Enriching surface-ordered defects on WO3 for photocatalytic CO2-to-CH4 conversion by water.

Defect engineering has been widely applied in semiconductors to improve photocatalytic properties by altering the surface structures. This study is about the transformation of inactive WO3 nanosheets to a highly effective CO2-to-CH4 conversion photocatalyst by introducing surface-ordered defects in abundance. The nonstoichiometric WO3-x samples were examined by using aberration-corrected electron microscopy. Results unveil abundant surface-ordered terminations derived from the periodic {013} stacking faults with a defect density of 20.2%. The {002} surface-ordered line defects are the active sites for fixation CO2, transforming the inactive WO3 nanosheets into a highly active catalyst (CH4: O2 = 8.2: 16.7 µmol h-1). We believe that the formation of the W-O-C-W-O species is a critical step in the catalytic pathways. This work provides an atomic-level comprehension of the structural defects of catalysts for activating small molecules.

Liquid Metal-Enabled Tunable Synthesis of Nanoporous Polycrystalline Copper for Selective CO2-to-Formate Electrochemical Conversion.

Copper-based catalysts exhibit high activity in electrochemical CO2 conversion to value-added chemicals. However, achieving precise control over catalysts design to generate narrowly distributed products remains challenging. Herein, a gallium (Ga) liquid metal-based approach is employed to synthesize hierarchical nanoporous copper (HNP Cu) catalysts with tailored ligament/pore and crystallite sizes. The nanoporosity and polycrystallinity are generated by dealloying intermetallic CuGa2 formed after immersing pristine Cu foil in liquid Ga in a basic or acidic solution. The liquid metal-based approach allows for the transformation of monocrystalline Cu to the polycrystalline HNP Cu with enhanced CO2 reduction reaction (CO2RR) performance. The dealloyed HNP Cu catalyst with suitable crystallite size (22.8 nm) and nanoporous structure (ligament/pore size of 45 nm) exhibits a high Faradaic efficiency of 91% toward formate production under an applied potential as low as -0.3 VRHE. The superior CO2RR performance can be ascribed to the enlarged electrochemical catalytic surface area, the generation of preferred Cu facets, and the rich grain boundaries by polycrystallinity. This work demonstrates the potential of liquid metal-based synthesis for improving catalysts performance based on structural design, without increasing compositional complexity.

Fundamentals and Recent Progress in Magnetic Field Assisted CO2 Capture and Conversion.

CO2 capture and conversion technology are highly promising technologies that definitely play a part in the journey towards carbon neutrality. Releasing CO2 by mild stimulation and the development of high efficiency catalytic processes are urgently needed. The magnetic field, as a thermodynamic parameter independent of temperature and pressure, is vital in the enhancement of CO2 capture and conversion process. In this review, the recent progress of magnetic field-enhanced CO2 capture and conversion is comprehensively summarized. The theoretical fundamentals of magnetic field on CO2 adsorption, release and catalytic reduction process are discussed, including the magnetothermal, magnetohydrodynamic, spin selection, Lorentz forces, magnetoresistance and spin relaxation effects. Additionally, a thorough review of the current progress of the enhancement strategies of magnetic field coupled with a variety of fields (including thermal, electricity, and light) is summarized in the aspect of CO2 related process. Finally, the challenges and prospects associated with the utilization of magnetic field-assisted techniques in the construction of CO2 capture and conversion systems are proposed. This review offers a reference value for the future design of catalysts, mechanistic investigations, and practical implementation for magnetic field enhanced CO2 capture and conversion.

Matched Redox Kinetics on Triazine-Based Carbon Nitride/Ni(OH)2 for Stoichiometric Overall Photocatalytic CO2 Conversion.

Mismatched reaction kinetics of CO2 reduction and H2O oxidation is the main obstacle limiting the overall photocatalytic CO2 conversion. Here, a molten salt strategy is used to construct tubular triazine-based carbon nitride (TCN) with more adsorption sites and stronger activation capability. Ni(OH)2 nanosheets are then grown over the TCN to trigger a proton-coupled electron transfer for a stoichiometric overall photocatalytic CO2 conversion via "3CO2 + 2H2O = CH4 + 2CO + 3O2." TCN reduces the energy barrier of H2O dissociation to promote H2O oxidation to O2 and supply sufficient protons to Ni(OH)2, whereby the CO2 conversion is accelerated due to the enhanced proton-coupled electron transfer process enabled by the sufficient proton supply from TCN. This work highlights the importance of matching the reaction kinetics of CO2 reduction and H2O oxidation by proton-coupled electron transfer on stoichiometric overall photocatalytic CO2 conversion.

Fast-growing cyanobacterial chassis for synthetic biology application.

Carbon neutrality by 2050 has become one of the most urgent challenges the world faces today. To address the issue, it is necessary to develop and promote new technologies related with CO2 recycling. Cyanobacteria are the only prokaryotes performing oxygenic photosynthesis, capable of fixing CO2 into biomass under sunlight and serving as one of the most important primary producers on earth. Notably, recent progress on synthetic biology has led to utilizing model cyanobacteria such as Synechocystis sp. PCC 6803 and Synechococcus elongatus PCC 7942 as chassis for "light-driven autotrophic cell factories" to produce several dozens of biofuels and various fine chemicals directly from CO2. However, due to the slow growth rate and low biomass accumulation in the current chassis, the productivity for most products is still lower than the threshold necessary for large-scale commercial application, raising the importance of developing high-efficiency cyanobacterial chassis with fast growth and/or higher biomass accumulation capabilities. In this article, we critically reviewed recent progresses on identification, systems biology analysis, and engineering of fast-growing cyanobacterial chassis. Specifically, fast-growing cyanobacteria identified in recent years, such as S. elongatus UTEX 2973, S. elongatus PCC 11801, S. elongatus PCC 11802 and Synechococcus sp. PCC 11901 was comparatively analyzed. In addition, the progresses on their recent application in converting CO2 into chemicals, and genetic toolboxes developed for these new cyanobacterial chassis were discussed. Finally, the article provides insights into future challenges and perspectives on the synthetic biology application of cyanobacterial chassis.

N-doped Porous Carbon Derived from the Pyrolysis of a Polydopamine-coated Hypercross-linked Polymer for Enhanced CO2 Adsorption.

Porous carbon materials can simultaneously capture and convert carbon dioxide, helping to reduce greenhouse gas emissions and using carbon dioxide as a feedstock for the production of valuable chemicals or fuel. In this work, a series of N-doped porous carbons (PDA@HCP(x:y)-T) was prepared; the CO2 adsorption capacity of the prepared PDA@HCP(x:y)-T was enhanced by coating polydopamine (PDA) on a hypercross-linked polymer (HCP) and then adjusting the mass ratio of PDA to HCP and the carbonization temperature. The results showed that the prepared PDA@HCP(1:1)-850 exhibited a high CO2 adsorption capacity due to abundant micropores (0.6762 cm3/g), a high specific surface area (1220.8 m²/g), and moderate surface nitrogen content (2.75%). Notably, PDA@HCP(1:1)-850 exhibited the highest CO2 uptake of 6.46 mmol/g at 0 °C and 101 kPa. Critically, these N-doped porous carbons can also be used as catalysts for the reaction of CO2 with epichlorohydrin to form chloropropylene carbonate, with chloropropylene carbonate yielding up to 64% and selectivity of the reaction reaching 94%. As a result, these N-doped porous carbons could serve as potential candidates for CO2 capture and conversion due to their high reactivity, excellent CO2 uptake, and good catalytic performance.

Construction of Co1-xZnxFe2xGa2-2xO4 (02 Reduction by H2O Vapour.

Solid solutions are garnering substantial attention in the realm of solar energy utilization due to their tunable electronic properties, encompassing band edge positions and charge-carrier mobilities. In this study, we designed and synthesized Co1-xZnxFe2xGa2-2xO4 (0

CO2 hydrogenation to methanol over Pt functionalized Hf-UiO-67 versus Zr-UiO-67.

Sustainable methanol formation from CO2/H2 is potentially a key process in the post-fossil chemical industry. In this study, Hf- and Zr-based metal-organic framework (MOF) materials with UiO-67 topology, functionalized with Pt nanoparticles, have been tested for CO2 hydrogenation at 30 bar and 170-240°C. The highest methanol formation rate, 14 molmethanol molPt-1 h-1, was obtained over a Hf-based catalyst, compared with the maximum of 6.2 molmethanol molPt-1 h-1 for the best Zr-based analogue. However, changing the node metal did not significantly affect product distribution or apparent activation energy for methanol formation (44-52 kJ mol-1), strongly indicating that the higher activity of the Hf-based analogues is associated with a higher number of active sites. Both catalysts showed stable catalytic performance during testing under kinetic conditions, but the addition of 2 vol% water to the feed induced catalyst deactivation, in particular the Hf-MOFs. Interestingly, mainly methanol and methane formation rates decreased, while CO formation rates were less affected by deactivation. No direct correlation was found between catalytic stability and framework stability (crystallinity, specific surface area). Experimental and computational studies suggest that water adsorption strength to the MOF node may affect the relative catalytic stability of Hf-UiO-67-Pt versus Zr-UiO-67-Pt methanol catalysts.This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

Tunable C2 Products via Photothermal Steam Reforming of CO2 over Surface-Modulated Mesoporous Cobalt Oxides.

The conversion of CO2 to high-value products by renewable energy is a promising approach for realizing carbon neutralization, but the selectivity and efficiency of C2+ products are not satisfying. Herein, we report the controllable preparation of highly ordered mesoporous cobalt oxides with modulated surface states to achieve efficient photothermal water-steam reforming of CO2 to C2 products with high activity and tunable selectivity. Pristine mesoporous Co3O4 exhibited an acetic acid selectivity of 96% with a yield rate of 73.44 µmol g-1 h-1. By rationally modifying mesoporous Co3O4 surface states, mesoporous Co3O4@CoO delivered a radically altered ∼100% ethanol selectivity with a yield rate of 14.85 µmol g-1 h-1. Comprehensive experiments revealed that the pH value could strongly influence the selectivity of C2 products over mesoporous cobalt oxides. Density functional theory verified that reduced surface states and rich oxygen vacancies on surface-modified mesoporous cobalt oxides could facilitate further variation of C2 products from acetic acid to ethanol.

Exploring carbon-based Cu-ZnO catalyst and substitutes for enhanced selective methanol production from CO2: An integrated experimental and computational study.

Methanol, produced through the hydrogenation of carbon dioxide, is an essential intermediate compound that plays a crucial function in the production of various organic chemicals. Enhancing the design of copper-containing catalysts for the transformation of CO2 to methanol is a popular strategy in scientific literature, although challenges persist in advancing the efficiency of carbon dioxide transformation and the selectivity of methanol production. This research aims at creating CuZnO-M/rGO (M = Mg, Mn, and Cr) catalysts using an efficient method for selectively converting CO2 to methanol. By optimizing the operational parameters of this system, methanol productivity and CO2 conversion efficiency are enhanced. Under optimal conditions, a CO2 conversion rate of 23.5%, methanol selectivity of 90%, and a space-time yield of 0.47 gMeOH.gcat-1.h-1 were achieved with the CuZnO-MgO (5)/rGO catalyst. These levels were maintained over a 100-h period, demonstrating the stability of the catalyst system. These findings are highly consistent with the density functional theory (DFT) calculations, revealing that the CuZnO-MgO (5)/rGO catalyst possesses a -0.35 eV adsorption energy for CO2 and a favorable reaction pathway with the overpotential of 1.16 V towards methanol production emphasizing the high conversion and selectivity obtained.

Catalytic Strategies for the Cycloaddition of CO2 to Epoxides in Aqueous Media to Enhance the Activity and Recyclability of Molecular Organocatalysts.

The cycloaddition of CO2 to epoxides to afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling of CO2. One of the main focuses of the current research in this area is the discovery of readily available, sustainable, and inexpensive catalysts, and of catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant in the cycloaddition process, is progressively emerging as a helpful reaction component. On the one hand, it serves as an inexpensive hydrogen bond donor (HBD) to enhance the performance of ionic compounds; on the other hand, aqueous media allow the development of diverse catalytic protocols that can boost catalytic performance or ease the recycling of molecular catalysts. An overview of the advances in the use of aqueous and biphasic aqueous systems for the cycloaddition of CO2 to epoxides is provided in this work along with recommendations for possible future developments.

The Effect of Bismuth and Tin on Methane and Acetate Production in a Microbial Electrosynthesis Cell Fed with Carbon Dioxide.

This study investigates the impacts of bismuth and tin on the production of CH4 and volatile fatty acids in a microbial electrosynthesis cell with a continuous CO2 supply. First, the impact of several transition metal ions (Ni2+, Fe2+, Cu2+, Sn2+, Mn2+, MoO42-, and Bi3+) on hydrogenotrophic and acetoclastic methanogenic microbial activity was evaluated in a series of batch bottle tests incubated with anaerobic sludge and a pre-defined concentration of dissolved transition metals. While Cu is considered a promising catalyst for the electrocatalytic conversion of CO2 to short chain fatty acids such as acetate, its presence as a Cu2+ ion was demonstrated to significantly inhibit the microbial production of CH4 and acetate. At the same time, CH4 production increased in the presence of Bi3+ (0.1 g L-1) and remained unchanged at the same concentration of Sn2+. Since Sn is of interest due to its catalytic properties in the electrochemical CO2 conversion, Bi and Sn were added to the cathode compartment of a laboratory-scale microbial electrosynthesis cell (MESC) to achieve an initial concentration of 0.1 g L-1. While an initial increase in CH4 (and acetate for Sn2+) production was observed after the first injection of the metal ions, after the second injection, CH4 production declined. Acetate accumulation was indicative of the reduced activity of acetoclastic methanogens, likely due to the high partial pressure of H2. The modification of a carbon-felt electrode by the electrodeposition of Sn metal on its surface prior to cathode inoculation with anaerobic sludge showed a doubling of CH4 production in the MESC and a lower concentration of acetate, while the electrodeposition of Bi resulted in a decreased CH4 production.

Nickel-based cerium zirconate inorganic complex structures for CO2 valorisation via dry reforming of methane.

The increasing anthropogenic emissions of greenhouse gases (GHG) is encouraging extensive research in CO2 utilisation. Dry reforming of methane (DRM) depicts a viable strategy to convert both CO2 and CH4 into syngas, a worthwhile chemical intermediate. Among the different active phases for DRM, the use of nickel as catalyst is economically favourable, but typically deactivates due to sintering and carbon deposition. The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts. XRD and TPR-H2 analyses confirmed the existence of different phases according to the Ni loading in these materials. Besides, superficial Ni is observed as well as the existence of a CeNiO3 perovskite structure. The catalytic activity was tested, proving that 10 wt.% Ni loading is the optimum which maximises conversion. This catalyst was also tested in long-term stability experiments at 600 and 800°C in order to study the potential deactivation issues at two different temperatures. At 600°C, carbon formation is the main cause of catalytic deactivation, whereas a robust stability is shown at 800°C, observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO2 and biogas mixtures upgrading catalysts.

Tailoring Electrochemical CO2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors.

Electrochemical CO2 reduction (CO2 RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion-CO2 adducts and a hydrogen bond donor (HBD) upon CO2 absorption to modulate CO2 RR on Cu in a non-aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface-enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum-mechanical/molecular mechanics (IC-QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO2 availability, reduced overpotential, and suppressed HER where C4 products are obtained. This study deepens the understanding of electrolyte effects in CO2 RR and the role of IL ions towards electrocatalytic microenvironment design.

Plasma-Driven Efficient Conversion of CO2 and H2O into Pure Syngas with Controllable Wide H2/CO Ratios over Metal-Organic Frameworks Featuring In Situ Evolved Ligand Defects.

While the mild production of syngas (a mixture of H2 and CO) from CO2 and H2O is a promising alternative to the coal-based chemical engineering technologies, the inert nature of CO2 molecules, unfavorable splitting pathways of H2O and unsatisfactory catalysts lead to the challenge in the difficult integration of high CO2 conversion efficiency with produced syngas with controllable H2/CO ratios in a wide range. Herein, we report an efficient plasma-driven catalytic system for mild production of pure syngas over porous metal-organic framework (MOF) catalysts with rich confined H2O molecules, where their syngas production capacity is regulated by the in situ evolved ligand defects and the plasma-activated intermediate species of CO2 molecules. Specially, the Cu-based catalyst system achieves 61.9 % of CO2 conversion and the production of pure syngas with wide H2/CO ratios of 0.05 : 1-4.3 : 1. As revealed by the experimental and theoretical calculation results, the in situ dynamic structure evolution of Cu-containing MOF catalysts favors the generation of coordinatively unsaturated metal active sites with optimized geometric and electronic characteristics, the adsorption of reactants, and the reduced energy barriers of syngas-production potential-determining steps of the hydrogenation of CO2 to *COOH and the protonation of H2O to *H.

Photocatalytic CO2 Reduction by Near-Infrared-Light (1200†nm) Irradiation and a Ruthenium-Intercalated NiAl-Layered Double Hydroxide.

Near-infrared light-driven photocatalytic CO2 reduction (NIR-CO2PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO2 with low energy NIR photons remains challenging. Herein, a novel NIR-driven photocatalyst comprising an anionic Ru complex intercalated between NiAl-layered double hydroxide nanosheets (NiAl-Ru-LDH) is shown to deliver efficient CO2 photoreduction (0.887 µmol h-1) with CO selectivity of 84.81 % under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression-related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light-induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO2PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO2 molecules and lowers the energy barriers for NIR-CO2PR to CO. To our knowledge, this is one of the first reports of NIR-CO2PR at wavelengths up to 1200 nm in LDH-based photocatalyst systems.

Modulating Inorganic Dimensionality of Ultrastable Lead Halide Coordination Polymers for Photocatalytic CO2 Reduction to Ethanol.

Lead halide hybrids have shown great potentials in CO2 photoreduction, but challenging to afford C2+ reduced products, especially using H2O as the reductant. This is largely due to the trade-off problem between instability of the benchmark 3D structures and low carrier mobility of quasi-2D analogues. Herein, the lead halide dimensionality of robust coordination polymers (CP) was modulated by organic ligands differing in a single-atom change (NH vs. CH2), in which the NH groups coordinate with interlamellar [PbI2] clusters to achieve the important 2D→3D transition. This first CP based on 3D cationic lead iodide sublattice possesses both high aqueous stability and a low exciton binding energy of 25 meV that is on the level of ambient thermal energy, achieving artificial photosynthesis of C2H5OH. Photophysical studies combined with theoretical calculations suggest the bridging [PbI2] clusters in the 3D structure not only results in enhanced carrier transport, but also promotes the intrinsic charge polarization to facilitate the C-C coupling. With trace loading of Rh cocatalyst, the apparent quantum efficiency of the 3D CP reaches 1.4 % at 400 nm with a high C2H5OH selectivity of 89.4 % (product basis), which presents one of the best photocatalysts for C2 products to date.

Perfluoroalkyl-Decorated Noble-Metal-Free MOFs for the Highly Efficient One-Pot Four-Component Coupling between Aldehydes, Amines, Alkynes, and Flue Gas CO2.

The non-noble-metal catalysed-multicomponent reactions between flue gas CO2 and cheap industrial raw stocks into high value-added fine chemicals is a promising manner for the ideal CO2 utilization route. To achieve this, the key fundamental challenge is the rational development of highly efficient and facile reaction pathway while establishing compatible catalytic system. Herein, through the stepwise solvent-assisted linker installation, post-synthetic fluorination and metalation, we report the construction of a series of perfluoroalkyl-decorated noble-metal-free metal-organic frameworks (MOFs) PCN-(BPY-CuI)-(TPDC-Fx ) [BPY=2,2'-bipyridine-5,5'-dicarboxylate, TPDC-NH2 =2'-amino-[1,1':4',1''-terphenyl]-4,4''-dicarboxylic acid] that can catalyze the one-pot four-component reaction between alkyne, aldehyde, amine and flue gas CO2 for the preparation of 2-oxazolidinones. Such assembly endows the MOFs with superhydrophobic microenvironment, superior water resistance and highly stable catalytic site, leading to 21 times higher turnover numbers than that of homogeneous counterparts. Mechanism investigation implied that the substrates can be efficiently enriched by the MOF wall and then the adsorbed amine species act as an extrinsic binding site towards dilute CO2 through their strong preferential formation to carbamate acid. Moreover, density functional theory calculations suggest the tetrahedral geometry of Cu in MOF offers special resistance towards amine poisoning, thus maintaining its high efficiency during the catalytic process.

New Insights for High-Throughput CO2 Hydrogenation to High-Quality Fuel.

In the case of CO2 thermal-catalytic hydrogenation, highly selective olefin generation and subsequent olefin secondary reactions to fuel hydrocarbons in an ultra-short residence time is a huge challenge, especially under industrially feasible conditions. Here, we report a pioneering synthetic process that achieves selective production of high-volume commercial gasoline with the assistance of fast response mechanism. In situ experiments and DFT calculations demonstrate that the designed NaFeGaZr presents exceptional carbiding prowess, and swiftly forms carbides even at extremely brief gas residence times, facilitating olefin production. The created successive hollow zeolite HZSM-5 further reinforces aromatization of olefin diffused from NaFeGaZr via optimized mass transfer in the hollow channel of zeolite. Benefiting from its rapid response mechanism within the multifunctional catalytic system, this catalyst effectively prevents the excessive hydrogenation of intermediates and controls the swift conversion of intermediates into aromatics, even in high-throughput settings. This enables a rapid one-step synthesis of high-quality gasoline-range hydrocarbons without any post-treatment, with high commercial product compatibility and space-time yield up to 0.9 kggasoline ⋅ kgcat -1 ⋅ h-1. These findings from the current work can provide a shed for the preparation of efficient catalysts and in-depth understanding of C1 catalysis in industrial level.

Defective Nb2 C MXene Cocatalyst on TiO2 Microsphere for Enhanced Photocatalytic CO2 Conversion to Methane.

Sustainable and scalable solar-energy-driven CO2 conversion into fuels requires earth-abundant and stable photocatalysts. In this work, a defective Nb2 C MXene as a cocatalyst and TiO2 microspheres as photo-absorbers, constructed via a coulombic force-driven self-assembly, is synthesized. Such photocatalyst, at an optimized loading of defective Nb2 C MXene (5% def-Nb2 C/TiO2 ), exhibits a CH4 production rate of 7.23 µmol g-1  h-1 , which is 3.8 times higher than that of TiO2 . The Schottky junction at the interface improves charge transfer from TiO2 to defective Nb2 C MXene and the electron-rich feature (nearly free electron states) enables multielectron reaction of CO2 , which apparently leads to high activity and selectivity to CH4 (sel. 99.5%) production. Moreover, DFT calculation demonstrates that the Fermi level (EF ) of defective Nb2 C MXene (-0.3 V vs NHE) is more positive than that of Nb2 C MXene (-1.0 V vs NHE), implying a strong capacity to accept photogenerated electrons and enhance carrier lifetime. This work gives a direction to modify the earth-abundant MXene family as cocatalysts to build high-performance photocatalysts for energy production.