Activity For CO2 Reduction Research Articles

Molybdenum diselenide/polymeric carbon nitride dual-homojunction photocatalyst with multi-step charge transfer for efficient catalytic carbon dioxide reduction

Due to the high dissociation energy of carbon dioxide (CO2) and sluggish charge transfer dynamics, photocatalytic CO2 reduction with high performance remains a huge challenge. Herein, we report a novel dual-homojunction photocatalyst comprising of cyano/cyanamide groups co-modified carbon nitride (CN-TH) intramolecular homojunction and 1 T/2H-MoSe2 homojunction (denoted as 1 T/2H-MoSe2/CN-TH) for enhanced photocatalytic CO2 reduction. In this dual-homojunction photocatalyst, the intramolecular CN-TH homojunction could promote the intralayer charge separation and transfer owing to the strong electron-withdrawing capabilities of the two-type cyanamide, while the 1 T/2H-MoSe2 homojunction mainly contributes to a promote interlayer charge transport of CN-TH. This could consequently induce a tandem multi-step charge transfer and accelerate the charge transfer dynamics, resulting in enhanced CO2 reduction activities. Thanks to this tandem multi-step charge transfer, the optimized 1 T/2H-MoSe2/CN-TH dual-homojunction photocatalyst presented a high CO yield of 27.36 μmol·g−1·h−1, which is 3.58 and 2.87 times higher than those of 1 T/2H-MoSe2/CN and 2H-MoSe2/CN-TH single homojunctions, respectively. This work provides a novel strategy for efficient CO2 reduction via achieving a tandem multi-step charge transfer through designing dual-homojunction photocatalyst.

Thermal‐Driven Dispersion of Bismuth Nanoparticles among Carbon Matrix for Efficient Carbon Dioxide Reduction

AbstractThe poor electrocatalytic stability and rapid deactivation of metal electrocatalysts are always present in the electrocatalytic conversion of carbon dioxide (CO2) due to the harsh reduction condition. Herein, we demonstrate the controllable dispersion of ultrafine bismuth nanoparticles among the hollow carbon shell (Bi@C‐700‐4) simply by a thermal‐driven diffusion process. The confinement effect of nitrogen‐doped carbon matrix is able to low the surface energy of bismuth nanoparticles against the easy aggregation commonly observed for the thermal treatment. On the basis of the synergistic effect and confinement effect between bismuth nanoparticles and carbon matrix, the highly dispersed active sites render the obviously improved electrocatalytic activity and stability for CO2 reduction into formate. The in situ experimental observations on the reduction process and theoretical calculations reveal that the incorporation of bismuth nanoparticles with nitrogen‐doped carbon matrix would promote the activation of CO2 and the easy formation of key intermediate (*OCHO), thus leading the enhanced electrocatalytic activity, with a Faradaic Efficiency (FE) of formate about 94.8 % and the long‐time stability. Furthermore, the coupling of an anode for 5‐hydroxymethylfurfural oxidation reaction (HMFOR) in solar‐driven system renders the high 2,5‐furandicarboxylic acid (FDCA) yield of 81.2 %, presenting the impressive solar‐to‐fuel conversion.

Charge Transport Approaches in Photocatalytic Supramolecular Systems Composing of Semiconductor and Molecular Metal Complex for CO2 Reduction.

The design of photocatalytic supramolecular systems composing of semiconductors and molecular metal complexes for CO2 reduction has attracted increasing attention. The supramolecular system combines the structural merits of semiconductors and metal complexes, where the semiconductor harvests light and undertakes the oxidative site, while the metal complex provides activity for CO2 reduction. The intermolecular charge transfer plays crucial role in ensuring photocatalytic performance. Here, we review the progress of photocatalytic supramolecular systems in reduction of CO2 and highlight the interfacial charge transfer pathways, as well as their state-of-the-art characterization methods. The remaining challenges and prospects for further design of supramolecular photocatalysts are also presented.

Bilayer Porous Electrocatalysts for Stable and Selective Electrochemical Reduction of CO2 to Formate in the Presence of Flue Gas Containing NO and SO2.

The development of stable and selective electrocatalysts for converting CO2 to value-added chemicals or fuels has gained much interest in terms of their potential to mitigate anthropogenic carbon emissions. Most of the electrocatalysts are tested under pure CO2; however, industrial outlet flue gas contains numerous impurities, such as NO and SO2, which poison the electrocatalysts and alter the product selectivity. Developing electrocatalysts that are resistant to such impurities is essential for commercial implementation. Herein, we prepared bilayer porous electrocatalysts, namely, Sn, Bi, and In, on porous Cu foam mesh (Sn/Cu-f, Bi/Cu-f, and In/Cu-f) by a two-step electrodeposition process and employed these electrodes for the electrochemical reduction of CO2 to formate. It was observed that the bilayer porous electrocatalysts exhibited high CO2 reduction activity compared to catalysts coated on a Cu mesh. Among bilayer porous electrocatalysts, Sn/Cu-f and Bi/Cu-f electrocatalysts showed more than 80% faradaic efficiency (FE) toward formate production, with a formate partial current density of around -16 and -10.4 mA cm-2, respectively, at -1.02 V vs RHE. In/Cu-f electrocatalyst showed nearly 40% formate FE with formate partial current density of -15 mA cm-2 at -1.22 V vs RHE. We investigated the effect of NO and SO2 impurities (500 ppm of NO, 800 ppm of SO2, and 500 ppm of NO + 800 ppm of SO2) on these electrocatalysts' selectivity and stability toward formate. It was observed that the Bi/Cu-f electrocatalyst showed 50 h stability with 80 ± 5% formate FE, and Sn/Cu-f showed 18 h stability with above 80 ± 5% efficiency in the presence of NO and SO2 mixed with CO2. Furthermore, we studied the effect of CO2 concentration with Sn/Cu-f and Bi/Cu-f catalysts in the range of 15-100% CO2, for which formate FEs of 45-80% were observed.

Enhanced photocatalytic CO2 reduction activity on the novel Z-scheme Co-MOF/Bi2MoO6 to form CO and CH4

Herein, a novel Z-scheme Co-MOF/Bi2MoO6 was synthesized by in-situ growth method. The photocatalytic CO2 reduction effect of Co-MOF/Bi2MoO6 was significantly improved, and the formation rates of CO and CH4 reached 19.76 and 8.24 μmol·g−1·h−1, which corresponded to 1.61 and 2.38 times of Co-MOF (CO: 12.31 μmol·g−1·h−1) and Bi2MoO6 (CH4: 3.46 μmol·g−1·h−1), respectively. The increased photocatalytic activity of Co-MOF/Bi2MoO6 resulted from the enhanced visible light capture capability and the Z-scheme heterojunction formed among Co-MOF and Bi2MoO6, which promoted the efficient separation of photogenerated carriers while retaining the highest redox capacity. The Z-scheme charge transfer direction of Co-MOF/Bi2MoO6 was confirmed by DRS, XPS, ESR, UPS, and the photocatalytic reaction mechanism was explained. In addition, the active substances and intermediates of Co-MOF/Bi2MoO6 in the photocatalytic CO2 reduction process were investigated using ESR and in-situ FT-IR. The work offers a idea for building MOFs-based heterojunctions to improve the effect of photocatalytic CO2 reduction.

In situ oxidized MXene improves CO2 reduction activity of CoPc

In situ oxidized MXene improves CO2 reduction activity of CoPc

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate‐Modified In: Water Activation and Active Site Tuning

AbstractElectrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P−O)δ− modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P−O)δ− has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P−O)δ− modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P−O)δ− modified oxide‐derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm−2 and a cathodic potential of −1.2 V vs. RHE in an alkaline electrolyte.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate-Modified In: Water Activation and Active Site Tuning.

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

Unlocking the Potential of Bi2S3-Derived Bi Nanoplates: Enhanced Catalytic Activity and Selectivity in Electrochemical and Photoelectrochemical CO2 Reduction to Formate.

Various electrocatalysts are extensively examined for their ability to selectively produce desired products by electrochemical CO2 reduction reaction (CO2RR). However, an efficient CO2RR electrocatalyst doesn't ensure an effective co-catalyst on the semiconductor surface for photoelectrochemical CO2RR. Herein, Bi2S3 nanorods are synthesized and electrochemically reduced to Bi nanoplates that adhere to the substrates for application in the electrochemical and photoelectrochemical CO2RR. Compared with commercial-Bi, the Bi2S3-derived Bi (S-Bi) nanoplates on carbon paper exhibit superior electrocatalytic activity and selectivity for formate (HCOO-) in the electrochemical CO2RR, achieving a Faradaic efficiency exceeding 93%, with minimal H2 production over a wide potential range. This highly selective S-Bi catalyst is being employed on the Si photocathode to investigate the behavior of electrocatalysts during photoelectrochemical CO2RR. The strong adhesion of the S-Bi nanoplates to the Si nanowire substrate and their unique catalytic properties afford exceptional activity and selectivity for HCOO- under simulated solar irradiation. The selectivity observed in electrochemical CO2RR using the S-Bi catalyst correlates with that seen in the photoelectrochemical CO2RR system. Combined pulsed potential methods and theoretical analyses reveal stabilization of the OCHO* intermediate on the S-Bi catalyst under specific conditions, which is critical for developing efficient catalysts for CO2-to-HCOO- conversion.

Harnessing the electrocatalytic potential of in-situ exsolution of Ni nanoparticles on lanthanum and calcium co-doped strontium titanate for CO2 reduction in solid oxide electrolysis cells

The exsolution phenomenon of metal nanoparticles from a perovskite oxide involves the creation of oxygen vacancies, contributing to improved catalytic activity for CO2 reduction. In this context, a B-site Ni-doped and A-site La, Ca co-doped strontium titanate, denoted as La0.20Sr0.25Ca0.45Ni0.05Ti0.95O3-δ (Ni-LSCT), is synthesized with the aim of serving as a highly efficient cathode in conjunction with LSM as the anode and YSZ as the electrolyte for CO2 reduction via solid oxide electrolysis process. The incorporation of 5 mol% Ni doping at the B-site of the perovskite is successfully achieved, leading to the subsequent release of highly dispersed nanoparticles upon exposure to a reducing environment. YSZ-electrolyte-supported SOECs featuring the Ni-LSCT cathode demonstrate a notable current density of 0.93 A/cm2 at an applied voltage of 2.5 V at 800 °C in pure CO2. Moreover, at the same temperature, the reduction current density measures 1.21 A/cm2 when the Ni-LSCT serves as the cathode in a 70/30 molar ratio (CO2/H2) environment and 1.73 A/cm2 with a 50/50 molar ratio of the feed gas, both at an applied voltage of 2.5 V. This suggests an enhanced CO2 reduction performance in a reducing atmosphere. The introduction of Ni doping into LSCT enhances the electrochemical activity of the cathode by augmenting oxygen vacancies, while the presence of Ni nanoparticles on the cathode surface intensifies the active sites. Collectively, this innovative electrocatalyst configuration presents promising prospects for CO2 electrolysis within the SOEC framework.

Effect of the nitrogen/carbon ratio in the organic ligand of a nickel single-atom catalyst on its electrochemical activity in CO2 reduction

Simple, large-scale synthesis of metal single-atom catalysts (SACs) is limited by the aggregation of metal atoms on the support material surface. The N atoms in small organic ligands (SOLs) can anchor single metal atoms, affording abundant surface-active sites. In this study, we investigated the effect of the nitrogen/carbon ratio (N/C) in SOLs on the properties of the resultant Ni single-atom confined nitrogen-doped carbon black (Ni-NCB). The N/C ratio affected the thermal stability of Ni-NCB_N/Cs during carbonization, and the optimal Ni-NCB (Ni-NCB_0.5) was synthesized with the SOL 2-methylimidazole. Ni-NCB_0.5 achieved a CO partial current density of > 500 mA cm–2 and high CO Faradaic efficiency (96.4 %) in the CO2 reduction reaction. The 3- and 4-cell stack systems with Ni-NCB_0.5 (25 cm2 area per unit cell) exhibited an overall current of 10 A, high CO selectivity (> 96.0 %), and long-term stability (50 h). This synthetic strategy for SACs can be commercialized and even extended to other industrial electrocatalysts.

Lattice-dislocated bismuth nanowires formed by in-situ chemical etching on copper foam for enhanced electrocatalytic CO2 reduction

Electrochemical CO2 reduction reaction (CO2RR) to HCOOH is one of the most feasible and economical methods to achieve carbon neutrality. Bismuth (Bi), as a metal catalyst for CO2RR, is considered to have great potential for application and has been widely studied due to its high formate selectivity, low toxicity, cheapness, and abundance. Unfortunately, low current density and short electrode lifetime have hindered its progress towards practical applications. In this work, we present a method that enables the chemical etching of Bi on Cu, which is capable of spontaneously accomplishing the loading of Bi on Cu foam in the liquid phase at room temperature. Additionally, to provide more abundant catalytically active sites, twisted Bi nanowires (BiNWs) with lattice dislocations were successfully prepared on the surface of Cu foam using a three-step chemical method involving oxidation, reduction, and in-situ etching. The Cu Foam@BiNWs was found to be a highly active electrocatalyst for CO2 reduction to formate at a low applied potential, achieving a faradaic efficiency for formate (FEFormate) of 95 % and a formate partial current density of ∼ 12 mA cm−2 at −0.78 V vs. RHE (reversible hydrogen electrode). Even within such a wide potential window of −0.68 ∼ -1.08 V vs. RHE, the FEFormate is consistently above 90 %. Such exceptional CO2 reduction activity can be attributed to the distortions and lattice dislocations present in the surface BiNWs. Furthermore, the Cu Foam@BiNWs electrode demonstrated a total current density close to 100 mA cm−2 at −0.98 V in an alkaline flow cell, while maintaining excellent catalytic stability over a prolonged 30-hour period of high current density electrochemical activity, thus showing potential for advancing the industrialisation of formate production. This work emphasizes the crucial role of size-dependent catalysis and crystal defect engineering strategies in the field of electrocatalysis, elucidates the mechanism of the rate-determining step (RDS) in the electrocatalytic CO2 reduction process on the developed catalysts, which can provide valuable insights into the design and development of high performance electrocatalysts not only in CO2RR but also in other fields.

Insights into the effect of Ni doping on In2S3 for enhanced activity and selectivity of photocatalytic CO2 reduction

The limited photocatalytic CO2 reduction performance mainly lies in the low utilization of photogenerated electrons during the reaction. In this work, we developed the defect level within the Ni-doped In2S3 nanotube photocatalysts via a simple solvothermal method to increase the available amount of photogenerated electrons for enhanced photocatalytic CO2 reduction performance than the pristine In2S3. The introduction of Ni element into the lattice of In2S3 could significantly improve the photocatalytic activity and selectivity without destruction of the nanotube structure of In2S3. The yield of CO reaches 243.2 μmol/g/h under visible light, which is the highest reported value among In2S3 photocatalysts, and is 8.2 times more than the pure In2S3. Moreover, by modulating the doping amount of Ni element, the selectivity of CO varied from 27.7% to 51.0%. Further characterizations suggest that the doping of Ni element altered the electronic bandgap arrangement of In2S3, where the position of the conduction band is conducive to the activation of CO2 molecules. Moreover, the defect level resulting from Ni-doping not only facilitates the separation of photoexcited electron-hole pairs but also suppresses the recombination of electrons and holes. This study provides an available and reliable strategy for enhancing the photocatalytic CO2 reduction performance of related sulfide photocatalytic materials in future studies.

Spin polarization in Fe-doped CsPbBr3 perovskite nanocrystals for enhancing photocatalytic CO2 reduction

Spin manipulation offers an effective strategy to enhance photocatalytic activity in metal halide perovskites by suppressing the recombination of photo-excited electrons. However, the scope of the magnetic dopant inducing spin polarization is still limited. Here, we introduce synergetic strategies to polarize the spin in photo-excited electrons and boost their photocatalytic activity for CO2 reduction. We dope iron cation (Fe2+) into CsPbBr3 perovskite nanocrystals (PNCs). Fe ions induce paramagnetism, fostering spin polarization within the Fe-doped CsPbBr3 PNCs (Fe-CsPbBr3 PNCs) under magnetic fields. The magnetic compositions in PNC tend to stabilize the spin polarized electrons within the PNC, mitigate the recombination of photo-excited electrons and enhance the redox reaction for photocatalytic CO2 reduction. The synergistic effects of magnetic element doping and the application of magnetic fields resulted in a photocatalytic CO2 reduction of 133.04 μmol g−1, which is 1.68-fold increase compared to the Fe-PNC without a magnetic field. This work provides a simple and environmentally friendly approach to CO2 reduction based on PNCs.

Unveiling the role of proton concentration in dinuclear metal complexes for boosting photocatalytic CO2 reduction

The reaction kinetics of photocatalytic CO2 reduction is highly dependent on the transfer rate of electrons and protons to the CO2 molecules adsorbed on catalytic centers. Studies on uncovering the proton effect in catalysts on photocatalytic activity of CO2 reduction are significant but rarely reported. In this paper, we, from the molecular level, revealed that the photocatalytic activity of CO2 reduction is closely related to the proton availability in catalysts. Specifically, four dinuclear Co(II) complexes based on Robson-type ligands with different number of carboxylic groups (-nCOOH; n = 0, 2, 4, 6) were designed and synthesized. All these complexes show photocatalytic activity for CO2 reduction to CO in a water-containing system upon visible-light illumination. Interestingly, the CO yields increase positively with the increase of the carboxylic-group number in dinuclear Co(II) complexes. The one containing -6COOH shows the best photocatalytic activity for CO2 reduction to CO, with the TON value reaching as high as 10,294. The value is 1.8, 3.4, and 7.8 times higher than those containing -4COOH, -2COOH, and -0COOH, respectively. The high TON value also makes the dinuclear Co(II) complex with -6COOH outstanding among reported homogeneous molecular catalysts for photocatalytic CO2 reduction. Control experiments and density functional theory calculation indicated that more carboxylic groups in the catalyst endow the catalyst with more proton relays, thus accelerating the proton transfer and boosting the photocatalytic CO2 reduction. This study, at a molecular level, elucidates that more carboxylic groups in catalysts are beneficial for boosting the reaction kinetics of photocatalytic CO2 reduction.

The Tandem Nitrate and CO2 Reduction for Urea Electrosynthesis: Role of Surface N-Intermediates in CO2 Capture and Activation.

Electrochemical reduction of CO2 and nitrate offers a promising avenue to produce valuable chemicals through the using of greenhouse gas and nitrogen-containing wastewater. However, the generally proposed reaction pathway of concurrent CO2 and nitrate reduction for urea synthesis requires the catalysts to be both efficient in both CO2 and nitrate reduction, thus narrowing the selection range of suitable catalysts. Herein, we demonstrate a distinct mechanism in urea synthesis, a tandem NO3 - and CO2 reduction, in which the surface amino species generated by nitrate reduction play the role to capture free CO2 and subsequent initiate its activation. When using the TiO2 electrocatalyst derived from MIL-125-NH2, it intrinsically exhibits low activity in aqueous CO2 reduction, however, in the presence of both nitrate and CO2, this catalyst achieves an excellent urea yield rate of 43.37 mmol ⋅ g-1 ⋅ h-1 and a Faradaic efficiency of 48.88 % at -0.9 V vs. RHE in a flow cell. Even at a low CO2 level of 15 %, the Faradaic efficiency of urea synthesis remains robust at 42.33 %. The tandem reduction procedure was further confirmed by in situ spectroscopies and theoretical calculations. This research provides new insights into the selection and design of electrocatalysts for urea synthesis.

The Tandem Nitrate and CO2 Reduction for Urea Electrosynthesis: Role of Surface N‐Intermediates in CO2 Capture and Activation

AbstractElectrochemical reduction of CO2 and nitrate offers a promising avenue to produce valuable chemicals through the using of greenhouse gas and nitrogen‐containing wastewater. However, the generally proposed reaction pathway of concurrent CO2 and nitrate reduction for urea synthesis requires the catalysts to be both efficient in both CO2 and nitrate reduction, thus narrowing the selection range of suitable catalysts. Herein, we demonstrate a distinct mechanism in urea synthesis, a tandem NO3− and CO2 reduction, in which the surface amino species generated by nitrate reduction play the role to capture free CO2 and subsequent initiate its activation. When using the TiO2 electrocatalyst derived from MIL‐125‐NH2, it intrinsically exhibits low activity in aqueous CO2 reduction, however, in the presence of both nitrate and CO2, this catalyst achieves an excellent urea yield rate of 43.37 mmol ⋅ g−1 ⋅ h−1 and a Faradaic efficiency of 48.88 % at −0.9 V vs. RHE in a flow cell. Even at a low CO2 level of 15 %, the Faradaic efficiency of urea synthesis remains robust at 42.33 %. The tandem reduction procedure was further confirmed by in situ spectroscopies and theoretical calculations. This research provides new insights into the selection and design of electrocatalysts for urea synthesis.

Structural and biochemical characterization of the M405S variant of Desulfovibrio vulgaris formate dehydrogenase.

Molybdenum- or tungsten-dependent formate dehydrogenases have emerged assignificant catalysts for the chemical reduction of CO2 to formate, with biotechnological applications envisaged in climate-change mitigation. The role of Met405 in the active site of Desulfovibrio vulgaris formate dehydrogenase AB (DvFdhAB) has remained elusive. However, its proximity to the metal site and the conformational change that it undergoes between the resting and active forms suggests a functional role. In this work, the M405S variant was engineered, which allowed the active-site geometry in the absence of methionine Sδ interactions with the metal site to be revealed and the role of Met405 in catalysis to be probed. This variant displayed reduced activity in both formate oxidation and CO2 reduction, together with an increased sensitivity to oxygen inactivation.

Ligand modulation of active center to promote lead-free Cs2AgInCl6 photocatalytic CO2 reduction

Metal halide perovskites (MHP) are potential candidates for the photocatalytic reduction of CO2 due to their long photogenerated carrier lifetime and charge diffusion length. However, the conventional long-chain ligand impedes the adsorption and activation of CO2 molecules in practical applications. Here, a ligand modulation technology is employed to enhance the photocatalytic CO2 reduction activity of lead-free Cs2AgInCl6 microcrystals (MCs). The Cs2AgInCl6 MCs passivated by Oleic acid (OLA) and Octanoic acid (OCA) are used for photocatalytic CO2 reduction. The results show that the surface defects and electronic properties of Cs2AgInCl6 MCs can be adjusted through ligand modulation. Compared with the OLA-Cs2AgInCl6, the OCA-Cs2AgInCl6 catalyst demonstrated a significant improvement in the catalytic yield of CO and CH4. The CO and CH4 catalytic yields of OCA-Cs2AgInCl6 reached 171.88 and 34.15 µmol g−1 h−1 which were 2.03 and 12.98 times higher than those of OLA- Cs2AgInCl6, and the total electron consumption rate of OCA-Cs2AgInCl6 was 615.2 µmol g−1 h−1 which was 3.25 times higher than that of OLA-Cs2AgInCl6. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs2AgInCl6 MCs induced by ligand modulation. This study illustrates the potential of lead-free Cs2AgInCl6 MCs for efficient photocatalytic CO2 reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Coupling electron donors with proton repulsion via Pt-N3-S sites to boost CO2 reduction in CO2/H2 fuel cell

A fuel cell involving CO2/H2 is an appealing energy system to convert CO2 into synthetic fuels as well as to generate electricity using only waste heat. However, overcoming the inherent activation barrier of CO2 to improve the CO2 conversion rate in CO2/H2 fuel cell is still challenging. Herein, we report a synergistic electron-donor and proton-repulsion group composed of Pt-N3-S-C sites to simultaneously modulate the electronic structure and CO2-protonation ability of Ru nanoclusters (RuNC) in RuNC/Pt-N3-S-C catalyst. Experiments combined with theoretical calculations indicate that Pt-N3-S sites not only function as electron donors to Ru nanoclusters to cooperatively induce the orbital hybridization of Ru 3d and the antibonding orbitals of CO2, affording the dissociation of CO bonds in CO2, but also as electronic structure “modulator” to create new active sites on the surface of RuNC to effectively activate molecular CO2. More importantly, an internal polarization field between Pt-N3-S-C and RuNC additionally makes single atom Pt sites repel protons while Ru atoms serve as proton capturers via hydrogen spillover effect, resulting in accelerated protonation of CO2. Consequently, the catalyst exhibits highly improved catalytic activities for CO2 reduction with a conversion rate of 559.1 μmol gcat−1 h−1. This approach helps with fine tuning the electronic structures and catalytic CO2 protonation ability of catalysts for thermal-coupled electrocatalysis.