RESUMO
Selective reduction of CO2 is an efficient solution for producing nonfossil-based chemical feedstocks and simultaneously alleviating the increasing atmospheric concentration of this greenhouse gas. With this aim, molecular electrocatalysts are being extensively studied, although selectivity remains an issue. In this work, a combined experimental-computational study explores how the molecular structure of Mn-based complexes determines the dominant product in the reduction of CO2 to HCOOH, CO, and H2. In contrast to previous Mn(bpy-R)(CO)3Br catalysts containing alkyl amines in the vicinity of the Br ligand, here, we report that bpy-based macrocycles locking these amines at the side opposite to the Br ligand change the product selectivity from HCOOH to H2. Ab initio molecular dynamics simulations of the active species showed that free rotation of the Mn(CO)3 moiety allows for the approach of the protonated amine to the reactive center yielding a Mn-hydride intermediate, which is the key in the formation of H2 and HCOOH. Additional studies with DFT methods showed that the macrocyclic moiety hinders the insertion of CO2 to the metal hydride favoring the formation of H2 over HCOOH. Further, our results suggest that the minor CO product observed experimentally is formed when CO2 adds to Mn on the side opposite to the amine ligand before protonation. These results show how product selectivity can be modulated by ligand design in Mn-based catalysts, providing atomistic details that can be leveraged in the development of a fully selective system.
RESUMO
Alkali metal (Li, Na, K) ion batteries with high energy density are urgently required for large-scale energy storage applications while the lack of advanced anode materials restricts their development. Recently, Bi-based materials have been recognized as promising electrode candidates for alkali metal-ion batteries due to their high volumetric capacity and suitable operating potential. Herein, the latest progress of Bi-based electrode materials for alkali metal-ion batteries is summarized, mainly focusing on synthesis strategies, structural features, storage mechanisms, and the corresponding electrochemical performance. Particularly, the optimization of electrode-electrolyte interphase is also discussed. In addition, the remaining challenges and further perspectives of Bi-based electrode materials are outlined. This review aims to provide comprehensive knowledge of Bi-based materials and offer a guideline toward more applications in high-performance batteries.
RESUMO
As an anode for lithium-ion batteries, metallic bismuth (Bi) can provide a superb volumetric capacity of 3800 mA h cm-3, showing perspective value for application. It is a pity that the severe volume swelling during the lithiation process leads to the dramatic deterioration of the cycling performances. To overcome this issue, Bi nanorods encapsulated in N-doped carbon nanotubes (yolk-shell Bi@C-N) are elaborately designed through in situ thermal reduction of Bi2S3@polypyrrole nanorods. In comparison with the commercial Bi, the lithium storage capacities of Bi@C-N are significantly enhanced, and it presents a stable volumetric capacity of 1700 mA h cm-3 over 500 cycles at a high current density of 1.0 A g-1, nearly 2.2 times that of graphite. The N-doped carbon nanotube and the cavity between the carbon wall and Bi jointly contribute to this superior performance. Especially, the failure mechanism of Bi nanorods and the protective effect of the carbon shell are revealed by ex situ TEM, which illuminates the decreasing tendency in the initial 10-20 cycles and the subsequent stable trend of cyclic performance.
RESUMO
Antimony sulfide (Sb2S3) has drawn widespread attention as an ideal candidate anode material for sodium-ion batteries (SIBs) due to its high specific capacity of 946 mA h g-1 in conversion and alloy reactions. Nevertheless, volume expansion, a common flaw for conversion-alloy type materials during the sodiation and desodiation processes, is bad for the structure of materials and thus obstructs the application of antimony sulfide in energy storage. A common approach to solve this problem is by introducing carbon or other matrices as buffer material. However, the common preparation of Sb2S3 could result in environmental pollution and excessive energy consumption in most cases. To incorporate green chemistry, natural stibnite ore (Sb2S3) after modification via carbon sheets was applied as a first-hand material in SIBs through a facile and efficient strategy. The unique composites exhibited an outstanding electrochemical performance with a higher reversible capacity, a better rate capability, as well as an excellent cycling stability compared to that of the natural stibnite ore. In short, the study is expected to offer a new approach to improve Sb2S3 composites as an anode in SIBs and a reference for the development of natural ore as a first-hand material in energy storage.
RESUMO
The transition-metal sulfide, CuS, is deemed a promising material for energy storage, mainly derived from its good chemisorption and conductivity, although serious capacity fading limits its advancement within reversible lithium storage. Learning from the gold extraction method utilizing the lime-sulfur-synthetic-solution, a CuS@S hybrid utilizing CaS x as both sulfur resource and reductant-oxidant is prepared, which is an efficient approach to apply the metallurgy for the preparation of electrode materials. Regulating the amount of CuCl2, the CuS@S is induced to reach a molecular-level hybrid. When utilized as an anode within a lithium-ion battery, it presents the specific capacity of 514.4 mA h g-1 at 0.1 A g-1 over 200 cycles. Supported by the analyses of pseudo-capacitive behaviors, it is confirmed that the CuS matrix with the suitable content of auxiliary sulfur could improve the durability of the CuS-based anode. Expanding the wider application within lithium-sulfur batteries, the synchronous growth of CuS@S exhibits stronger chemisorption with polysulfides than the mechanical mixture of CuS and S. A suite of in situ electrochemical impedance spectroscopy studies further investigates the stable resistances of the CuS@S within the charge/discharge process, corresponding to the reversible structure evolution. This systematic work may provide a practical fabricating route of metal sulfides for scalable energy storage applications.
RESUMO
Transition metal sulfides (TMSs) have been extensively studied as electrode materials for sodium-ion batteries by virtue of their high theoretical capacity. However, the poor cyclability limits the practical application of TMSs in sodium ion batteries. In this study, N-rich carbon-coated Co3S4 ultrafine nanocrystal (Co3S4@NC) was prepared by utilizing ZIF-67 as a precursor through continuous carbonization and sulfuration processes, exhibiting ultrafine nanocrystals with a diameter of about 5 nm. When utilized as the anode for sodium ion batteries, the nanohybrid material exhibits remarkable cycling performance with a high specific capacity of 420.9 mA h g-1 at the current density of 100 mA g-1 after 100 cycles, indicating that the cycling performance is strengthened by the nitrogen-doped carbon coating. Impressively, the obtained material shows good rate performances with reversible specific capacities of 386.7, 284.0, and 151.2 mA h g-1 at 400, 1000, and 1400 mA g-1, respectively, due to the high surface-capacitance contribution and porous structure inherited from the precursor, which finally results in the increase in infiltration of electrolyte and the accelerating diffusion rate of Na+. This study sheds light on the routes to improve the performance of TMSs@nitrogen-doped carbon nanohybrid materials for sodium ion batteries.
