Visible Light-Driven Highly Selective CO2 Reduction to CH4 Using Potassium-Doped g-C3N5.

Establishment of an efficient and robust artificial photocatalytic system to convert solar energy into chemical fuels through CO2 conversion is a cherished goal in the fields of clean energy and environmental protection. In this work, we have explored an emergent low-Z nitrogen-rich carbon nitride material g-C3N5 (analogue of g-C3N4) for CO2 conversion under visible light illumination. A significant enhancement of the CH4 production rate was detected for g-C3N5 in comparison to that of g-C3N4. Notably, g-C3N5 also showed a very impressive selectivity of 100% toward CH4 as compared to 21% for g-C3N4. The photocatalytic CO2 conversion was performed without using sacrificial reagents. We found that 1% K doping in g-C3N5 enhanced its performance even further without compromising the selectivity. Moreover, 1% K-doped g-C3N5 also exhibited better photostability than undoped g-C3N5. We have also employed density functional theory calculation-based analyses to understand and elucidate the possible reasons for the better photocatalytic performance of K-doped g-C3N5.

Designing Nanoengineered Photocatalysts for Hydrogen Generation by Water Splitting and Conversion of Carbon Dioxide to Clean Fuels.

Semiconductor photocatalysis has received tremendous attention in the past decade as it has shown great promise in the context of clean energy harvesting for environmental remediation. Sunlight is an inexhaustible source of energy available to us throughout the year, although it is rather dilutely dispersed. Semiconductor based photocatalysis presents one of the best ways to harness this source of energy to carry out chemical reactions of interest that require external energy input. Photocatalytic hydrogen generation by splitting of water, CO2 mitigation, and CO2 conversion to green fuel have therefore become the highly desirable clean and sustainable processes for a better tomorrow. Although numerous efforts have been made and continue to be expended to search and develop new classes of photocatalyst materials in recent years, several significant challenges still remain to be resolved before photocatalysis can reach its commercial potential. Therefore, major attention is required towards improving the efficiencies of the existing photocatalysts by further manipulating them and parallelly employing newer strategies for novel photocatalyst designs. This personal account aims to provide a broad overview of the field primarily invoking examples of our own research contributions in the field, which include photocatalytic hydrogen generation and CO2 reduction to value added chemicals. This account reviews the state-of-the-art research activities and scientific possibilities which a functional material can offer if its properties are put to best use through goal-oriented design by combining with other compatible materials. We have addressed fundamental principles of photocatalysis, different kind of functional photocatalysts, critical issues associated with them and various strategies to overcome the related hurdles. It is our hope that this current personal account will provide a platform for young researchers to address the bottleneck issues in the field of photocatalysis and photocatalysts with a sense of clarity, and to find innovative solutions to resolve them by a prudent choice of materials, synthesis protocols, and approaches to boost the photocatalysis output. We emphasize that a targeted or goal-directed photocatalyst nanoengineering as perhaps the only way to realize an early success in this multiparametric domain.

The Perfect Imperfections in Electrocatalysts.

Modern day electrochemical devices find applications in a wide range of industrial sectors, from consumer electronics, renewable energy management to pollution control by electric vehicles and reduction of greenhouse gas. There has been a surge of diverse electrochemical systems which are to be scaled up from the lab-scale to industry sectors. To achieve the targets, the electrocatalysts are continuously upgraded to meet the required device efficiency at a low cost, increased lifetime and performance. An atomic scale understanding is however important for meeting the objectives. Transitioning from the bulk to the nanoscale regime of the electrocatalysts, the existence of defects and interfaces is almost inevitable, significantly impacting (augmenting) the material properties and the catalytic performance. The intrinsic defects alter the electronic structure of the nanostructured catalysts, thereby boosting the performance of metal-ion batteries, metal-air batteries, supercapacitors, fuel cells, water electrolyzers etc. This account presents our findings on the methods to introduce measured imperfections in the nanomaterials and the impact of these atomic-scale irregularities on the activity for three major reactions, oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Grain boundary (GB) modulation of the (ABO3 )n type perovskite oxide by noble metal doping is a propitious route to enhance the OER/ORR bifunctionality for zinc-air battery (ZAB). The perovskite oxides can be tuned by calcination at different temperatures to alter the oxygen vacancy, GB fraction and overall reactivity. The oxygen defects, unsaturated coordination environment and GBs can turn a relatively less active nanostructure into an efficient redox active catalyst by imbibing plenty of electrochemically active sites. Obviously, the crystalline GB interface is a prerequisite for effective electron flow, which is also applicable for the crystalline surface oxide shell on metal alloy core of the nanoparticles (NPs). The oxygen vacancy of two-dimensional (2D) perovskite oxide can be made reversible by the A-site termination of the nanosheets, facilitating the reversible entry and exit of a secondary phase during the redox processes. In several instances, the secondary phases have been observed to introduce the right proportion of structural defects and orbital occupancies for adsorption and desorption of reaction intermediates. Also, heterogeneous interfaces can be created by wrapping the perovskite oxide with negatively charged surface by layered double hydroxide (LDH) can promote the OER process. In another approach, ion intercalation at the 2D heterointerfaces steers the interlayer spacing that can influence the mass diffusion. Similar to anion vacancy, controlled formation of the cation vacancies can be achieved by exsolving the B-site cations of perovskite oxides to surface anchored catalytically active metal/alloy NPs. In case of the alloy electrocatalysts, incomplete solid solution by two or more mutually immiscible metals results in heterogeneous alloys having differently exposed facets with complementary functionalities. From the future perspective, new categories of defect structures including the 2D empty spaces or voids leading to undercoordinated sites, the multiple interfaces in heterogeneous alloys, antisite defects between anions and cations, and the defect induced inverse charge transfer should bring new dimensionalities to this riveting area of research.

Fluorescence correlation spectroscopy based insights into diffusion in electrochemical energy systems.

Fluorescence Correlation Spectroscopy, a commonly used technique for measuring diffusion of biomolecules and tracer dyes in different solvents, is employed to characterise the local transport properties in battery electrolytes. Diffusion of ions, a major limiting factor in battery capacity and charging rates, depends on the local interactions and structuredness of the electrolytic species. Structuredness in the electrolyte results from typical solvation behaviour of diffusing ions/molecules leading to long-range interactions. In this work, we have used FCS to measure tracer diffusion of Coumarin 343 in a mixture of Ethylene Carbonate (EC) and Dimethyl Carbonate (DMC), commonly used as electrolyte solvent in Li-ion batteries. The measured diffusion is found to depend on lithium-ion concentrations. It is found that the addition of LiPF6to an EC-DMC equimolar mixture slows down tracer diffusion significantly. Indeed, the bulk viscosity of the electrolyte added with LiPF6salt varies with salt concentration. However, the change in bulk viscosity (global behaviour) at high ion concentrations does not match the one inferred from applying Stoke-Einstein's relation to the diffusion data (local behaviour). This indicates that the homogeneity of the electrolyte does not extend spatially to molecular scales around the diffusing tracer molecule. Measurements made on coin cells prepared with different concentrations of LiPF6show battery performance limited at higher concentrations, characterized by specific capacity loss at faster charging cycles. This limitation is directly related to the local behaviour of the electrolyte as quantified by measurements of tracer diffusion, which slows down, which remarkably outweighs the advantage of high carrier densities.

Construction of a 2D/2D g-C3N5/NiCr-LDH Heterostructure to Boost the Green Ammonia Production Rate under Visible Light Illumination.

Photocatalytic N2 fixation has emerged as one of the most useful ways to produce NH3, a useful asset for chemical industries and a carbon-free energy source. Recently, significant progress has been made toward designing efficient photocatalysts to achieve this objective. Here, we introduce a highly active type-II heterojunction fabricated via integrating two-dimensional (2D) nanosheets of exfoliated g-C3N5 with nickel-chromium layered double hydroxide (NiCr-LDH). With an optimized loading of NiCr-LDH on exfoliated g-C3N5, excellent performance is realized for green ammonia synthesis under ambient conditions without any noble metal cocatalyst(s). Indeed, the g-C3N5/NiCr-LDH heterostructure with 2 wt % of NiCr-LDH (CN-NCL-2) exhibits an ammonia yield of about 2.523 mmol/g/h, which is about 7.51 and 2.86 times higher than that of solo catalysts, i.e., NiCr-LDH (NC-L) and exfoliated g-C3N5 (CN-5), respectively, where methanol is used as a sacrificial agent. The enhancement of NH3 evolution by the g-C3N5/NiCr-LDH heterostructure can be attributed to the efficient charge transfer, a key factor to the photocatalytic N2 fixation rate enhancement. Additionally, N2 vacancies present in the system help adsorb N2 on the surface, which improves the ammonia production rate further. The best-performing heterostructure also shows long-term stability with the NH3 production rate remaining nearly constant over 20 h, demonstrating the excellent robustness of the photocatalyst.

Ultrafine Mix-Phase SnO-SnO2 Nanoparticles Anchored on Reduced Graphene Oxide Boost Reversible Li-Ion Storage Capacity beyond Theoretical Limit.

Tin-based materials with high specific capacity have been studied as high-performance anodes for Li-ion storage devices. Herein, a mix-phase structure of SnO-SnO2@rGO (rGO = reduced graphene oxide) was designed and prepared via a simple chemical method, which leads to the growth of tiny nanoparticles of a mixture of two different tin oxide phases on the crumbled graphene nanosheets. The three-dimensional structure of graphene forms the conductive framework. The as-prepared mix phase SnO-SnO2@rGO exhibits a large Brunauer-Emmett-Teller surface area of 255 m2 g-1 and an excellent ionic diffusion rate. When the resulting mix-phase material was examined for Li-ion battery anode application, the SnO-SnO2@rGO was noted to deliver an ultrahigh reversible capacity of 2604 mA h g-1 at a current density of 0.1 A g-1. It also exhibited superior rate capabilities and more than 82% retention of capacity after 150 charge-discharge cycles at 0.1 A g-1, lasting until 500 cycles at 1 A g-1 with very good retention of the initial capacity. Owing to the uniform defects on the rGO matrix, the formation of LiOH upon lithiation has been suggested to be the primary cause of this very high reversible capacity, which is beyond the theoretical limit. A Li-ion full cell was assembled using LiNi0.5Mn0.3Co0.2O2 (NMC-532) as a high-capacity cathodic counterpart, which showed a very high reversible capacity of 570 mA h g-1 (based on the anode weight) at an applied current density of 0.1 A g-1 with more than 50% retention of capacity after 100 cycles. This work offers a favorable design of electrode material, namely, mix-phase tin oxide-nanocarbon matrix, exhibiting adequate electrochemical performance for Li storage applications.

Efficient Nitrate Conversion to Ammonia on f-Block Single-Atom/Metal Oxide Heterostructure via Local Electron-Deficiency Modulation.

Exploring single-atom catalysts (SACs) for the nitrate reduction reaction (NO3-; NitRR) to value-added ammonia (NH3) offers a sustainable alternative to both the Haber-Bosch process and NO3--rich wastewater treatment. However, due to the insufficient electron deficiency and unfavorable electronic structure of SACs, resulting in poor NO3--adsorption, sluggish proton (H*) transfer kinetics, and preferred hydrogen evolution, their NO3--to-NH3 selectivity and yield rate are far from satisfactory. Herein, a systematic theoretical prediction reveals that the local electron deficiency of an f-block Gd single atom (GdSA) can be significantly regulated upon coordination with oxygen-defect-rich NiO (GdSA-D-NiO400) support. Thus, facilitating stronger NO3- adsorption via strong Gd5d-O2p orbital coupling and further improving the protonation kinetics of adsorption intermediates by rapid H* capture from water dissociation catalyzed by the adjacent oxygen vacancy site along with suppressed H* dimerization synergistically boosts the NH3 selectivity/yield rate. Motivated by DFT prediction, we delicately stabilized electron-deficient (strongly electrophilic) GdSA on D-NiO400 (∼84% strong electrophilic sites), which exhibited excellent alkaline NitRR activity (NH3 Faradaic efficiency ∼97% and yield rate ∼628 µg/(mgcat h)) along with superior structural stability, as revealed by in situ Raman spectroscopy, significantly outperforming weakly electrophilic Gd nanoparticles, defect-free GdSA-P-NiO400, and reported state-of-the-art catalysts.

Oxygen-Defect-Rich Cobalt Ferrite Nanoparticles for Practical Water Electrolysis with High Activity and Durability.

The scope of any metal oxide as a catalyst for driving electrocatalytic reactions depends on its electronic structure, which is correlated to its oxygen-defect density. Likewise, to transform a spinel oxide, such as cobalt ferrite (CoFe2 O4 ), into a worthy universal-pH, bifunctional electrocatalyst for the hydrogen and oxygen evolution reactions (HER and OER, respectively), oxygen defects need to be regulated. Prepared by coprecipitation and inert calcination at 650 °C, CoFe2 O4 nanoparticles (NPs) require 253 and 300 mV OER overpotentials to reach current densities of 10 and 100 mA cm-2 , respectively, if nickel foam is used as a substrate. With cost-effective carbon fiber paper, the OER overpotential increases to 372 mV at 10 mA cm-2 at pH 14. The NPs prepared at 550 °C require HER overpotentials of 218, 245, and 314 mV at -10 mA cm-2 in alkaline, acidic, and neutral pH, respectively. The intrinsic activity is reflected from turnover frequencies of >3 O2 s-1 and >5 H2 s-1 at overpotentials of 398 and 259 mV, respectively. If coupled for overall water splitting, the extremely durable two-electrode electrolyzer requires a cell potential of only 1.63 V to reach 10 mA cm-2 at pH 14. The homologous couple also splits seawater at impressively low cell voltages of 1.72 and 1.47 V at room temperature and 80 °C, respectively.

Surfactant-Mediated Resistance to Surface Oxidation in MnO Nanostructures.

The intrinsic physical properties of nanostructures of metals and their oxides are altered when they are prone to surface oxidation in ambient atmosphere. To overcome this limitation, novel synthesis methodologies are required. In this study, solid octahedral shapes of MnO limit the inward oxygen diffusion compared to that of the MnO-nanoparticle-assembled octahedra. In addition to morphology control, which restricts the thickness of the Mn3O4 surface layer, the binding chemistry of the surfactants plays an essential role. For example, the Mn3O4 surface layer is 0.4 nm thinner with trioctylphosphine oxide than with trioctylamine as the surfactant. The nanostructures were prepared by varying the surfactants, surfactant-to-precursor molar ratio, accelerating agent, and reaction heating rate. The surface oxidation of MnO nano-octahedra was probed by Rietveld analysis of X-ray diffraction patterns and X-ray photoelectron spectroscopy and characterized by magnetic measurements, as the presence of ferrimagnetic Mn3O4 shell on the antiferromagnetic MnO core provides an exchange coupling at the core-shell interface. Thicker the Mn3O4 shell, higher is the exchange-biased hysteresis loop shift.