Balancing the Components of Biomass and the Reactivity of Pyrolysis Gas: Biomass-Assisted Recycling of Spent LiCoO2 Batteries.

Waste biomass is one of the promising feedstocks to supply syngas that can be used as fuels, chemicals, reductants, etc. However, the relationship between the component of biomass and the constituent of pyrolysis gas remains unclear. Here, we study the pyrolysis behaviors of various biomasses and reveal the relationship between the biomass components and gas compositions. Further, different pyrolysis gases are applied for the reduction of spent lithium cobalt oxide (LiCoO2) below 500 °C. The pyrolysis gas with a higher concentration of CO has a higher reductivity to convert LiCoO2 to CoO and Li2CO3 with a conversion rate close to 100% in 1 h at 500 °C. The biomass rich in cellulose and with a lower content of lignin tends to produce pyrolysis gas with a high concentration of CO, which comes from the deliberate breakdown of carboxyl, carbonyl, ether, and ester linkages. Moreover, LiCoO2 exerts catalytic functions over the deoxygenation and enhancement of oxygenates and single-ring aromatics. Overall, this paper offers a tailored approach to regulating biomass pyrolysis gases, enabling highly efficient battery recycling and syngas production.

Recovery of valuable metals from spent lithium-ion batteries through biomass pyrolysis gas-induced reduction.

The development of spent lithium-ion batteries (LIBs) recycling technologies can effectively alleviate environmental pressure and conserve metal resources. We propose a win-win strategy for pyrolysis gas reduction by lignocellulosic biomass, ensuring gas-induced reduction by spatial isolation of biomass and lithium transition metal oxides (LiTMOX (TM = Ni, Co, Mn)), and avoiding the separation of solid carbon and TMOX (TM = Ni, Co, Mn). In the spent LiCoO2 batteries, the lithium recovery efficiency reaches 99.99% and purity reaches 98.3% at 500 °C. In addition, biomass pyrolysis gas reduction is also applicable to treat spent LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 batteries. Thermodynamic analysis verifies that CO dominates the gas reduction recovery process. DFT calculation indicates that the gas reduction induces the collapse of the oxygen framework of LiTMOX (TM = Ni, Co, Mn). Everbatt-based economic and environmental analysis illustrates that this is an environment-friendly and energy-saving method.

Recycling Spent Lithium-Ion Batteries Using Waste Benzene-Containing Plastics: Synergetic Thermal Reduction and Benzene Decomposition.

Spent lithium-ion batteries (LIBs) and benzene-containing polymers (BCPs) are two major pollutants that cause serious environmental burdens. Herein, spent LIBs and BCPs are copyrolyzed in a sealed reactor to generate Li2CO3, metals, and/or metal oxides without emitting toxic benzene-based gases. The use of a closed reactor allows the sufficient reduction reaction between the BCP-derived polycyclic aromatic hydrocarbon (PAH) gases and lithium transition metal oxides, achieving the Li recovery efficiencies of 98.3, 99.9, and 97.5% for LiCoO2, LiMn2O4, and LiNi0.6Co0.2Mn0.2O2, respectively. More importantly, the thermal decomposition of PAHs (e.g., phenol and benzene) is further catalyzed by the in situ generated Co, Ni, and MnO2 particles, which forms metal/carbon composites and thus prevent the emissions of toxic gases. Overall, the copyrolysis in a closed system paves a green way to synergistically recycle spent LIBs and handle waste BCPs.

An iron-base oxygen-evolution electrode for high-temperature electrolyzers.

High-temperature molten-salt electrolyzers play a central role in metals, materials and chemicals production for their merit of favorable kinetics. However, a low-cost, long-lasting, and efficient high-temperature oxygen evolution reaction (HT-OER) electrode remains a big challenge. Here we report an iron-base electrode with an in situ formed lithium ferrite scale that provides enhanced stability and catalytic activity in both high-temperature molten carbonate and chloride salts. The finding is stemmed from a discovery of the ionic potential-stability relationship and a basicity modulation principle of oxide films in molten salt. Using the iron-base electrode, we build a kiloampere-scale molten carbonate electrolyzer to efficiently convert CO2 to carbon and oxygen. More broadly, the design principles lay the foundations for exploring cheap, Earth-abundant, and long-lasting HT-OER electrodes for electrochemical devices with molten carbonate and chloride electrolytes.

Thermal reduction-desorption of cadmium from contaminated soil by a biomass co-pyrolysis process.

Thermal desorption is one of the methods commonly used for the remediation of contaminated soil. However, its suitability for the treatment of widespread Cd-contaminated soil was seldom investigated, because the desorption of Cd was found to be difficult, even at a high heating temperature. In the present study, a biomass co-pyrolysis (BCP) method is proposed for the thermal treatment of Cd-contaminated soil. The results showed that, when the mixture of biomass and contaminated soil was pyrolyzed at ~550 oC, the gaseous pyrolytic products (such as CO and hydrocarbon gases) from the biomass could chemically reduce the Cd(II) into volatile Cd0, thereby allowing the evaporation of vaporized Cd0 from the soil within a short operating time. The BCP method can achieve a highly efficient removal of Cd from the soil samples spiked with a large amount of Cd(II). The remediated soil, containing the remaining biochars, showed a good regreening potential and a significant decrease in Cd bioavailability. It also showed a good performance for the remediation of field soils from four contaminated sites (>92% removal efficiencies), and one of the treated soils could even meet the Cd screening level of agricultural land of China.

Degradation of 2,4-DCP using persulfate and iron/E-carbon micro-electrolysis coupling system.

The greenhouse gas carbon dioxide (CO2) was converted to a novel CO2 conversion material (electrolytic carbon, EC) by molten salt electrochemical conversion, which served as the carbon source to prepare an iron-carbon composite (Fe-EC). The composite was used to activate persulfate (PS) and degrade 2,4-dichlorophenol (2,4-DCP) in an aqueous solution. The effects of several essential operating parameters such as PS dosage and pH on 2,4-DCP degradation were investigated. The removal efficiency of 2,4-DCP (20 mg L-1) was 97.8% in the presence of Fe-EC (50 mg L-1) and PS (1 mmol L-1). Moreover, the average % reaction stoichiometric efficiency (RSE) (calculated for all selected times 5-60 min) was maintained at 23.07%. Electron paramagnetic resonance (EPR), classical radical scavenging experiments, and density functional theory (DFT) calculations were integrated for a mechanistic study, which disclosed that the active species in the system were identified as SO4⦁-, •OH, and O2⦁-. Moreover, the iron-carbon micro-electrolysis/PS (ICE-PS) system had a high tolerance to a wide range of pH, which would provide theoretical guidance for the treatment of organic pollutants in practical industrial wastewater.

Molten Electrolyte-Modulated Electrosynthesis of Multi-Anion Mo-Based Lamellar Nanohybrids Derived from Natural Minerals for Boosting Hydrogen Evolution.

The multi-anion molybdenum-based nanohybrids, N-doped ß-Mo2C/MoP/MoOx (denoted as MoCPO), serving as a highly efficient catalyst for hydrogen evolution reaction (HER), are fabricated via a simple and scalable electrosynthesis in molten NaCl-KCl, which integrates pyrolysis/electroreduction/compounding into a one-pot strategy using polyphosphazenes (PPAs) and earth-abundant molybdenite (mainly MoS2) as precursors. The deliberately selected PPA and molten electrolyte ensure the unique lamellar nanostructures and the blending of multiple anions of C, N, P, and O in the obtained catalyst, specifically, triggering the in situ formation of the structural oxygen vacancies (VO) in MoCPO. The nature of the hybrids can be regulated by adjusting the synthesis condition. The optimized hybrid displays a low overpotential of 99.2 mV at 10 mA cm-2 for HER in 0.5 M H2SO4 and stays active over a broad pH range. The theoretical calculations reveal that VO in the hybrids serves as favorable active sites, thus contributing to the superior HER activity. Moreover, MoCPO is also effective for overall water splitting as a bifunctional catalyst.

Concentration-Dependent Enhancing Effect of Dissolved Silicate on the Oxidative Degradation of Sulfamethazine by Zero-Valent Iron under Aerobic Conditions.

Dissolved silicate, as a ubiquitous inorganic component in natural waters, is reported to depress the reactivity of zero-valent iron (ZVI) for reductive reactions under anoxic conditions, but it is unclear if the same inhibitory effect occurs for a ZVI/O2 system. In this study, the role of dissolved silicate for the reactivity of micron-sized ZVI (mZVI) was revisited under aerobic conditions, and different observations were found. Silicate had a volcano-type enhancing effect on the performance of the ZVI/O2 system for sulfamethazine (SMT) degradation. The results showed that, under a circum-neutral or alkaline pH condition (pH 6.0-9.0), the presence of dissolved silicate could significantly enhance the degradation of SMT because silicate coordinated with ferrous ions and further led to the generation of reactive oxygen species (ROS). This study suggests that silicate can act as both a ligand and corrosion inhibitor in a ZVI/O2 system: the coordination of silicate and ferrous iron accelerated the oxidative degradation of organic pollutants in an oxic aqueous solution, while the corrosion inhibitory effect of surface-bound silicate at higher concentrations may decrease the reactivity of the ZVI/O2 system, thereby offsetting the enhancing effect from the silicate-coordinated ferrous iron. This study not only redefines the role of naturally occurring silicate for a ZVI reaction system but also gives clues to develop high-efficiency ZVI/O2 technologies for water remediation.

Disilicate-Assisted Iron Electrolysis for Sequential Fenton-Oxidation and Coagulation of Aqueous Contaminants.

Sodium disilicate (SD), an inorganic and environmentally friendly ligand, is introduced into the conventional iron electrolysis system to achieve an oxidizing Fenton process to degrade organic pollutants. Electrolytic ferrous ions, which are complexed by the disilicate ions, can chemically reduce dioxygen molecules via consecutive reduction steps, producing H2O2 for the Fenton-oxidation of organics. At the near-neutral pH (from 6 to 8), the disilicate-Fe(II) complexes possess strong reducing capabilities; therefore, a near-neutral pH rather than an acid condition is preferable for the disilicate-assisted iron electrolysis (DAIE) process. Following the DAIE process, the different complexing capacities of disilicate for ferrous/ferric ions and calcium ions can be used to break the disilicate-iron complexes. The addition of CaO or CaCl2 can precipitate ferrous/ferric ions, disilicates and possibly heavy metals in the wastewater. Compared to previously reported organic and phosphorus ligands, SD is a low-cost inorganic agent that does not lead to secondary pollution, and would not compete with the target organic pollutants for •OH; therefore, it would greatly expand the application fields of the O2 activation process. The combination of DAIE and CaO treatments is envisioned to be a versatile and affordable method for treating wastewater with complicated pollutants (e.g., mixtures of biorefractory organics and heavy metals).

Ionic liquids assisted formation of an oil/water emulsion stabilised by a carbon nanotube/ionic liquid composite layer.

Assisted by ionic liquids, a facile way of preparing size controllable emulsions stabilised by a CNT/IL composite has been demonstrated. The functionally and structurally tunable CNT/IL composite layer will potentially enhance the application of emulsion in template synthesis, biphase catalysis and interface electron/charge transfer.