Tailoring Oxygen-Depleted and Unitary Ti3C2Tx Surface Terminals by Molten Salt Electrochemical Etching Enables Dendrite-Free Stable Zn Metal Anode.

Two-dimensional Ti3C2Tx MXene materials, with metal-like conductivities and versatile terminals, have been considered to be promising surface modification materials for Zn-metal-based aqueous batteries (ZABs). However, the oxygen-rich and hybridized terminations caused by conventional methods limit their advantages in inhibiting zinc dendrite growth and reducing corrosion-related side reactions. Herein, -O-depleted, -Cl-terminated Ti3C2Tx was precisely fabricated by the molten salt electrochemical etching of Ti3AlC2, and controlled in situ terminal replacement from -Cl to unitary -S or -Se was achieved. The as-prepared -O-depleted and unitary-terminal Ti3C2Tx as Zn anode coatings provided excellent hydrophobicity and enriched zinc-ionophilic sites, facilitating Zn2+ horizontal transport for homogeneous deposition and effectively suppressing water-induced side reactions. The as-assembled Ti3C2Sx@Zn symmetric cell achieved a cycle life of up to 4200 h at a current density and areal capacity of 2 mA cm-2 and 1 mAh cm-2, respectively, with an impressive cumulative capacity of up to 7.25 Ah cm-2 at 5 mA cm-2//2 mAh cm-2. These findings provide an effective electrochemical strategy for tailoring -O-depleted and unitary Ti3C2Tx surface terminals and advancing the understanding of the role of specific Ti3C2Tx surface chemistry in regulating the plating/stripping behaviors of metal ions.

One-step Synthesis of Organic Terminal 2D Ti3C2Tx MXene Nanosheets by Etching of Ti3AlC2 in an Organic Lewis Acid Solvent.

The surface and interface chemistry are critical for controlling the properties of two-dimensional transition metal carbides and nitrides (MXenes). Numerous efforts have been devoted to the functionalization of MXenes with small inorganic ligands; however, few etching methods have been reported on the direct bonding of organic groups to MXene surfaces. In this work, we demonstrated an efficient and rapid strategy for the direct synthesis of 2D Ti3C2Tx MXene nanosheets with organic terminal groups in an organic Lewis acid (trifluoromethanesulfonic acid) solvent, without introducing additional intercalations. The dissolution of aluminum and the subsequent in situ introduction of trifluoromethanesulfonic acid resulted in the extraction of Ti3C2Tx MXene (T=CF3SO3 -) (denoted as CF3SO3H-Ti3C2Tx) flakes with sizes reaching 15 µm and high productivity (over 70 %) of monolayers or few layers. More importantly, the large CF3SO3H-Ti3C2Tx MXene nanosheets had high colloidal stability, making them promising as efficient electrocatalysts for the hydrogen evolution reaction.

Electronic Modulation in Cu Doped NiCo LDH/NiCo Heterostructure for Highly Efficient Overall Water Splitting.

Layered double hydroxides (LDHs), promising bifunctional electrocatalysts for overall water splitting, are hindered by their poor conductivity and sluggish electrochemical reaction kinetics. Herein, a hierarchical Cu-doped NiCo LDH/NiCo alloy heterostructure with rich oxygen vacancies by electronic modulation is tactfully designed. It extraordinarily effectively drives both the oxygen evolution reaction (151 mV@10 mA cm-2) and the hydrogen evolution reaction (73 mV@10 mA cm-2) in an alkaline medium. As bifunctional electrodes for overall water splitting, a low cell voltage of 1.51 V at 10 mA cm-2 and remarkable long-term stability for 100 h are achieved. The experimental and theoretical results reveal that Cu doping and NiCo alloy recombination can improve the conductivity and reaction kinetics of NiCo LDH with surface charge redistribution and reduced Gibbs free energy barriers. This work provides a new inspiration for further design and construction of nonprecious metal-based bifunctional electrocatalysts based on electronic structure modulation strategies.

A universal and scalable transformation of bulk metals into single-atom catalysts in ionic liquids.

Single-atom catalysts (SACs) with maximized metal atom utilization and intriguing properties are of utmost importance for energy conversion and catalysis science. However, the lack of a straightforward and scalable synthesis strategy of SACs on diverse support materials remains the bottleneck for their large-scale industrial applications. Herein, we report a general approach to directly transform bulk metals into single atoms through the precise control of the electrodissolution-electrodeposition kinetics in ionic liquids and demonstrate the successful applicability of up to twenty different monometallic SACs and one multimetallic SAC with five distinct elements. As a case study, the atomically dispersed Pt was electrodeposited onto Ni3N/Ni-Co-graphene oxide heterostructures in varied scales (up to 5 cm × 5 cm) as bifunctional catalysts with the electronic metal-support interaction, which exhibits low overpotentials at 10 mA cm-2 for hydrogen evolution reaction (HER, 30 mV) and oxygen evolution reaction (OER, 263 mV) with a relatively low Pt loading (0.98 wt%). This work provides a simple and practical route for large-scale synthesis of various SACs with favorable catalytic properties on diversified supports using alternative ionic liquids and inspires the methodology on precise synthesis of multimetallic single-atom materials with tunable compositions.

Recent Advances in Electrochemical-Based Silicon Production Technologies with Reduced Carbon Emission.

Sustainable and low-carbon-emission silicon production is currently one of the main focuses for the metallurgical and materials science communities. Electrochemistry, considered a promising strategy, has been explored to produce silicon due to prominent advantages: (a) high electricity utilization efficiency; (b) low-cost silica as a raw material; and (c) tunable morphologies and structures, including films, nanowires, and nanotubes. This review begins with a summary of early research on the extraction of silicon by electrochemistry. Emphasis has been placed on the electro-deoxidation and dissolution-electrodeposition of silica in chloride molten salts since the 21st century, including the basic reaction mechanisms, the fabrication of photoactive Si films for solar cells, the design and production of nano-Si and various silicon components for energy conversion, as well as storage applications. Besides, the feasibility of silicon electrodeposition in room-temperature ionic liquids and its unique opportunities are evaluated. On this basis, the challenges and future research directions for silicon electrochemical production strategies are proposed and discussed, which are essential to achieve large-scale sustainable production of silicon by electrochemistry.

Molten salt electrosynthesis of Cr2GeC nanoparticles as anode materials for lithium-ion batteries.

The two-dimensional MAX phases with compositional diversity are promising functional materials for electrochemical energy storage. Herein, we report the facile preparation of the Cr2GeC MAX phase from oxides/C precursors by the molten salt electrolysis method at a moderate temperature of 700°C. The electrosynthesis mechanism has been systematically investigated, and the results show that the synthesis of the Cr2GeC MAX phase involves electro-separation and in situ alloying processes. The as-prepared Cr2GeC MAX phase with a typical layered structure shows the uniform morphology of nanoparticles. As a proof of concept, Cr2GeC nanoparticles are investigated as anode materials for lithium-ion batteries, which deliver a good capacity of 177.4 mAh g-1 at 0.2 C and excellent cycling performance. The lithium-storage mechanism of the Cr2GeC MAX phase has been discussed based on density functional theory (DFT) calculations. This study may provide important support and complement to the tailored electrosynthesis of MAX phases toward high-performance energy storage applications.

Experimental and computational approaches to study the chlorination mechanism of pentlandite with ammonium chloride.

Pentlandite (Fe4.5Ni4.5S8) is the primary source for the metallurgical production of nickel worldwide, however it usually coexists with copper sulfide in nature. To develop an efficient and green process for the separation and extraction of valuable metals from the nickel sulfide concentrate, herein we conducted experimental studies and density functional theory (DFT) calculations to elucidate the chlorination mechanism of pentlandite using ammonium chloride (NH4Cl). First, low-temperature chlorination roasting experiments with NH4Cl were performed in which pentlandite was successfully converted into the corresponding metal chlorides (FeCl2 and NiCl2). Then, the chlorination product was analyzed via energy dispersive spectrometry to reveal the elemental distribution at the cross-section. Results reveal that Fe atoms in pentlandite underwent preferential chlorination to form a chloride layer, whereas Ni atoms remained at the center of the grain. Furthermore, density functional theory calculations were performed to investigate the chlorination mechanism of pentlandite by exploring two possible pathways, involving the adsorption of oxygen (O2), ammonium chloride (NH4Cl) and chlorine (Cl2) on both the (001) and (010) surfaces of pentlandite. Considering that the chlorination of pentlandite was achieved in air atmosphere, we first consider the direct chlorination of pentlandite by NH4Cl in the presence of oxygen. Dissociative oxygen adsorption was found to promote the chlorination process by providing oxygen sites for the dissociation of HCl, which is decomposed from NH4Cl, eventually leading to the formation of H2O and FeCl2 species. Alternatively, the reaction between pentlandite and Cl2 was proved to be feasible thermodynamically.

Efficient Synchronous Extraction of Nickel, Copper, and Cobalt from Low-Nickel Matte by Sulfation Roasting‒Water Leaching Process.

Considering that the low recovery efficiency and the massive loss of valuable metals by the traditional pyrometallurgical process smelting low‒nickel matte. Therefore, this paper focuses on studying the optimal process parameters and the mechanism of sulphation roasting followed by water leaching achieving efficient synchronous extraction of nickel (Ni), copper (Cu), and cobalt (Co) from low‒nickel matte with sodium sulfate as the sulfating addictive. Under optimal conditions, the recovery efficiency of Ni, Cu, and Co metals can achieve 95%, 99%, and 94%, respectively, whereas the recovery efficiency of Fe metal is less than 1%. The results revealed that the mechanism of the sulfating roasting pretreatment could form a liquidus eutectic compound sulfates [Na2Me(SO4)2] (Me = Ni, Cu, Co) at the solid-solid interface, which plays a significant role in promoting the leaching efficiency of valuable metals. Not only enhance the reaction kinetics of sulfation, but improve the utilization efficiency of SO2/SO3. Thus, the sulfation roasting‒water leaching process developing an efficient and eco-friendly pathway to simultaneous extraction of Ni, Cu, and Co valuable metals from low grade sulfide ores.

Mechanistic studies on millerite chlorination with ammonium chloride.

Millerite (NiS) is the main source for metallurgical production of nickel worldwide. To improve the extraction rate of nickel, chlorination is usually carried out, as the resulting nickel chloride (NiCl2) can easily dissolve in water and be separated. Although molecular chlorine (Cl2) can be used as the chlorination reagent, greener reagents such as ammonium chloride (NH4Cl) are preferable from a process design perspective. However, the efficiency of NH4Cl as a chlorination reagent must be further improved for this process to be viable for industrial applications, and mechanistic understanding is imperative to this end. Here, we performed extensive density functional theory (DFT) calculations to elucidate the chlorination mechanism of NiS by exploring three possible pathways. We first considered the direct chlorination of NiS by Cl2, which was suggested to form by the reaction between NH4Cl and SO3 catalyzed by a metal oxide. Alternatively, NH4Cl was found to react favorably with the partially or fully oxidized NiS surface in the presence of oxygen (O2). During the oxidation of NiS, sulfur dioxide (SO2) may form. Furthermore, sulfur or oxygen vacancy was predicted to form during the chlorination of NiS or NiO with NH4Cl. Based on the available experimental evidence and our computational results, three possible mechanisms for the chlorination of NiS using NH4Cl as the chlorination reagent in the presence of O2 were proposed.

Alkali carbonates promote CO2 capture by sodium orthosilicate.

Sodium orthosilicate was synthesized by a wet chemical method with further calcination at 600 °C. Mixtures of Na4SiO4 and alkali (Li/Na/K) carbonates were prepared by a mechanical mixing method. The CO2 capture performance of the samples was characterized by dynamic thermogravimetric analyses and in situ XRD and Raman spectroscopy in 80 vol% CO2 mixed with 20 vol% N2. It was found that sodium orthosilicate could be used for CO2 sorption, and its maximum capacity could reach up to 19.2 wt%. The addition of alkali carbonates, which serve as promoters, led to the enhancement of the CO2 capture performance of Na4SiO4, especially at low temperatures, because of the formation of C2O52-. The existence of C2O52- in the mixture exposed to 80 vol% CO2 was confirmed by in situ Raman spectra, and its geometric structure was presented by DFT calculations. The formation of C2O52- within carbonates exhibited a positive influence on the CO2 capture at low temperatures and the enhancement of CO2 diffusion by Grotthuss-like transport through the carbonate product shell at high temperatures besides the formation of eutectic carbonate melts.

Energy dispersive spectrometry and first principles studies on the oxidation of pentlandite.

Experimental and computational studies were carried out to investigate the oxidation of pentlandite (Fe4.5Ni4.5S8). The oxidation product was first analyzed by energy dispersive spectrometry to reveal the elemental distribution at the cross section. Our experimental study shows that the Fe atoms in pentlandite migrated to the surface and were preferentially oxidized to form a thin layer of Fe2O3, whereas the Ni atoms remained at the center of the grain. Furthermore, density functional theory calculations were performed to investigate the adsorption and diffusion of atomic oxygen as well as the adsorption and dissociation of molecular oxygen on the (001) and (010) surfaces of pentlandite. From the calculated adsorption energies of atomic oxygen at the different sites of the (001) and (010) surfaces, we found that oxidation of the Fe sites was preferable to that of the Ni sites when exposed to an oxidizing atmosphere. For molecular oxygen adsorption on the surfaces of pentlandite, the bridge sites (Fe-Ni and Fe-Fe) were found to be the most favorable adsorption sites. The dissociative adsorption of O2 is thermodynamically more favorable than the molecular adsorption. Calculated dissociation barriers show that the oxidation is feasible during high temperature roasting.

In-situ XRD and EDS method study on the oxidation behaviour of Ni-Cu sulphide ore.

The oxidation mechanism of sulfides is the key issue during the sulphide-metallurgy process. In this study, the phase transformation and element migration were clearly demonstrated by in-situ laboratory-based X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS), respectively. The reaction sequence and a four-step oxidation mechanism were proposed and identified. The elemental distribution demonstrated that at a low temperature, the Fe atoms diffused outward and the Ni/Cu atoms migrated toward the inner core, whereas the opposite diffusion processes were observed at a higher temperature. Importantly, the unique visual presentation of the oxidation behaviour provided by the combination of in-situ XRD and EDS might be useful for optimising the process parameters to improve the Ni/Cu extraction efficiency during Ni-Cu sulphide metallurgy.