Efficient CO2 Reduction Research Articles

S‑scheme heterojunction of thin-layer O-modified graphitic carbon nitride/cobalt porphyrin to promote photocatalytic CO2 conversion

The emissions of CO2 are increasing year by year, which have led to serious environmental problems. Converting CO2 into valuable fuels through photocatalysis is a promising strategy. In this research, oxygen atoms were successfully innovated into graphitic carbon nitride (CN). Additionally, cobalt porphyrin (CoTPP) was successfully loaded onto the modified carbon nitride (Co/CN). The generation of interfacial electric fields and bending bands between CN and CoTPP was demonstrated experimentally. The electrons in the CN and the holes in the CoTPP were combined to form a unique S-scheme heterojunction structure, and efficient separation of carriers was promoted. As a result, the CO conversion under visible light irradiation reached an impressive 100.70 μmol g−1 h−1. By integrating theoretical and experimental findings, this study underscores the critical role of catalyst design in enabling efficient photocatalytic CO2 reduction.

Enhancing Efficiency and High-Value Chemicals Generation through Coupling Photocatalytic CO2 Reduction with Propane Oxidation.

Conversion of CO2 into high-value chemicals using solar energy is one of promising approaches to achieve carbon neutrality. However, the oxidation of water in the photocatalytic CO2 reduction is kinetically unfavorable due to multi-electron and proton transfer processes, along with the difficulty in generating O-O bonds. To tackle these challenges, this study investigated the coupling reaction of photocatalytic CO2 reduction and selective propane oxidation using the Pd/P25 (1 wt%) catalyst. Our findings reveal a significant improvement in CO2 reduction, nearly fivefold higher, achieved by substituting water oxidation with selective propane oxidation. This substitution not only accelerates the process of CO2 reduction but also yields valuable propylene. The relative ease of propane oxidation, compared to water, appears to increase the density of photogenerated electrons, ultimately enhancing the efficiency of CO2 reduction. We further found that hydroxyl radicals and reduced intermediate (carboxylate species) played important roles in the photocatalytic reaction. These findings not only propose a potential approach for the efficient utilization of CO2 through the coupling of selective propane oxidation into propylene, but also provide insights into the mechanistic understanding of the coupling reaction.

Photocatalytic CO2 Reduction Using Mixed Catalytic Systems Comprising an Iron Cation with Bulky Phenanthroline Ligands.

This study reports on efficient photocatalytic CO2 reduction reactions using mixed catalytic systems of an Fe ion source and various 1,10-phenanthroline derivatives (R1R2p) as ligands in the presence of triethanolamine (TEOA). As the relatively bulky substituents at positions 2 and 9 of R1R2p weakened the ability to coordinate to the Fe ion, the Fe ion formed TEOA complexes. The free R1R2p accepted an electron from the reduced photosensitizer through proton-coupled electron transfer (PCET) using protons of TEOA dissolved in a CH3CN solution in a CO2 atmosphere as the initial step of the catalytic cycle. Although the mixed system of the nonsubstituted 1,10-phenanthroline generates a stable tris(phenanthroline)-Fe(II) complex in solution, this complex could not function as a CO2 reduction catalyst. The mechanism in which R1R2p interacts with the Fe ion after PCET was proposed for this efficient photocatalytic CO2 reduction. The proposed photocatalytic system using the 2,9-di-sec-butyl-phenanthroline ligand could produce CO with high efficiency (quantum yield of 8.2%) combined with a dinuclear Cu(I) complex as a photosensitizer.

High Entropy Alloys Enable Durable and Efficient Lithium-Mediated CO2 Redox Reactions.

Designing electrocatalysts with high activity and durability for multistep reduction and oxidation reactions is challenging. High-entropy alloys (HEAs) are intriguing due to their tunable geometric and electronic structure through entropy effects. However, understanding the origin of their exceptional performance and identifying active centers is hindered by the diverse microenvironment in HEAs. Herein, NiFeCoCuRu HEAs designed with an average diameter of 2.17 nm, featuring different adsorption capacities for various reactants and intermediates in Li-mediated CO2 redox reactions, are introduced. The electronegativity-dependent nature of NiFeCoCuRu HEAs induces significant charge redistribution, shifting the d-band center closer to Fermi level and forming highly active clusters of Ru, Co, and Ni for Li-based compounds adsorptions. This lowers energy barriers and simultaneously stabilizes *LiCO2 and LiCO3+CO intermediates, enhancing the efficiency of both CO2 reduction and Li2CO3 decomposition over extended periods. This work provides insights into specific active site interactions with intermediates, highlighting the potential of HEAs as promising catalysts for intricate CO2 redox reactions.

Crystal Engineering of MOF-Derived Bimetallic Oxide Solid Solution Anchored with Au Nanoparticles for Photocatalytic CO2 Reduction to Syngas and C2 Hydrocarbons.

Considering that CO2 reduction is mostly a multielectron reaction, it is necessary for the photocatalysts to integrate multiple catalytic sites and cooperate synergistically to achieve efficient photocatalytic CO2 reduction to various products, such as C2 hydrocarbons. Herein, through crystal engineering, we designed and constructed a metal-organic framework-derived Zr/Ti bimetallic oxide solid solution support, which was confirmed by X-ray diffraction, electron microscopy and X-ray absorption spectroscopy. After anchoring Au nanoparticles, the composite photocatalyst exhibited excellent performances toward photocatalytic CO2 reduction to syngas (H2 and CO production rates of 271.6 and 260.6 μmol g-1 h-1) and even C2 hydrocarbons (C2H4 and C2H6 production rates of 6.80 and 4.05 μmol g-1 h-1). According to the control experiments and theoretical calculations, the strong interaction between bimetallic oxide solid solution support and Au nanoparticles was found to be beneficial for binding intermediates and reducing CO2 reduction, highlighting the synergy effect of the catalytic system with multiple active sites.

Crystal Engineering of MOF‐Derived Bimetallic Oxide Solid Solution Anchored with Au Nanoparticles for Photocatalytic CO2 Reduction to Syngas and C2 Hydrocarbons

AbstractConsidering that CO2 reduction is mostly a multielectron reaction, it is necessary for the photocatalysts to integrate multiple catalytic sites and cooperate synergistically to achieve efficient photocatalytic CO2 reduction to various products, such as C2 hydrocarbons. Herein, through crystal engineering, we designed and constructed a metal–organic framework‐derived Zr/Ti bimetallic oxide solid solution support, which was confirmed by X‐ray diffraction, electron microscopy and X‐ray absorption spectroscopy. After anchoring Au nanoparticles, the composite photocatalyst exhibited excellent performances toward photocatalytic CO2 reduction to syngas (H2 and CO production rates of 271.6 and 260.6 μmol g−1 h−1) and even C2 hydrocarbons (C2H4 and C2H6 production rates of 6.80 and 4.05 μmol g−1 h−1). According to the control experiments and theoretical calculations, the strong interaction between bimetallic oxide solid solution support and Au nanoparticles was found to be beneficial for binding intermediates and reducing CO2 reduction, highlighting the synergy effect of the catalytic system with multiple active sites.

Ligand-Bound CO2 as a Nonclassical Route toward Efficient Photocatalytic CO2 Reduction with a Ni N-Confused Porphyrin.

Implementing the synergistic effects between the metal and the ligand has successfully streamlined the energetics for CO2 activation and gained high catalytic activities, establishing the important breakthroughs in photocatalytic CO2 reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N-H group. It is readily deprotonated and exists in an anion form during catalysis. Owing to this functional site, NiNCP gave rise to an outstanding turnover number (TON) as high as 217,000 with a 98% selectivity for CO2 reduction to CO, while the parent Ni(II) porphyrin (NiTPP) was found to be nearly inactive. Our mechanistic analysis revealed a nonclassical reaction pattern where CO2 was effectively activated via the attack of the Lewis-basic ligand. The resulting ligand-bound CO2 adduct could be further reduced to produce CO. This new metal-ligand synergistic effect is anticipated to inspire the design of highly active catalysts for small molecule activations.

Non-trivial topological surface states regulation of 1 T-OsCoTe2 enables selective C―C coupling for highly efficient photochemical CO2 reduction toward C2+ hydrocarbons

Despite ongoing research, the rational design of non-trivial topological semimetal surface states for the selective photocatalytic CO2 conversion into valuable products remains full of challenges. Herein, we present the synthesis of lattice-matched 1 T-OsCoTe2 for the photoreduction upgrading of CO2 to tri-carbon (C3) alkane (propane, C3H8) by the integration of experimental work and theory prediction/calculation. Experimental studies suggested a high electron-based selectivity of 71.2 % for C3H8 and an internal quantum efficiency of 54.6 % at 380 nm. In-situ X-ray photoelectron spectroscopy and X-ray absorption fine structure spectroscopy demonstrated that Co and Os atoms coordinated with Te atoms enable an efficient Os―Te―Co electron transfer to activate the generation of *CH3, *CHOCO and *CH2OCOCO. Density functional theory calculations further confirmed Os―Te―Co electron bridging on the improved CO2 conversion kinetics. To our knowledge, this is the first report suggesting the role of Os atoms in accelerating the photocatalytic CO2 conversion activity of the topological semimetal 1 T-OsCoTe2.

Ligand-engineered Cu-based halide perovskite for highly efficient near-infrared photocatalytic CO2 reduction

A key challenge in harvesting solar energy for efficient chemical conversion is the lack of photocatalysts with wide activation wavelengths. Herein, we propose for the first time to utilize halide perovskite to absorb the full spectrum (200–2500 nm), including ultraviolet (UV), visible (Vis), and near-infrared (NIR) light, to directly power photocatalytic CO2 reduction. This full-spectrum light-responsive occurs on metal halide perovskite Cs2CuCl4 microcrystals (MCs), and the ligand soybean lecithin is applied to optimize the active phase of Cs2CuCl4 photocatalyst, such as morphology, particle size, crystal face and electronic structure. As revealed by optical absorption analysis, the Cs2CuCl4 and ligand soybean lecithin modified Cs2CuCl4 (SL-Cs2CuCl4) MCs exhibit significant optical absorption in the UV, Vis light and NIR light regions. The photocatalytic CO2 reduction performance was assessed under simulated sunlight (200–2500 nm), and the SL-Cs2CuCl4 MCs achieved a CO fuel yield of 254.46 µmol g−1, which increased the yield by 5 times relative to the initial sample. Based on in-situ Fourier transform infrared, electron spin resonance and X-ray photoelectron spectroscopy, the active substances and reaction intermediates at the active site of SL-Cs2CuCl4 MCs were dynamically monitored, and the photocatalytic mechanism was revealed together with density functional theory (DFT) calculations. The DFT calculation shows that the photocatalytic reduction of CO2 to CO by Cs2CuCl4 is proposed to involve the concerted action of both Cs and Cu sites.

Photocatalytic Efficiency for CO2 Reduction of Co and Cluster Co2O2 Supported on g-C3N4: A Density Functional Theory and Machine Learning Study.

It is well known from experimental results that a single atom of cobalt supported on g-C3N4 is an efficient photocatalyst for the reduction of CO2 to CO, with a better photocatalytic activity than g-C3N4. In this work, we investigate the performance as catalysts for the CO2 reduction of single atoms of cobalt and Co2O2 clusters supported on graphitic carbon nitride (g-C3N4). Employing density functional theory plus Hubbard (DFT + U) calculations, we investigate in detail the reduction mechanisms to CO and HCOOH for the first time. We find that deposition of cobalt on g-C3N4 decreases the work function of g-C3N4 to 6.6 eV and provides a better candidate for the reduction reaction. In addition, we find that the preferred product of CO2 reduction on Co@g-C3N4 is CO, with a rate-determining barrier of 0.97 eV, while on Co2O2@g-C3N4, CO2 reduces to formate with a rate-determining barrier of 0.44 eV. We determine the creation of CO2 from COOH to only take place on Co2O2@g-C3N4, with a (relatively high) barrier of 2.27 eV. In order to obtain more easily the transition state energies of the reactions mentioned above, we applied machine learning methods to search for high-importance descriptors for these quantities, in the case of single transition metal atoms supported on C3N4. Interestingly, our results show that our quantities of interest are closely related to the adsorption energies of products and normalized valence electrons of the products of the elementary reactions as well as those of the metal atoms. The former of these two sets of features can be straightforwardly obtained via DFT, while the latter energies are extensively tabulated. Our results offer guidance for the design of catalysts and photocatalysts for CO2 reduction on single-metal atoms supported on C3N4.

S-scheme heterojunction Cu-porphyrin/TiO2 nanosheets with highly efficient photocatalytic reduction of CO2 in ambient air

Directly capturing CO2 in ambient air and converting it into value-added fuels using photocatalysis is a potentially valuable technology. In this study, Cu-porphyrin (tetrakis-carboxyphenyl porphyrin copper, CuTCPP) was innovatively anchored on the surface of TiO2 (titanium dioxide) nanosheets to form an S-scheme heterojunction. Based on this, a photocatalytic reaction system for stably converting CO2 in ambient air into value-added fuels at the gas–solid interface was constructed without addition of sacrificial agents and alkaline liquids. Under the illumination of visible light and sunlight, the evolution rate of CO is 56 μmol·g−1·h−1 and 73 μmol·g−1·h−1, respectively, with a potential CO2 conversion rate of 35.8 % and 50.4 %. The enhanced of photocatalytic performance is attributed to the introduction of CuTCPP, which provides additional active sites, significantly improves capture capacity of CO2 and the utilization of electrons. Additionally, the formation of S-scheme heterojunction expands the redox range and improves the separation efficiency of photo-generated charges.

High-Volumetric Density Atomic Cobalt on Multishell ZnxCd1-xS Boosts Photocatalytic CO2 Reduction.

The volumetric density of the metal atomic site is decisive to the operating efficiency of the photosynthetic nanoreactor, yet its rational design and synthesis remain a grand challenge. Herein, we report a shell-regulating approach to enhance the volumetric density of Co atomic sites onto/into multishell ZnxCd1-xS for greatly improving CO2 photoreduction activity. We first establish a quantitative relation between the number of shell layers, specific surface areas, and volumetric density of atomic sites on multishell ZnxCd1-xS and conclude a positive relation between photosynthetic performance and the number of shell layers. The triple-shell ZnxCd1-xS-Co1 achieves the highest CO yield rate of 7629.7 μmol g-1 h-1, superior to those of the double-shell ZnxCd1-xS-Co1 (5882.2 μmol g-1 h-1) and single-shell ZnxCd1-xS-Co1 (4724.2 μmol g-1 h-1). Density functional theory calculations suggest that high-density Co atomic sites can promote the mobility of photogenerated electrons and enhance the adsorption of Co(bpy)32+ to increase CO2 activation (CO2 → CO2* → COOH* → CO* → CO) via the S-Co-bpy interaction, thereby enhancing the efficiency of photocatalytic CO2 reduction.

Recent Progress on the Surface and Bulk Modification of Carbon Nitrides for Photocatalytic Carbon Dioxide Reduction

Photocatalytic CO2 reduction has been considered as a green and sustainable approach to solve energy and environmental problems. However, the CO2 reduction efficiency of various types of semiconductor photocatalysts studied at this stage is far from realizing practical applications. The challenge of photocatalytic CO2 reduction is to design photocatalysts with excellent catalytic performance. This article summarizes the carbon nitride materials for efficient CO2 reduction and obtaining high value‐added products. The physicochemical properties of carbon nitride materials are discussed in terms of the photocatalytic mechanisms (bandgap tuning, high specific surface area, shorter electron–hole transmission paths, increasing the number of active sites, etc.). The present review provides the latest research progress of carbon nitride modification strategies. The prospects and challenges for the application of carbon nitride materials for CO2 reduction are presented. This review article will provide useful guidance for further research on carbon nitride materials for efficient photocatalytic CO2 reduction.

Amorphous ZnSnOx Hollow Spheres Enable Highly Efficient CO2 Reduction.

Carbon dioxide (CO2) adsorption and electron transport play an important role in CO2 reduction reaction (CO2RR). Herein, we have demonstrated a new class of diverse hollow ZnSnOx (ZSO) through the amorphization of hydroxides to enhance CO2 adsorption and accelerate electron transport. The amorphization is occurred by calcination process, as indicated by Fourier transform infrared spectroscopy and Raman spectra. In particular, the ZnSnOx hollow spheres (ZSO HSs) achieve a high Faradaic efficiency (FE) of HCOOH up to 92.7 % at best, outperforming the commercial ZSO (Comm. ZSO, 85.7 %). ZSO HSs also exhibit durable stability with negligible activity decay after 10 h of successive electrolysis. In-situ attenuated total reflectance infrared absorption spectroscopy further reveals strong adsorption of CO2 and rapid intermediate configuration transformation in amorphous ZSO HSs. This work demonstrates the practical application of ZSO for CO2RR and provides a new insight to create efficient CO2RR electrocatalysts.

Engineering NH2-Cu-NH2 Triple-atom Sites in Defective MOFs for Selective Overall Photoreduction of CO2 into CH3COCH3.

Selective photoreduction of CO2 to multicarbon products, is an important but challenging task, due to high CO2 activation barriers and insufficient catalytic sites for C-C coupling. Herein, a defect engineering strategy for incorporating copper sites into the connected nodes of defective metal-organic framework UiO-66-NH2 for selective overall photo-reduction of CO2 into acetone. The Cu2+ site in well-modified CuN2O2 units served as a trapping site to capture electrons via efficient electron-hole separation, forming the active Cu+ site for CO2 reduction. Two NH2 groups in CuN2O2 unit adsorb CO2 and cooperated with copper ion to functionalize as a triple atom catalytic site, each interacting with one CO2 molecule to strengthen the binding of *CO intermediate to the catalytic site. The deoxygenated *CO attached to the Cu site interacted with *CH3 fixed at one amino group to form the key intermediate CO*-CH3, which interacted with the third reduction intermediate on another amino group to produce acetone. Our photocatalyst realizes efficient overall CO2 reduction to C3 product acetone CH3COCH3 with an evolution rate of 70.9 μmol gcat -1 h-1 and a selectivity up to 97 % without any adducts, offering a promising avenue for designing triple-atomic sites to producing C3 product from photosynthesis with water.

Cr dopants and S vacancies in ZnS to trigger efficient photocatalytic H2 evolution and CO2 reduction

Driven by endless solar energy, photocatalytic H2 evolution from water splitting and CO2 conversion to hydrocarbon fuels over semiconductor photocatalysts are of great potential to simultaneously settle the greenhouse effect and energy shortage. Herein, Cr-doped zinc sulfide (ZnS) with accompanying sulphur vacancies (Vs) photocatalytic materials is developed by a facile hydrothermal method. The Cr dopants centralize photoinduced holes and Vs trap electrons, forming a synergistic effect for accelerating charge separation and transfer. The reaction energy barrier for both H2 evolution and CO2 reduction has been optimized. Therefore, in the absence of a cocatalyst, the optimal catalyst (Zn0.94Cr0.06S) achieves an outstanding H2 evolution activity of 20.3 mmol g−1 h−1, which is approximately 2.9 times higher than 6.9 mmol g−1 h−1 for pristine ZnS. In addition, in the gas-solid reaction system without co-catalysts or sacrificial agents, the Zn0.94Cr0.06S exhibits a considerable CO evolution rate of 19.56 μmol g−1 h−1, about 10.1 times higher than ZnS (1.94 μmol g−1 h−1). Both the performances for H2 evolution and CO2 reduction of Zn0.94Cr0.06S outperform most of the previously reported photocatalysts. Particularly, the Zn0.94Cr0.06S possesses superior stability, the photoactivity of which exhibits no noticeable deactivation after six cycles’ reactions. This work may shed light on the rational design and fabrication of highly efficient materials via combining individual element doping and defect engineering.

Engineering NH2‐Cu‐NH2 Triple‐atom Sites in Defective MOFs for Selective Overall Photoreduction of CO2 into CH3COCH3

AbstractSelective photoreduction of CO2 to multicarbon products, is an important but challenging task, due to high CO2 activation barriers and insufficient catalytic sites for C−C coupling. Herein, a defect engineering strategy for incorporating copper sites into the connected nodes of defective metal–organic framework UiO‐66‐NH2 for selective overall photo‐reduction of CO2 into acetone. The Cu2+ site in well‐modified CuN2O2 units served as a trapping site to capture electrons via efficient electron‐hole separation, forming the active Cu+ site for CO2 reduction. Two NH2 groups in CuN2O2 unit adsorb CO2 and cooperated with copper ion to functionalize as a triple atom catalytic site, each interacting with one CO2 molecule to strengthen the binding of *CO intermediate to the catalytic site. The deoxygenated *CO attached to the Cu site interacted with *CH3 fixed at one amino group to form the key intermediate CO*‐CH3, which interacted with the third reduction intermediate on another amino group to produce acetone. Our photocatalyst realizes efficient overall CO2 reduction to C3 product acetone CH3COCH3 with an evolution rate of 70.9 μmol gcat−1 h−1 and a selectivity up to 97 % without any adducts, offering a promising avenue for designing triple‐atomic sites to producing C3 product from photosynthesis with water.

Introduction of a Conductive Layer into Flood-Resistant Gas Diffusion Electrodes with Polymer Substrate for an Efficient Electrochemical CO2 Reduction with Copper Oxide.

Conversion of atmospheric carbon dioxide (CO2) into valuable feedstocks is a crucial technology, and electrochemical reduction of CO2 is a promising approach that can provide a useful source of ethylene (C2H4). Gas diffusion electrodes (GDEs) placed at the interface of the CO2 gas and electrolyte can achieve high current density through a sufficient supply of dissolved CO2 to the reaction site, making them indispensable in industrial applications. However, conventional GDEs with carbon substrate have suffered from electrolyte flooding and consequent loss of efficiency, posing an obstacle for practical application. While flood-resistant GDEs with hydrophobic polymer substrate have been proposed recently, only conductive materials can be employed as electrocatalysts because of their insulative properties, despite the high activities of oxide materials such as copper oxide. Here, we introduce an aluminum conductive layer in GDE with polymer substrate to enable the use of electrically resistive catalysts. Cuprous oxide (Cu2O) with silver particles was tested as a model material and has shown prolonged stability (>17 h) with high C2H4 Faraday efficiency (>50%) while suppressing flooding. A thorough characterization revealed that the conductive layer makes Cu2O an efficient electrocatalyst, even on the polymer substrate, by providing sufficient electrons through its conduction path. This research significantly expands the scope of electrode design by enabling the incorporation of a wide range of nonelectrically conductive materials on GDEs with polymer substrate.

S-dopant and O-vacancy of mesoporous ZnO nanosheets induce high efficiency and selectivity of electrocatalytic CO2 reduction to CO

Surface engineering can adjust the electronic properties of catalysts, thereby boosting their electrocatalytic performances. Herein, S-doped and O-vacant mesoporous ZnO nanosheets (ZnO-VO-S) were synthesized through the plasma-treatment method, exhibiting highly electrocatalytic selectivity and activity in the conversion of CO2 to CO. Synchrotron X-ray absorption fine structure (XAFS) investigations were used to further clarify the valence state and local coordination structure of Zn, concretely affirming the reduced electron density of Zn in ZnO-VO-S. Specifically, at −1.1 V vs. RHE, the as-prepared ZnO-VO-S demonstrated a high Faradaic efficiency of 90%. Experiments and density functional theory (DFT) suggest that the electron deficiency of Zn caused by the introduction of S dopant and O vacancy, reduces the energy barrier of CO2 to CO by improving the adsorption behavior of the intermediate *COOH.

Highly efficient electrocatalytic CO2 reduction by a CrIII quaterpyridine complex

Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO2 reduction, especially for the rarely studied Cr-based ones. Herein, a quaterpyridyl CrIII catalyst is found to be highly active for CO2 electroreduction to CO with 99.8% Faradaic efficiency in DMF/phenol medium. A nearly one order of magnitude higher turnover frequency (86.6 s-1) over the documented Cr-based catalysts (<10 s-1) can be achieved at an applied overpotential of only 190 mV which is generally 300 mV lower than these precedents. Such a high performance at this low driving force originates from the metal-ligand cooperativity that stabilizes the low-valent intermediates and serves as an efficient electron reservoir. Moreover, a synergy of electrochemistry, spectroelectrochemistry, electron paramagnetic resonance, and quantum chemical calculations allows to characterize the key CrII, CrI, Cr0, and CO-bound Cr0 intermediates as well as to verify the catalytic mechanism.