H via dehydrogenation, and the cracking of CO during carbonization of biochar in the pyrolysis were also observed during pyrolysis of FR. Activation of the FR-derived biochar generated abundant micropores and mesopores, rendering the activated carbon with superior specific capacitance as electrodes of electrocapacitors (329 Fg-1) and the excellent adsorption efficiency of phosphate (up to 98.81%).

Iodine-Doped Hollow Carbon Nanocages without Templates Strategy for Boosting Zinc-Ion Storage by Nucleophilicity.

Zn-ion hybrid supercapacitors (ZHCs) combining merits of battery-type and capacitive electrodes are considered to be a prospective candidate in energy storage systems. Tailor-made carbon cathodes with high zincophilicity and abundant physi/chemisorption sites are critical but it remains a great challenge to achieve both features by a sustainable means. Herein, a hydrogen-bonding interaction-guided self-assembly strategy is presented to prepare iodine-doped carbon nanocages without templates for boosting zinc-ion storage by nucleophilicity. The biomass ellagic acid contains extensional hydroxy and acyloxy groups with electron-donating ability, which interact with melamine and ammonium iodide to form organic supermolecules. The organic supermolecules further self-assemble into a nanocage-like structure with cavities under hydrothermal processes via hydrogen-bonding and π-π stacking. The carbon nanocages as ZHCs cathodes enable the high approachability of zincophilic sites and low ion migration resistance resulting from the interconnected conductive network and nanoscale architecture. The experimental analyses and theoretical simulations reveal the pivotal role of iodine dopants. The I5-/I3- doping anions in carbon cathodes have a nucleophilicity to preferentially adsorb the Zn2+ cation by the formation of C+-I5--Zn2+ and C+-I3--Zn2+. Of these, the C+-I3- shows stronger bonding with Zn2+ than C+-I5-. As a result, the iodine-doped carbon nanocages produced via this template-free strategy deliver a high capacity of 134.2 mAh/g at 1 A/g and a maximum energy and power density of 114.1 Wh/kg and 42.5 kW/kg.

Cross-linking and self-assembly synthesis of tannin-based carbon frameworks cathode for Zn-ion hybrid supercapacitors.

Carbon frameworks with well-developed porosity present broad application prospects in energy-related materials, and green preparation still face challenges. Herein, the tannins-derived framework-like carbon material is obtained by cross-linking and self-assembly strategy.The phenolic hydroxyl and quinones in tannin cross-linking react with the amine groups in the methenamine by simple stirring, which drives the self-assembly of tannins and methenamine,contributing to the reaction products being precipitated in solution as aggregates with framework-like structure. The porosity and micromorphology of framework-like structures are further enriched by the thermal stability difference between tannin and methenamine. The methenamine of framework-like structures is entirely removed by the sublimation and decomposition and the tannin is transformed into carbon materials inheriting framework-like structures after the carbonization, which offers the path for rapid electron transport. The framework-like structure, excellent specific surface area and nitrogen doping give the assembled Zn-ion hybrid supercapacitors a superior specific capacitance of 165.3 mAh·g-1 (350.4 F·g-1). This device could be charged to 1.87 V to power the bulb by using solar panels. This study proves that the tannin-derived framework-like carbon is a promising electrode of the Zn-ion hybrid supercapacitors, which is beneficial for value-added and industrial supercapacitors application of green feedstocks.

Synergy of Oxygen Vacancies and Acid Sites on N-Doped WO3 Nanobelts for Efficient C-C Coupling Synthesis of Benzoin Isopropyl Ether.

The surface property of a photocatalyst, including surface acid sites and oxygen vacancies, plays a pivotal role in photocatalytic organic synthesis reactions. Benzoin isopropyl ether (BIE) is usually produced via polycondensation of benzaldehyde and catalyzed with highly toxic cyanide. Here, we report a green photocatalytic approach for the selective synthesis of BIE over WO3 driven by a green-light-emitting diode. The improved photocatalytic activity can be attributed to the synergy of oxygen vacancies (VOs) and acid sites over N-doped WO3 nanobelts. The results revealed that reactant molecules were predominantly adsorbed and activated on surface oxygen vacancies (VOSs) and the Brønsted acid promoted the etherification reaction; the introduction of VOs and nitrogen altered the band structure and electronic properties, resulting in improved photocatalytic activity. Our work provides an efficient approach to the selective photocatalytic synthesis of organics over photocatalysts with finely tuned surface properties and band structures via defect and doping engineering.

Hydrogen-bonded frameworks crystals-assisted synthesis of flower-like carbon materials with penetrable meso/macropores from heavy fraction of bio-oil for Zn-ion hybrid supercapacitors.

The application of biomass-based carbon materials in electrode materials are usually subject to their deficient adsorption sites as well as sluggish diffusion of electrolyte ions. Herein, flower-like carbons are obtained from the heavy fraction of bio-oil with the auxiliary of Hydrogen-bonded frameworks (HOFs) crystals. During the co-carbonization of the both, the HOFs crystals are removed on account of its poor stability, which directs the formation of flower-like morphology and generates the penetrable meso/macropores across petal-like carbon nanosheets. In addition, the pyrolysis gases serve as the agents for activation to enrich the active sites without the further activation. The degree of graphitization and the contents of pyridine nitrogen for carbon materials could be flexibly adjusted with the contents of HOFs. Owing to the beneficial 3D flower-like structure, high specific surface area (1076 m2/g), large pore volume (2.59 cm3/g), and rational N species, the assembled Zn//BH-4 hybrid supercapacitor reaches a superior energy density of 117.5 Wh/kg at 890 W/kg and maintains 60.7 Wh/kg even at 16.2 kW/kg.

In Situ Electrochemical Fabrication of Ultrasmall Ru-Based Nanoparticles for Robust N2H4 Oxidation.

Ultrasmall Ru nanoparticles is expected as a potential alternative to Pt for efficient hydrazine oxidation (HzOR). However, preparation of ultrasmall and well-distributed Ru nanoparticles usually suffered from the steps of modification of supports, coordination, reduction with strong reducing reagents (e.g., NaBH4) or pyrolysis, imposing the complexity. Based on the self-reducibility of C-OH group and physical adsorption ability of commercial Ketjen black (KB), we developed an efficient, stable and robust Ru-based electrocatalyst (A-Ru-KB) by coupling impregnation of KB in RuCl3 solution and simple in situ electrochemical activation strategy, which endowed the formation of ultrasmall and well-distributed Ru nanoparticles. Benefiting from an enhanced exposure of Ru sites and the faster mass transport, A-Ru-KB achieved 63.4 and 3.9-fold enhancements of mass activity compared with Pt/C and Ru/C, respectively, accompanied by a ∼144 mV lower onset potential and faster catalytic kinetics than Pt/C. In the hydrazine fuel cell, the open-circuit voltage and maximal mass power density of A-Ru-KB was 130 mV and ∼3.8-fold higher than those of Pt/C, respectively, together with the long-term stability. This work would provide a facile and sustainable approach for large-scale production of other robust metal (electro)catalysts with ultrasmall nanosize for various energy conversion and electrochemical organic synthesis.

Boosting Oxygen Electroreduction over Strained Silver.

Manipulating the strain effect of Ag without any foreign metals to boost its intrinsic oxygen reduction reaction (ORR) activity is intriguing, but it remains a challenge. Herein, we developed a class of Ag-based electrocatalysts with tunable strain structures for efficient ORR via ligand-assisted competitive decomposition of Ag-organic complexes (AgOCs). Benefiting from the superior coordination capability, 4,4'-bipyridine as a ligand triggered a stronger competition with NaBH4 for Ag ions during reduction-induced decomposition of AgOCs in comparison with the counterparts of the pyrazine ligand and the NO3- anion, which moderately modulated the compressive strain structure to upshift the d-band center of the catalyst and increase the electron density of Ag. Accordingly, the O2 adsorption was obviously improved, and the stronger repulsion effect between the Ag sites and the 4e ORR product, i.e., the electron-rich OH-, was generated to promote the desorption of OH- via the Ag-OH bond cleavage, which enabled more Ag sites to be regenerated after ORR. Both of these led to an enhancement to the intrinsic ORR activity of the Ag-based catalyst. This competitive decomposition of metal-organic complex strategy would provide a facile method to design other catalysts with the well-tuned strain structures for energy conversion and heterocatalysis.

Mimicking Hydrazine Dehydrogenase for Efficient Electrocatalytic Oxidation of N2H4 by Fe-NC.

Pursuing nonprecious doped carbon with Pt-like electrocatalytic N2H4 oxidation activity for hydrazine fuel cells (HzFCs) remains a challenge. Herein, we present a Fe/N-doped carbon (Fe-NC) catalyst with mesopore-rich channel and highly dispersed Fe-N sites incorporated in N-doped carbon, as an analogue of hydrazine dehydrogenase (HDH), showing the structure-dependent activity for electrocatalytic oxidation of N2H4. The maximal turnover frequency of the N2H4 oxidation reaction (HzOR) over the Fe-N sites (62870 h-1) is 149-fold that over the pyridinic-N sites of N-doped carbon. The Fe mass activity of HzOR and maximal power density of HzFCs driven by Fe-NC approximately surpass those of Pt/C by 2.3 and 2.2 times, respectively. Theoretical calculation reveals that the Fe-N sites improve the dehydrogenation process of HzOR-related intermediates. One of the roles of the mesoporous structure in Fe-NC resembles that of a substrate channel in HDH for enhancing the transport of N2H4 besides exposing Fe-N sites and improving storage capacity of HzOR-related species.

Oxidase-Inspired Selective 2e/4e Reduction of Oxygen on Electron-Deficient Cu.

Development of low-cost and efficient (electro)catalysts with tunable 2e/4e oxygen reduction reaction (ORR) selectivity toward energy conversion, biomimetic catalysis, and biosensing has attracted growing interest. Herein, we reported that carbon nanohybrids with O- or N-coordinated Cu (Cu-OC or Cu-NC) showed superior activity for 2e and 4e electrocatalytic ORR with selectivities of 84.0% and 97.2%, respectively. Experimental evidence demonstrated that the strong electron-rich O-doped carbon in Cu-OC donated electrons to Cu2+, weakening the binding strength of H2O2 at Cu-O centers and facilitating the 2e ORR pathway for selective production of H2O2. However, the poor electron-donor ability of the N-doped carbon in Cu-NC made Cu-N sites more electron deficient due to the reduced electron transfer from N-doped carbon to Cu2+, promoting 4e ORR by enhancing adsorption of O2 and the ORR intermediates. The high 4e ORR activity of Cu-NC rendered its potential for application in a Zn-air battery and oxidase-mimicking activity for 3,3',5,5'-tetramethylbenzidine (TMB) and ascorbic acid (AA) oxidation. The maximal velocity (Vmax) of TMB and AA oxidation over Cu-NC was higher than some natural oxidases and noble-metal-based artificial enzymes. The lower activation energy for AA oxidation over Cu-NC resulted in a 263-fold higher oxidative rate than TMB, further prompting nonenzymatic sensing of AA by the competitive oxidation strategy.

Fe3O4@Carbon Nanosheets for All-Solid-State Supercapacitor Electrodes.

Fe3O4@carbon nanosheet composites were synthesized using ammonium ferric citrate as the Fe3O4/carbon precursor and graphene oxide as the structure-directing agent under a hydrothermal process. The surface chemical compositions, pore structures, and morphology of the composite were analyzed and characterized by nitrogen adsorption isotherms, TG analysis, FT-IR, X-ray photoelectron energy spectrum, transmission electron microscopy, and scanning electron microscopy. The composites showed excellent specific capacitance of 586 F/g, 340 F/g at 0.5 A/g and 10 A/g. The all-solid-state asymmetric supercapacitor device assembled using carbon nanosheets in situ embedded Fe3O4 composite and porous carbon showed a largest energy density of 18.3 Wh/kg at power density of 351 W/kg in KOH/PVA gel electrolyte. The synergism of high special surface to volume ratio, mesoporous structure, graphene-based conduction paths, and Fe3O4 nanoparticles provided a high surface area of ion-accessibility, high electric conductivity, and the utmost utilization of Fe3O4 and resulted in excellent specific capacitance, outstanding rate capability and cycling life as all-solid-state supercapacitor electrodes.

Carbon Nanosheets: Synthesis and Application.

Carbon nanosheets (CNSs) with tunable sizes, morphologies, and pore structures have been synthesized through several chemical routes. Graphitized CNSs have been synthesized through exfoliation, chemical vapor deposition, or high-temperature carbonization. Porous CNSs have been synthesized by using various methods, including pyrolysis, self-assembly, or a solvothermal method in connection with carbonization. These CNSs have successfully been used as detectors for metal ions, as cathodes for field electron emissions, as electrodes for supercapacitors and fuel cells, and as supports for photocatalytic and catalytic oxygen reduction. Therefore, the synthesis and application of CNSs are receiving increasing levels of interest, particularly as application benefits, in the context of future energy/chemical industry, are becoming recognized. This review provides a summary of the most recent and important progress in the production of CNSs and highlights their application in environmental and energy-related fields.