Altering the CO2 electroreduction pathways towards C1 or C2+ products via engineering the strength of interfacial Cu-O bond.

Copper (Cu)-based catalysts have established their unique capability for yielding wide value-added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squarate (C4O4) and cyclohexanhexanone (C6O6)). It is revealed that the strength of Cu-O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6-Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7% at -1.0 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4-Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8% for C2+ products with enhanced capability of C-C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm-2 at -1.0 VRHE, i.e. is already at the boarder of practical relevance. This study sheds light on the rational design of Cu-based catalysts for directing the CO2RR reaction pathway.

Materials Advances in Photocatalytic Solar Hydrogen Production: Integrating Systems and Economics for a Sustainable Future.

Photocatalytic solar hydrogen generation, encompassing both overall water splitting and organic reforming, presents a promising avenue for green hydrogen production. This technology holds the potential for reduced capital costs in comparison to competing methods like photovoltaic-electrocatalysis and photoelectrocatalysis, owing to its simplicity and fewer auxiliary components. However, the current solar-to-hydrogen efficiency of photocatalytic solar hydrogen production has predominantly remained low at ≈1-2% or lower, mainly due to curtailed access to the entire solar spectrum, thus impeding practical application of photocatalytic solar hydrogen production. This review offers an integrated, multidisciplinary perspective on photocatalytic solar hydrogen production. Specifically, the review presents the existing approaches in photocatalyst and system designs aimed at significantly boosting the solar-to-hydrogen efficiency, while also considering factors of cost and scalability of each approach. In-depth discussions extending beyond the efficacy of material and system design strategies are particularly vital to identify potential hurdles in translating photocatalysis research to large-scale applications. Ultimately, this review aims to provide understanding and perspective of feasible pathways for commercializing photocatalytic solar hydrogen production technology, considering both engineering and economic standpoints.

Single-zinc vacancy unlocks high-rate H2O2 electrosynthesis from mixed dioxygen beyond Le Chatelier principle.

Le Chatelier's principle is a basic rule in textbook defining the correlations of reaction activities and specific system parameters (like concentrations), serving as the guideline for regulating chemical/catalytic systems. Here we report a model system breaking this constraint in O2 electroreduction in mixed dioxygen. We unravel the central role of creating single-zinc vacancies in a crystal structure that leads to enzyme-like binding of the catalyst with enhanced selectivity to O2, shifting the reaction pathway from Langmuir-Hinshelwood to an upgraded triple-phase Eley-Rideal mechanism. The model system shows minute activity alteration of H2O2 yields (25.89~24.99 mol gcat-1 h-1) and Faradaic efficiencies (92.5%~89.3%) in the O2 levels of 100%~21% at the current density of 50~300 mA cm-2, which apparently violate macroscopic Le Chatelier's reaction kinetics. A standalone prototype device is built for high-rate H2O2 production from atmospheric air, achieving the highest Faradaic efficiencies of 87.8% at 320 mA cm-2, overtaking the state-of-the-art catalysts and approaching the theoretical limit for direct air electrolysis (~345.8 mA cm-2). Further techno-economics analyses display the use of atmospheric air feedstock affording 21.7% better economics as comparison to high-purity O2, achieving the lowest H2O2 capital cost of 0.3 $ Kg-1. Given the recent surge of demonstrations on tailoring chemical/catalytic systems based on the Le Chatelier's principle, the present finding would have general implications, allowing for leveraging systems "beyond" this classical rule.

Revisiting the phosphonium salt chemistry for P-doped carbon synthesis: toward high phosphorus contents and beyond the phosphate environment.

The introduction of phosphorus and nitrogen atoms in carbo-catalysts is a common way to tune the electronic density, and thereby the reactivity, of the material, as well as to introduce surface reactive sites. Numerous environments are reported for the N atoms, but the P-doping chemistry is less explored and focuses on surface POx groups. A one-step synthesis of P/N-doped carbonaceous materials is presented here, using affordable and industrially available urea and tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the N and P sources, respectively. In contrast to most of the synthetic pathways toward P-doped carbonaceous materials, the THPC precursor only displays P-C bonds along the carbon backbone. This resulted in unusual phosphorus environments for the materials obtained from direct thermal treatment of THPC-urea, presumably of type C-P-N according to 31P NMR and XPS. Alternatively, the in situ polymerization and calcination of the precursors were run in calcium chloride hydrate, used as a combined reaction medium and porogen agent. Following this salt-templating strategy led to particularly high phosphorus contents (up to 18 wt%), associated with porosities up to 600 m2 g-1. The so-formed P/N-doped porous materials were employed as metal-free catalysts for the mild oxidative dehydrogenation of N-heterocycles to N-heteroarenes at room temperature and in air.

Lignosulfonate-Based Carbon-Supported Pellets Catalyst to Enhance Sustainable Biofuel Production from Waste Cooking Oil.

In this study, a cost-effective and stable heterogeneous acidic carbocatalyst (CZnLS950) derived from Na-lignosulfonate (LS), a side product of the paper industry, was employed to produce hydrocarbon fuels through the pyrolysis of waste cooking oil (WCO) and crude natural-oil extracted from sunflower seeds, aligning with the principles of the circular economy. To enhance its practicality in industrial settings, the catalyst was synthesized in pellet form, enabling easy separation from the biofuel produced during the reaction. CZnLS950 exhibited remarkable catalytic efficiency in the pyrolysis of WCO, resulting in a 71 wt. % liquid biofuel yield under mild conditions. This performance is attributed to the unique synthesis procedure of acidic carbocatalyst, which utilizes LS and nano ZnO (20 nm) to create a hierarchical pore structure with acidic properties (1.1 mmol of NH3 g-1). Stability and reusability of the carbocatalyst were evaluated, and the results showed excellent stability with small catalytic deactivation (~5 wt. %) after the fourth use. Attempts at distinct catalytic mechanisms for WCO and sunflower seeds crude natural-oil pyrolysis were provided to understand the processes involved in obtaining the two different biofuels produced. Overall, this study sets the stage for exploring Lignosulfonate-based materials to achieve renewable biofuel from recycling streams.

Atomic Ruthenium-Promoted Cadmium Sulfide for Photocatalytic Production of Amino Acids from Biomass Derivatives.

Amino acids are the building blocks of proteins and are widely used as important ingredients for other nitrogen-containing molecules. Here, we report the sustainable production of amino acids from biomass-derived hydroxy acids with high activity under visible-light irradiation and mild conditions, using atomic ruthenium-promoted cadmium sulfide (Ru1/CdS). On a metal basis, the optimized Ru1/CdS exhibits a maximal alanine formation rate of 26.0 molAla ⋅ gRu -1 ⋅ h-1, which is 1.7 times and more than two orders of magnitude higher than that of its nanoparticle counterpart and the conventional thermocatalytic process, respectively. Integrated spectroscopic analysis and density functional theory calculations attribute the high performance of Ru1/CdS to the facilitated charge separation and O-H bond dissociation of the α-hydroxy group, here of lactic acid. The operando nuclear magnetic resonance further infers a unique "double activation" mechanism of both the CH-OH and CH3-CH-OH structures in lactic acid, which significantly accelerates its photocatalytic amination toward alanine.

Metal Poly(heptazine imides) as Multifunctional Photocatalysts for Solar Fuel Production.

Solar-driven photocatalysis employing particulate semiconductors represents a promising approach for sustainable production of valuable chemical feedstock. Metal poly(heptazine imide) (MPHI), a novel 2D ionic carbon nitride, has been recognized as an emerging photocatalyst with distinctive properties. In this minireview, we first delineate the forefront innovations of MPHI photocatalysts, spanning from synthetic strategies and solving structures to the exploration of novel properties. We place special emphasis on the structural design principles aimed at developing high-performance MPHI systems toward photocatalytic solar fuel production such as H2 evolution, H2O oxidation, H2O2 production and CO2 reduction. Finally, we discuss crucial insights and challenges in leveraging highly active MPHIs for efficient solar-to-chemical energy conversion.

Reactive Eutectic Media for Lignocellulosic Biomass Fractionation.

This study introduces an alternative approach towards lignocellulosic biomass fractionation. For this purpose, reactive eutectic media (REM) based on ammonium formate and different organic acids are investigated, possible products are identified, and the REM are employed for lignin extraction and terminal isolation of cellulose pulp from beech wood. The method promises a considerable process intensification by simultaneous separation of high purity cellulose pulp, lignin isolation as a cationically modified species, and production of value-added chemicals from reaction products of the REM. This study puts a further focus on the generated cellulose pulp and investigates it with respect to surface charge and fiber length.

Entropy-Driven Direct Air Electrofixation.

According to the principles of chemical thermodynamics, the catalytic activation of small molecules (like N2 in air and CO2 in flue gas) generally exhibits a negative activity dependence on O2 owning to the competitive oxygen reduction reaction (ORR). Nevertheless, some catalysts can show positive activity dependence for N2 electrofixation, an important route to produce ammonia under ambient condition. Here we report that the positive activity dependence on O2 of (Ni0.20Co0.20Fe0.20Mn0.19Mo0.21)3S4 catalyst arises from high-entropy mechanism. Through experimental and theoretical studies, we demonstrate that under the reaction condition in the mixed N2/O2, the adsorption of O2 on high-entropy catalyst contributes to activating N2 molecules characteristic of elongated N≡N bond lengths. As comparison to the low- and medium-entropy counterparts, high entropy can play the second role of attenuating competitive ORR by displaying a negative exponential entropy-ORR activity relationship. Accordingly, benefiting from the O2, the system for direct air electrofixation has demonstrated an ammonia yield rate of 47.70 µg h-1 cm-2, which is even 1.5 times of pure N2 feedstock (31.92 µg h-1 cm-2), overtaking all previous reports for this reaction. We expect the present finding providing an additional dimension to high entropy that leverages systems beyond the constraint of traditional rules.

Red Carbon Mediated Formation of Cu2O Clusters Dispersed on the Oxocarbon Framework by Fehling's Route and their Use for the Nitrate Electroreduction in Acidic Conditions.

The oligomers of carbon suboxide, known as red carbon, exhibit a highly conjugated structure and semiconducting properties. Upon mild heat treatment, it transforms into a carbonaceous framework rich in oxygen surface terminations, called oxocarbon. In this study, the abundant oxygen functionalities are harnessed as anchors to create oxocarbon-supported nanohybrid electrocatalysts. Starting with single atomic Cu (II) strongly coordinated to oxygen atoms on red carbon, the Fehling reaction leads to the formation of Cu2O clusters. Simultaneously, a covalent oxocarbon framework emerges via cross-linking, providing robust support for Cu2O clusters. Notably, the oxocarbon support effectively stabilizes Cu2O clusters of very small size, ensuring their high durability in acidic conditions and the presence of ammonia. The synthesized material exhibits a superior electrocatalytic activity for nitrate reduction under acidic electrolyte conditions, with a high yield rate of ammonium (NH4 +) at 3.31 mmol h-1 mgcat -1 and a Faradaic efficiency of 92.5% at a potential of -0.4 V (vs RHE).

Emerging Two-Dimensional Carbonaceous Materials for Electrocatalytic Energy Conversions: Rational Design of Active Structures through High-Temperature Chemistry.

Electrochemical energy conversion and storage technologies involving controlled catalysis provide a sustainable way to handle the intermittency of renewable energy sources, as well as to produce green chemicals/fuels in an ecofriendly manner. Core to such technology is the development of efficient electrocatalysts with high activity, selectivity, long-term stability, and low costs. Here, two-dimensional (2D) carbonaceous materials have emerged as promising contenders for advancing the chemistry in electrocatalysis. We review the emerging 2D carbonaceous materials for electrocatalysis, focusing primarily on the fine engineering of active structures through thermal condensation, where the design, fabrication, and mechanism investigations over different types of active moieties are summarized. Interestingly, all the recipes creating two-dimensionality on the carbon products also give specific electrocatalytic functionality, where the special mechanisms favoring 2D growth and their consequences on materials functionality are analyzed. Particularly, the structure-activity relationship between specific heteroatoms/defects and catalytic performance within 2D metal-free electrocatalysts is highlighted. Further, major challenges and opportunities for the practical implementation of 2D carbonaceous materials in electrocatalysis are summarized with the purpose to give future material design guidelines for attaining desirable catalytic structures.

Artificial Humic Acid Mediated Carbon-Iron Coupling to Promote Carbon Sequestration.

Fe (hydr)oxides have a substantial impact on the structure and stability of soil organic carbon (SOC) pools and also drive organic carbon turnover processes via reduction-oxidation reactions. Currently, many studies have paid much attention to organic matter-Fe mineral-microbial interactions on SOC turnover, while there is few research on how exogenous carbon addition abiotically regulates the intrinsic mechanisms of Fe-mediated organic carbon conversion. The study investigated the coupling process of artificial humic acid (A-HA) and Fe(hydr)oxide, the mechanism of inner-sphere ligands, and the capacity for carbon sequestration using transmission electron microscopy, thermogravimetric, x-ray photoelectron spectroscopy, and wet-chemical disposal. Furthermore, spherical aberration-corrected scanning transmission electron microscopy-electron energy loss spectroscopy and Mössbauer spectra have been carried out to demonstrate the spatial heterogeneity of A-HA/Fe (hydr)oxides and reveal the relationship between the increase in Fe-phase crystallinity and redox sensitivity and the accumulation of organic carbon. Additionally, the dynamics of soil structures on a microscale, distribution of carbon-iron microdomains, and the cementing-gluing effect can be observed in the constructing nonliving anthropogenic soils, confirming that the formation of stable aggregates is an effective approach to achieving organic carbon indirect protection. We propose that exogenous organic carbon inputs, specifically A-HA, could exert a substantial but hitherto unexplored effect on the geochemistry of iron-carbon turnover and sequestration in anoxic water/solid soils and sediments.

Microporous Sulfur-Carbon Materials with Extended Sodium Storage Window.

Developing high-performance carbonaceous anode materials for sodium-ion batteries (SIBs) is still a grand quest for a more sustainable future of energy storage. Introducing sulfur within a carbon framework is one of the most promising attempts toward the development of highly efficient anode materials. Herein, a microporous sulfur-rich carbon anode obtained from a liquid sulfur-containing oligomer is introduced. The sodium storage mechanism shifts from surface-controlled to diffusion-controlled at higher synthesis temperatures. The different storage mechanisms and electrode performances are found to be independent of the bare electrode material's interplanar spacing. Therefore, these differences are attributed to an increased microporosity and a thiophene-rich chemical environment. The combination of these properties enables extending the plateau region to higher potential and achieving reversible overpotential sodium storage. Moreover, in-operando small-angle X-ray scattering (SAXS) reveals reversible electron density variations within the pore structure, in good agreement with the pore-filling sodium storage mechanism occurring in hard carbons (HCs). Eventually, the depicted framework will enable the design of high-performance anode materials for sodium-ion batteries with competitive energy density.

Triazine-Based Graphitic Carbon Nitride Thin Film as a Homogeneous Interphase for Lithium Storage.

Triazine-based graphitic carbon nitride is a semiconductor material constituted of cross-linked triazine units, which differs from widely reported heptazine-based carbon nitrides. Its triazine-based structure gives rise to significantly different physical chemical properties from the latter. However, it is still a great challenge to experimentally synthesize this material. Here, we propose a synthesis strategy via vapor-metal interfacial condensation on a planar copper substrate to realize homogeneous growth of triazine-based graphitic carbon nitride films over large surfaces. The triazine-based motifs are clearly shown in transmission electron microscopy with high in-plane crystallinity. An AB-stacking arrangement of the layers is orientationlly parallel to the substrate surface. Eventually, the as-prepared films show dense electrochemical lithium deposition attributed to homogeneous charge transport within this thin film interphase, making it a promising solution for energy storage.

Beyond Conventional Carbon Activation: Creating Porosity without Etching Using Cesium Effect.

Facile synthesis of porous carbon with high yield and high specific surface area (SSA) from low-cost molecular precursors offers promising opportunities for their industrial applications. However, conventional activation methods using potassium and sodium hydroxides or carbonates suffer from low yields (<20%) and poor control over porosity and composition especially when high SSAs are targeted (>2000 m2 g-1) because nanopores are typically created by etching. Herein, a non-etching activation strategy is demonstrated using cesium salts of low-cost carboxylic acids as the sole precursor in producing porous carbons with yields of up to 25% and SSAs reaching 3008 m2 g-1. The pore size and oxygen content can be adjusted by tuning the synthesis temperature or changing the molecular precursor. Mechanistic investigation unravels the non-classical role of cesium as an activating agent. The cesium compounds that form in situ, including carbonates, oxides, and metallic cesium, have extremely low work function enabling electron injection into organic/carbonaceous framework, promoting condensation, and intercalation of cesium ions into graphitic stacks forming slit pores. The resulting porous carbons deliver a high capacity of 252 mAh g-1 (567 F g-1) and durability of 100 000 cycles as cathodes of Zn-ion capacitors, showing their potential for electrochemical energy storage.

Tin (II) Chloride Salt Melts as Non-Innocent Solvents for the Synthesis of Low-Temperature Nanoporous Oxo-Carbons for Nitrate Electrochemical Hydrogenation.

Carbonaceous electrocatalysts offer advantages over metal-based counterparts, being cost-effective, sustainable, and electrochemically stable. Their high surface area increases reaction kinetics, making them valuable for environmental applications involving contaminant removal. However, their rational synthesis is challenging due to the applied high temperatures and activation steps, leading to disordered materials with limited control over doping. Here, a new synthetic pathway using carbon oxide precursors and tin chloride as a p-block metal salt melt is presented. As a result, highly porous oxygen-rich carbon sheets (with a surface area of 1600 m2 g-1) are obtained at relatively low temperatures (400 °C). Mechanistic studies reveal that Sn(II) triggers reductive deoxygenation and concomitant condensation/cross-linking, facilitated by the Sn(II) → Sn(IV) transition. Due to their significant surface area and oxygen doping, these materials demonstrate exceptional electrocatalytic activity in the nitrate-to-ammonia conversion, with an ammonia yield rate of 221 mmol g-1 h-1 and a Faradic efficiency of 93%. These results surpass those of other carbon-based electrocatalysts. In situ Raman studies reveal that the reaction occurs through electrochemical hydrogenation, where active hydrogen is provided by water reduction. This work contributes to the development of carbonaceous electrocatalysts with enhanced performance for sustainable environmental applications.

Brønsted-Lowry Acid-Based Aqueous Eutectic Electrolyte for Practical Zinc Batteries.

Aqueous highly concentrated electrolytes (AHCEs) have recently emerged as an innovative strategy to enhance the cycling stability of aqueous Zinc (Zn) batteries (AZB). Particularly, thanks to high Zn Chloride (ZnCl2 ) solubility in water, AHCEs based on ZnCl2 feature remarkable Zn anode stability. However, due to their inherently acidic pH and Cl- anion reactivity, these electrolytes face compatibility challenges with other battery components. Here, an aqueous eutectic electrolyte (AEE) based on Brønsted-Lowry concept is reported-allowing the usage of cheap and abundant salts, ZnCl2, and sodium acetate (NaAc). The reported, pH buffered, AEE displays a higher coordination of water at an even lower salt concentration, by simply balancing the acceptor-donor H─bonding. This results in impressive improvement of electrolyte properties such as high electrochemical stability, high transport properties and low glass transition temperature. The developed AEE displays higher compatibility with vanadium oxide-based cathode with a 50% increase in capacity retention in comparison to sat. ZnCl2 . More importantly, the pH buffered AEE solves the incompatibility issues of ZnCl2 toward commonly used aluminium (Al) current collector as well as cellulose separator. This work presents an efficient, simple, and low-cost strategy for the development of aqueous electrolytes for the practical application of Zn batteries.

Visualization of charge carriers in photocatalysts.

Surface photovoltage techniques combined with time-resolved spectroscopy methods provide an effective way to visualize the charge transfer dynamics in photocatalytic reactions.

Photocharging of Carbon Nitride Thin Films for Controllable Manipulation of Droplet Force Gradient Sensors.

Intentional generation, amplification, and discharging of chemical gradients is central to many nano- and micromanipulative technologies. We describe a straightforward strategy to direct chemical gradients inside a solution via local photoelectric surface charging of organic semiconducting thin films. We observed that the irradiation of carbon nitride thin films with ultraviolet light generates local and sustained surface charges in illuminated regions, inducing chemical gradients in adjacent solutions via charge-selective immobilization of surfactants onto the substrate. We studied these gradients using droplet force gradient sensors, complex emulsions with simultaneous and independent responsive modalities to transduce information on transient gradients in temperature, chemistry, and concentration via tilting, morphological reconfiguration, and chemotaxis. Fine control over the interaction between local, photoelectrically patterned, semiconducting carbon nitride thin films and their environment yields a new method to design chemomechanically responsive materials, potentially applicable to micromanipulative technologies including microfluidics, lab-on-a-chip devices, soft robotics, biochemical assays, and the sorting of colloids and cells.

Extent of carbon nitride photocharging controls energetics of hydrogen transfer in photochemical cascade processes.

Graphitic carbon nitride is widely studied in organic photoredox catalysis. Reductive quenching of carbon nitride excited state is postulated in many photocatalytic transformations. However, the reactivity of this species in the turn over step is less explored. In this work, we investigate electron and proton transfer from carbon nitride that is photocharged to a various extent, while the negative charge is compensated either by protons or ammonium cations. Strong stabilization of electrons by ammonium cations makes proton-coupled electron transfer uphill, and affords air-stable persistent carbon nitride radicals. In carbon nitrides, which are photocharged to a smaller extent, protons do not stabilize electrons, which results in spontaneous charge transfer to oxidants. Facile proton-coupled electron transfer is a key step in the photocatalytic oxidative-reductive cascade - tetramerization of benzylic amines. The feasibility of proton-coupled electron transfer is modulated by adjusting the extent of carbon nitride photocharging, type of counterion and temperature.