A Heterogeneous Carbon Nitride–Nickel Photocatalyst for Efficient Low‐Temperature CO2 Methanation

The Sabatier reaction, i.e., the hydrogenation of CO₂ to methane (CH₄) using hydrogen (H₂), constitutes a potentially scalable method to store energy in a product with a high energy density. However, up to today, this reaction has been mainly thermally driven and conducted at high temperatures (typically 400–600 °C). Using light as a renewable energy source will allow for a more sustainable process by lowering the reaction temperature. Here, it is demonstrated that Ni nanoparticles support on graphitic carbon nitride (g‐CN) are a highly efficient and stable photocatalyst for the gas‐phase CO₂ methanation at low temperature (150 °C). Detailed mechanistic studies reveal a very low activation energy for the reaction and high activity under visible light, leading to a remarkable and continuous CH₄ production of 28 µmol g^?1 h^?1 of CH₄ for 24 h.     

Solar‐Light‐Driven CO2 Reduction by CH4 on Silica‐Cluster‐Modified Ni Nanocrystals with a High Solar‐to‐Fuel Efficiency and Excellent Durability

Catalytic CO₂ reforming of CH₄ (CRM) to produce syngas (H₂ and CO) provides a promising approach to reducing global CO₂ emissions and the extensive utilization of natural gas resources. However, the rapid deactivation of the reported catalysts due to severe carbon deposition at high reaction temperatures and the large energy consumption of the process hinder its industrial application. Here, a method for almost completely preventing carbon deposition is reported by modifying the surface of Ni nanocrystals with silica clusters. The obtained catalyst exhibits excellent durability for CRM with almost no carbon deposition and deactivation after reaction for 700 h. Very importantly, it is found that CRM on the catalyst can be driven by focused solar light, thus providing a promising new approach to the conversion of renewable solar energy to fuel due to the highly endothermic characteristics of CRM. The reaction yields high production rates of H₂ and CO (17.1 and 19.9 mmol min^?1 g^?1, respectively) with a very high solar‐to‐fuel efficiency (η, 12.5%). Even under focused IR irradiation with a wavelength above 830 nm, the η of the catalyst remains as high as 3.1%. The highly efficient catalytic activity arises from the efficient solar‐light‐driven thermocatalytic CRM enhanced by a novel photoactivation effect.     

Highly Efficient Ambient Temperature CO2 Photomethanation Catalyzed by Nanostructured RuO2 on Silicon Photonic Crystal Support

Sunlight‐driven catalytic hydrogenation of CO₂ is an important reaction that generates useful chemicals and fuels and if operated at industrial scales can decrease greenhouse gas CO₂ emissions into the atmosphere. In this work, the photomethanation of CO₂ over highly dispersed nanostructured RuO₂ catalysts on 3D silicon photonic crystal supports, achieving impressive conversion rates as high as 4.4 mmol g_cat^?1 h^?1 at ambient temperatures under high‐intensity solar simulated irradiation, is reported. This performance is an order of magnitude greater than photomethanation rates achieved over control samples made of nanostructured RuO₂ on silicon wafers. The high absorption and unique light‐harvesting properties of the silicon photonic crystal across the entire solar spectral wavelength range coupled with its large surface area are proposed to be responsible for the high methanation rates of the RuO₂ photocatalyst. A density functional theory study on the reaction of CO₂ with H₂ revealed that H₂ splits on the surface of the RuO₂ to form hydroxyl groups that participate in the overall photomethanation process.     

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO2 Batteries

Li–CO₂ batteries are attractive electrical energy storage devices; however, they still suffer from unsatisfactory electrochemical performance, and the kinetics of CO₂ reduction and evolution reactions must be improved significantly. Herein, a composite of ruthenium–copper nanoparticles highly co‐dispersed on graphene (Ru–Cu–G) as efficient air cathodes for Li–CO₂ batteries is designed. The Li–CO₂ batteries with Ru–Cu–G cathodes exhibit ultra‐low overpotential and can be operated for 100 cycles with a fixed capacity of 1000 mAh g^?1 at 200 and 400 mA g^?1. The synergistic effect between Ru and Cu not only regulates the growth of discharge products, but also promotes CO₂ reduction and evolution reactions by changing the electron cloud density of the surface between Ru and Cu. This work may provide new directions and strategies for developing highly efficient air cathodes for Li–CO₂ batteries, or even practical Li–air batteries.     

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO2 Batteries

With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO₂ battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO₂ battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li₂CO₃/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g^?1 at a current density of 400 mA g^?1, the cycling performance of the Li–CO₂ battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO₂ batteries as well as other rechargeable metal–gas batteries.     

Complete Dehydrogenation of N2H4BH3 over Noble‐Metal‐Free Ni0.5Fe0.5–CeOx/MIL‐101 with High Activity and 100% H2 Selectivity

Efficient and selective dehydrogenation of hydrazine borane (HB), a novel hydrogen storage material with very high hydrogen content (HB, 15.4 wt%), is a key challenge for a fuel‐cell‐based hydrogen economy. However, even using the noble metal catalysts for HB decomposition, the activities are still far from satisfying, to say nothing of non‐noble‐metal‐containing catalysts. In response, as a proof‐of‐concept experiment, herein, noble‐metal‐free NiFe–CeO_x nanoparticles are successfully immobilized on an MIL‐101 support without surfactant by a simple liquid impregnation method. Unexpectedly, the resultant Ni_0.5Fe_0.5–CeO_x/MIL‐101 catalyst shows good performance, including 100% H₂ selectivity, 100% conversion, and record catalytic activity (351.3 h^?1) for hydrogen generation at mild temperature, which is even better than most of the noble metal heterogeneous catalysts and might be attributed to the good dispersion and uniform particle size of the Ni_0.5Fe_0.5–CeO_x nanoparticles due to steric restrictions effect of the MIL‐101 support. Additionally, extending MIL‐101 to some other important kinds of metal–organic framework (MOF) structures, the resultant NiFe–CeO_x/MOF catalysts all show good catalytic activity toward HB decomposition, showing the universality of the MOF supported NiFe–CeO_x catalysts.     

Ni–Fe–La(Sr)Fe(Mn)O3 as a New Active Cermet Cathode for Intermediate‐Temperature CO2 Electrolysis Using a LaGaO3‐Based Electrolyte

Various additives to Ni–Fe systems are studied as cermet cathodes for CO₂ electrolysis (973–1173 K) using a La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ (LSGM) electrolyte, which is one of the most promising oxide‐ion conductors for intermediate‐temperature solid‐oxide electrolysis cells in terms of ionic‐transport number and conductivity. It is found that Ni–Fe–La_0.6Sr_0.4Fe_0.8Mn_0.2O₃ (Ni–Fe–LSFM) exhibits a remarkable performance with a current density of 2.32 A cm^?2 at 1.6 V and 1073 K. The cathodic overpotential is significantly decreased by mixing the LSFM powder with Ni–Fe, which is related to the increase in the number of reaction sites for CO₂ reduction. For Ni–Fe–LSFM, much smaller particles (<200 nm) are sustained under CO₂ electrolysis conditions at high temperatures than for Ni–Fe. X‐ray diffraction analysis suggests that the main phases of Ni–Fe–LSFM are Ni and LaFeO₃; thus, the oxide phase of LaFeO₃ is also maintained during CO₂ electrolysis. Analysis of the gaseous products indicates that only CO is formed, and the rate of CO formation agrees well with that of a four‐electron reduction process, suggesting that the reduction of CO₂ to CO proceeds selectively. It is also confirmed that almost no coke is deposited on the Ni–Fe–LSFM cathode after CO₂ electrolysis.     

Modifying La0.6Sr0.4MnO3 Perovskites with Cr Incorporation for Fast Isothermal CO2‐Splitting Kinetics in Solar‐Driven Thermochemical Cycles

Perovskites are promising oxygen carriers for solar‐driven thermochemical fuel production due to higher oxygen exchange capacity. Despite their higher fuel yield capacity, La_0.6Sr_0.4MnO₃ perovskite materials present slow CO₂‐splitting kinetics compared with state‐of‐the‐art CeO₂. In order to improve the CO production rates, the incorporation of Cr in La_0.6Sr_0.4MnO₃ is explored based on thermodynamic calculations that suggest an enhanced driving force toward CO₂ splitting at high temperatures for La_0.6Sr_0.4Cr_xMn_1?xO₃ perovskites. Here, reported is a threefold faster CO fuel production for La_0.6Sr_0.4Cr_0.85Mn_0.15O₃ compared to conventional La_0.6Sr_0.4MnO₃, and twofold faster than CeO₂ under isothermal redox cycling at 1400 °C, and high stability upon long‐term cycling without any evidence of microstructural degradation. The findings suggest that with the proper design in terms of transition metal ion doping, it is possible to adjust perovskite compositions and reactor conditions for improved solar‐to‐fuel thermochemical production under nonconventional solar‐driven thermochemical cycling schemes such as the here presented near isothermal operation.     

Uncovering Atomic‐Scale Stability and Reactivity in Engineered Zinc Oxide Electrocatalysts for Controllable Syngas Production

In this study, scalable, flame spray synthesis is utilized to develop defective ZnO nanomaterials for the concurrent generation of H₂ and CO during electrochemical CO₂ reduction reactions (CO₂RR). The designed ZnO achieves an H₂/CO ratio of ≈1 with a large current density (j) of 40 mA cm^?2 during long‐term continuous reaction at a cell voltage of 2.6 V. Through in situ atomic pair distribution function analysis, the remarkable stability of these ZnO structures is explored, addressing the knowledge gap in understanding the dynamics of oxide catalysts during CO₂RR. Through optimization of synthesis conditions, ZnO facets are modulated which are shown to affect reaction selectivity, in agreement with theoretical calculations. These findings and insights on synthetic manipulation of active sites in defective metal‐oxides can be used as guidelines to develop active catalysts for syngas production for renewable power‐to‐X to generate a range of fuels and chemicals.     

Fast and Stable Proton Conduction in Heavily Scandium‐Doped Polycrystalline Barium Zirconate at Intermediate Temperatures

The environmental benefits of fuel cells and electrolyzers have become increasingly recognized in recent years. Fuel cells and electrolyzers that can operate at intermediate temperatures (300–450 °C) require, in principle, neither the precious metal catalysts that are typically used in polymer‐electrolyte‐membrane systems nor the costly heat‐resistant alloys used in balance‐of‐plant components of high‐temperature solid oxide electrochemical cells. These devices require an electrolyte with high ionic conductivity, typically more than 0.01 S cm^?1, and high chemical stability. To date, however, high ionic conductivities have been found in chemically unstable materials such as CsH₂PO₄, In‐doped SnP₂O₇, BaH₂, and LaH_3?2xO_x. Here, fast and stable proton conduction in 60‐at% Sc‐doped barium zirconate polycrystal, with a total conductivity of 0.01 S cm^?1 at 396 °C for 200 h is demonstrated. Heavy doping of Sc in barium zirconate simultaneously enhances the proton concentration, bulk proton diffusivity, specific grain boundary conductivity, and grain growth. An accelerated stability test under a highly concentrated and humidified CO₂ stream using in situ X‐ray diffraction shows that the perovskite phase is stable over 240 h at 400 °C under 0.98 atm of CO₂. These results show great promises as an electrolyte in solid‐state electrochemical devices operated at intermediate temperatures.     

Modified Ceria for “Low‐Temperature” CO2 Utilization: A Chemical Looping Route to Exploit Industrial Waste Heat

Efficient CO₂ utilization is key to limit global climate change. Carbon monoxide, which is a crucial feedstock for chemical synthesis, can be produced by splitting CO₂. However, existing thermochemical routes are energy intensive requiring high operating temperatures. A hybrid redox process (HRP) involving CO₂‐to‐CO conversion using a lattice oxygen‐deprived redox catalyst at relatively low temperatures (<700 °C) is reported. The lattice oxygen of the redox catalyst, restored during CO₂‐splitting, is subsequently used to convert methane to syngas. Operated at temperatures significantly lower than a number of industrial waste heat sources, this cyclic redox process allows for efficient waste heat‐utilization to convert CO₂. To enable the low temperature operation, lanthanum modified ceria (1:1 Ce:La) promoted by rhodium (0.5 wt%) is reported as an effective redox catalyst. Near‐complete CO₂ conversion with a syngas yield of up to 83% at low temperatures is achieved using Rh‐promoted LaCeO_4?x. While La improves low‐temperature bulk redox properties of ceria, Rh considerably enhances the surface catalytic properties for methane activation. Density functional theory calculations further illustrate the underlying functions of La‐substitution. The highly effective redox catalyst and HRP scheme provide a potentially attractive route for chemical production using CO₂, industrial waste heat, and methane, with appreciably lowered CO₂ emissions.     

Activation of Ni Particles into Single Ni–N Atoms for Efficient Electrochemical Reduction of CO2

Electrochemical reduction of carbon dioxide (CO₂) to fuels and value‐added industrial chemicals is a promising strategy for keeping a healthy balance between energy supply and net carbon emissions. Here, the facile transformation of residual Ni particle catalysts in carbon nanotubes into thermally stable single Ni atoms with a possible NiN₃ moiety is reported, surrounded with a porous N‐doped carbon sheath through a one‐step nanoconfined pyrolysis strategy. These structural changes are confirmed by X‐ray absorption fine structure analysis and density functional theory (DFT) calculations. The dispersed Ni single atoms facilitate highly efficient electrocatalytic CO₂ reduction at low overpotentials to yield CO, providing a CO faradaic efficiency exceeding 90%, turnover frequency approaching 12 000 h^?1, and metal mass activity reaching about 10 600 mA mg^?1, outperforming current state‐of‐the‐art single atom catalysts for CO₂ reduction to CO. DFT calculations suggest that the Ni@N₃ (pyrrolic) site favors *COOH formation with lower free energy than Ni@N₄, in addition to exothermic CO desorption, hence enhancing electrocatalytic CO₂ conversion. This finding provides a simple, scalable, and promising route for the preparation of low‐cost, abundant, and highly active single atom catalysts, benefiting future practical CO₂ electrolysis.     

Self‐quenching in the electrochemiluminescence of Ru(bpy)32+ using ascorbic acid as co‐reactant

In this study, electrochemiluminescence (ECL) of Ru(bpy)₃²⁺ (bpy = 2,2′‐bipyridyl) using ascorbic acid (H₂A) as co‐reactant was investigated in an aqueous solution. When H₂A was co‐existent in a Ru(bpy)₃²⁺‐containing buffer solution, ECL peaks were observed at a potential corresponding to the oxidation of Ru(bpy)₃²⁺, and the intensity was proportional to H₂A concentration at lower concentration levels. The formation of the excited state *Ru(bpy)₃²⁺ was confirmed to result from the co‐reaction between Ru(bpy)₃³⁺and the intermediate of ascorbate anion radical (A⁻•), which showed the maximum ECL at pH = 8.8. It is our first finding that the ECL intensity would be quenched significantly when the concentration of H₂A was relatively higher, or upon ultrasonic irradiation. In most instances, quenching is observed with four‐fold excess of H₂A over Ru(bpy)₃²⁺. The diffusional self‐quenching scheme as well as the possible reaction pathways involved in the Ru(bpy)₃²⁺–H₂A ECL system are discussed in this study. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrochemical CO2 Reduction with Atomic Iron‐Dispersed on Nitrogen‐Doped Graphene

Electrochemical reduction of CO₂ provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO₂ emissions from fuel use are collected and converted back to fuels. The reduction of CO₂ to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO₂ conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO₂ reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO₂ reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N₄) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.     

Edge‐Exposed Molybdenum Disulfide with N‐Doped Carbon Hybridization: A Hierarchical Hollow Electrocatalyst for Carbon Dioxide Reduction

Electrochemical CO₂ reduction (CO₂RR) is a promising technology to produce value‐added fuels and weaken the greenhouse effect. Plenty of efforts are devoted to exploring high‐efficiency electrocatalysts to tackle the issues that show poor intrinsic activity, low selectivity for target products, and short‐lived durability. Herein, density functional theory calculations are firstly utilized to demonstrate guidelines for design principles of electrocatalyst, maximum exposure of catalytic active sites for MoS₂ edges, and electron transfer from N‐doped carbon (NC) to MoS₂ edges. Based on the guidelines, a hierarchical hollow electrocatalyst comprised of edge‐exposed 2H MoS₂ hybridized with NC for CO₂RR is constructed. In situ atomic‐scale observation for catalyst growth is performed by using a specialized Si/SiN_x nanochip at a continuous temperature‐rise period, which reveals the growth mechanism. Abundant exposed edges of MoS₂ provide a large quantity of active centers, which leads to a low onset potential of ≈40 mV and a remarkable CO production rate of 34.31 mA cm^?2 with 92.68% of Faradaic efficiency at an overpotential of 590 mV. The long‐term stability shows negligible degradation for more than 24 h. This work provides fascinating insights into the construction of catalysts for efficient CO₂RR.     

UV‐Rearranged PIM‐1 Polymeric Membranes for Advanced Hydrogen Purification and Production

Polymers of intrinsic microporosity (PIM‐1) have been known for their super high permeability but average selectivity for medium‐size gas pairs. They have unimpressive selectivity for H₂ and CO₂ separation (i.e., α (H₂/CO₂) = 0.6). For the first time, we have discovered that ultraviolet (UV)‐rearranged polymers of PIM‐1 membranes can be used for H₂/CO₂ separation with far superior separation performance to others in literatures. The PIM‐1 membrane after UV radiation for 4 hours shows H₂ permeability of 452 barrer with H₂/CO₂ selectivity of 7.3. Experimental data and molecular simulation reveal that the polymer chains of PIM‐1 undergo 1,2‐migration reaction and transform to close‐to‐planar like rearranged structure after UV radiation. As a result, the UV‐irradiated PIM‐1 membrane shows considerable drops in both fractional free volume (FFV) and size of micro‐pores. Positron annihilation lifetime (PAL) results have confirmed the chemical and structural changes, suggesting the FFV and pore size drops are mainly ascribed to the destructed spiro‐carbon centre during UV radiation. Sorption and x‐ray diffractor (XRD) analyses indicate that the impressive H₂/CO₂ selectivity arises from the significantly enhanced diffusivity selectivity induced by UV radiation, followed by molecular rearrangement, conformation change and chain packing.     

Potential‐resolved electrochemiluminescence of Ru(bpy)32+/C2O42− system on gold electrode

The electrogenerated chemiluminescence of Ru(bpy)₃²⁺/C₂O₄^2? system on a pre‐polarized Au electrode was studied using a potential‐resolved electrochemiluminescence (PRECL) method. Two anodic ECL peaks were observed at 1.22 V (vs. SCE) (EP1), 1.41 V (vs. SCE) (EP2), respectively. The effects of the concentration of oxalate and Ru(bpy)₃²⁺, adsorbed sulphur, CO₂, O₂, pH of the solution and pretreatment of the Au electrode on the two PRECL peaks were examined. The surface state of the pre‐oxidized gold electrode was also studied using the X‐ray photoelectron spectroscopy (XPS) technique. Moreover, comparative studies on i–E and I–E curves were carried out and a possible mechanism involving both the catalytic and the direct electro‐oxidation pathways was proposed for the ECL of Ru(bpy)₃²⁺/C₂O₄^2? system. EP1 is attributed to the Ru(bpy)₃^2/3+ reaction catalysed by C₂O₄^2? to generate Ru(bpy)₃^2+*. EP2 is likely because C₂O₄^2? was oxidized at the electrode to form CO₂^?·, followed by reaction with Ru(bpy)₃³⁺ to generate Ru(bpy)₃^2+*. Copyright © 2002 John Wiley & Sons, Ltd.     

2D Metal Organic Framework Nanosheet: A Universal Platform Promoting Highly Efficient Visible‐Light‐Induced Hydrogen Production

2D metal organic frameworks (MOF) have received tremendous attention due to their organic–inorganic hybrid nature, large surface area, highly exposed active sites, and ultrathin thickness. However, the application of 2D MOF in light‐to‐hydrogen (H₂) conversion is rarely reported. Here, a novel 2D MOF [Ni(phen)(oba)]_n·0.5nH₂O (phen = 1,10‐phenanthroline, oba = 4,4′‐oxybis(benzoate)) is for the first time employed as a general, high‐performance, and earth‐abundant platform to support CdS or Zn_0.8Cd_0.2S for achieving tremendously improved visible‐light‐induced H₂‐production activity. Particularly, the CdS‐loaded 2D MOF exhibits an excellent H₂‐production activity of 45 201 µmol h^?1 g^?1, even exceeding that of Pt‐loaded CdS by 185%. Advanced characterizations, e.g., synchrotron‐based X‐ray absorption near edge structure, and theoretical calculations disclose that the interactive nature between 2D MOF and CdS, combined with the high surface area, abundant reactive centers, and favorable band structure of 2D MOFs, synergistically contribute to this distinguished photocatalytic performance. The work not only demonstrates that the earth‐abundant 2D MOF can serve as a versatile and effective platform supporting metal sulfides to boost their photocatalytic H₂‐production performance without noble‐metal co‐catalysts, but also paves avenues to the design and synthesis of 2D‐MOF‐based heterostructures for catalysis and electronics applications.     

Enhanced Stability and Thickness‐Independent Oxygen Evolution Electrocatalysis of Heterostructured Anodes with Buried Epitaxial Bilayers

Achieving high oxygen evolution reaction (OER) activity while maintaining performance stability is a key challenge for designing perovskite structure oxide OER catalysts, which are often unstable in alkaline environments transforming into an amorphous phase. While the chemical and structural transformation occurring during electrolysis at the electrolyte–catalyst interface is now regarded as a crucial factor influencing OER activity, here, using La_0.7Sr_0.3CoO_3?δ (LSCO) as an active OER catalyst, the critical influence of buried layers on the oxidation current stability in nanoscopically thin, chemically and structurally evolving, catalyst layers is revealed. The use of epitaxial thin films is demonstrated to engineer both depletion layer widths and chemical stability of the catalyst support structure resulting in heterostructured anodes that maintain facile transport kinetics across the electrolyte–anode interface for atomically thin (2–3 unit cells) LSCO catalyst layers and greatly enhanced oxidation current stability as the perovskite structure OER catalysts chemically and structurally transform. This work opens up an approach to design robust and active heterostructured anodes with dynamically evolving ultrathin OER electrocatalyst layers for future green fuel technologies such as conformal coatings of high‐density 3D anode topologies for water splitting.