CO2 Reduction Research Articles

Understanding the Electrochemical Carbon Dioxide Reduction Reaction Mechanism of Lattice Tuning of Copper by Silver Single-Crystal Surface.

Intermolecular interactions and adsorbate coverage on a metal electrode's surface/interface play an important role in CO2 reduction reaction (CO2RR). Herein, the activity and selectivity of CO2RR on bimetallic electrode, where a full monoatomic Cu layer covers on Ag surface (CuML/Ag) are investigated by using density functional theory calculations. The surface geometric and electronic structure results indicate that there is high electrocatalytic activity for CO2RR on the CuML/Ag electrode. Specifically, the CuML/Ag surface can accelerate the H2O and CO2 adsorption and hydrogenation while lowering the reaction energy of the rate-determining step. The structure parameters of chemisorbed CO2 with and without H2O demonstrate that activated H2O not only promotes the C-O dissociation but also provides the protons required for CO2RR on the CuML/Ag electrode surface. Furthermore, the various reaction mechanism diagrams indicate that the CuML/Ag electrode has high selectivity for CO2RR, and the efficiency of products can be regulated by modulating the reaction's electric potential.

Bioremediation petroleum wastewater and oil-polluted soils by the non-toxigenic indigenous fungi.

Soil and wastewater samples contaminated by petroleum-related industries were collected from various locations in Saudi Arabia, a country known for its vast oil reserves. The samples were analyzed for their physicochemical properties, including the presence of metals, petroleum hydrocarbons, and aromatic compounds. A total of 264 fungal isolates were analyzed and categorized into eight groups of Aspergillus (194 isolates) and four groups of Penicillium (70 isolates). The potential of these fungal groups to grow in oil or its derivatives was investigated. Two isolates, Aspergillus tubingensis FA-KSU5 and A. niger FU-KSU69, were utilized in two remediation experiments-one targeting wastewater and the other focusing on polluted soil. The FA-KSU5 strain demonstrated complete removal of Fe3+, As3+, Cr6+, Zn2+, Mn2+, Cu2+ and Cd2+, with bioremediation efficiency for petroleum hydrocarbons in the wastewater from these sites ranging between 90.80 and 98.58%. Additionally, the FU-KSU69 strain achieved up to 100% reduction of Co2+, Ba2+, B3+, V+, Ni2+, Pb2+ and Hg2+, with removal efficiency ranging from 93.17 to 96.02% for aromatic hydrocarbons after 180min of wastewater treatment. After 21days of soil incubation with Aspergillus tubingensis FA-KSU5, there was a 93.15% to 98.48% reduction in total petroleum hydrocarbons (TPHs) and an 88.11% to 97.31% decrease in polycyclic aromatic hydrocarbons (PAHs). This strain exhibited the highest removal rates for Cd2+ and As3+ followed by Fe3+, Zn2+, Cr6+, Se4+ and Cu2+. Aspergillus niger FU-KSU69 achieved a 90.37% to 94.90% reduction in TPHs and a 95.13% to 98.15% decrease in PAHs, with significant removal of Ni2+, Pb2+ and Hg2+, followed by Co2+, V+, Ba2+ and B3+. The enzymatic activity in the treated soils increased by 1.54- to 3.57-fold compared to the polluted soil. Although the mixture of wastewater and polluted soil exhibited high cytotoxicity against normal human cell lines, following mycoremediation, all treated soils and effluents with the dead fungal biomass showed no toxicity against normal human cell lines at concentrations up to 500 µL/mL, with IC50 values ≥ 1000 µL/mL. SEM and IR analysis revealed morphological and biochemical alterations in the biomass of A. tubingensis FA-KSU5 and A. niger FA-KSU69 when exposed to petroleum effluents. This study successfully introduces non-toxigenic and environmentally friendly fungal strains play a crucial role in the bioremediation of contaminated environments. Both strains serve as low-cost and effective adsorbents for bio-remediating petroleum wastewater and oil-contaminated soil. Heavy metals and hydrocarbons, the primary pollutants, were either completely removed or reduced to permissible levels according to international guidelines using the dead biomass of FA-KSU5 and FA-KSU69 fungi. Consequently, the environments associated with this globally significant industry are rendered biologically safe, particularly for humans, as evidenced by the absence of cytotoxicity in samples treated with A. tubingensis FA-KSU5 and A. niger FA-KSU69 on various human cell types.

Supercritical carbon dioxide likely served as a prebiotic source of methanethiol in primordial ocean hydrothermal systems

Abiotic synthesis of methanethiol through CO2 reduction is a presumptive initiation reaction of protometabolism in primordial ocean hydrothermal systems. However, reported artificial means of methanethiol production indicate the necessity of gas-phase condition, rather than aqueous-phase setting, for this prebiotic reaction to occur. Here we show that, under supercritical CO2 with a geochemically feasible concentration of hydrogen, up to 7.9% conversion of hydrogen sulfide to methanethiol is attained through a 14-day reaction at 200 °C on molybdenum sulfide catalyst deposited in a carbonate-NaCl solution. On the present ocean floor, discharges of liquid/supercritical CO2 occasionally occur in close vicinity to hydrothermal vents. Geological records of ancient seafloor suggest prevalence of such CO2 fluxes associated with hydrothermal activities. Our experimental results link these facts with the protometabolism scenario, leading to the possibility that the generation and transportation of methanethiol through the subseafloor CO2 fluxes constituted the beginning step of protometabolism in primordial ocean hydrothermal systems. Thus, the supply of supercritical-CO2-derived materials likely assisted the chemical evolution of life in combination with the known geochemical processes at the vent-ocean interface.

Accounting of weathering enhancement by mafic mineral spreading for CO 2 storage

The reduction of atmospheric CO 2 is an urgent global issue in the mitigation of global warming. Carbonate acts as a carbon sink in Earth's surface layer, and the weathering of terrestrial silicates and the deposition of oceanic calcium carbonate and organic matter mainly determine atmospheric and oceanic carbon dynamics on geological time scales. Various CO 2 reduction approaches have been evaluated, and the weathering acceleration method is expected to be a low-cost approach. This study attempts to estimate carbonate precipitation potential and dissolution rate from alkali leaching rates using weathering tests on mafic rocks. Based on Japan's annual average rainfall, the in situ carbonate precipitation potential obtained by spreading an olivine mineral or basalt rock powder at 40 ton-powder/ha was on the order of 10 -3 ton/year/ton-rock. This weathering rate could not be greatly accelerated under natural temperature conditions and fine granulation of the minerals.

Hierarchically Ordered Pore Engineering of Carbon Supports with High-Density Edge-Type Single-Atom Sites to Boost Electrochemical CO2 Reduction.

Metal sites at the edge of the carbon matrix possess unique geometric and electronic structures, exhibiting higher intrinsic activity than in-plane sites. However, creating single-atom catalysts with high-density edge sites remains challenging. Herein, the hierarchically ordered pore engineering of metal-organic framework-based materials to construct high-density edge-type single-atomic Ni sites for electrochemical CO2 reduction reaction (CO2RR) is reported. The created ordered macroporous structure can expose enriched edges, further increased by hollowing the pore walls, which overcomes the low edge percentage in the traditional microporous substrates. The prepared single-atomic Ni sites on the ordered macroporous carbon with ultra-thin hollow walls (Ni/H-OMC) exhibit Faraday efficiencies of CO above 90% in an ultra-wide potential window of 600mV and a turnover frequency of 3.4×104h-1, much superior than that of the microporous material with dominant plane-type sites. Theory calculations reveal that NiN4 sites at the edges have a significantly disrupted charge distribution, forming electron-rich Ni centers with enhanced adsorption ability with *COOH, thereby boosting CO2RR efficiency. Furthermore, a Zn-CO2 battery using the Ni/H-OMC cathode shows an unprecedentedly high power density of 15.9mW cm-2 and maintains an exceptionally stable charge-discharge performance over 100h.

Insights into the Effect of Crystal Facets and Sulfur Defects on the Product Selectivity of Various CdS Configurations for CO2 Photoreduction: A DFT Study

CO2 photoreduction into valuable hydrocarbons, such as CO, CH4, and C2H4, delivers a promising approach to address both environmental and energy challenges. Transition metal chalcogenides, particularly cadmium sulfide (CdS), have emerged as prominent candidates due to their tunable electronic properties and availability. This study delves into a comprehensive investigation of how CdS crystalline facets and sulfur-deficient surfaces modulate the product selectivity. Through employing density functional theory (DFT), we unravel the catalytic performance of various CdS crystal orientations and sulfur vacancy configurations. The results have shown that different CdS facets exhibit unique electronic characteristics and surface energetics, which influence the adsorption dynamics and reaction pathways. The introduction of sulfur vacancies further modulates the nature of active sites, leading to substantial shifts in product selectivity. A detailed investigation on the reaction mechanisms unveils that specific facets preferentially facilitate the formation of CO, while others are more conducive to the generation of hydrocarbons such as CH4 and C2H4, due to the variations in activation barriers and intermediate stabilities. These findings underscore the importance of crystal facet engineering and defect manipulation in tailoring catalyst performance thus providing valuable insights for the rational design of efficient and selective CO2 reduction metal catalysts.

Regulating the Layer Stacking Configuration of CTF-TiO2 Heterostructure for Improving the Photocatalytic CO2 Reduction.

Herein, covalent triazine frameworks in eclipsed AA and staggered AB stacking modes are respectively used for the in-situ growth of TiO2, and two heterostructures are obtained. Due to the highly organized stacking of the molecular layer in CTF-AA that strengthens the interlayer interaction, the light absorption and carrier migration of CTF-AA/TiO2 are both enhanced in comparison to those of its component or CTF-AB/TiO2. Correspondently, the photocatalytic CO2 reduction reaction (CO2RR) of CTF-AA/TiO2 proffers 9.19 μmol·g-1·h-1 CH4 and 2.32 μmol·g-1·h-1 CO production, about 9.2 and 4.3 times greater than that of pristine TiO2, respectively. Even though the innate photoresponse of the triazine unit endows CTF-AB/TiO2 with augmented light capturing, its photocatalytic CO2 conversion is relatively insignificant. According to the analyses of the planar-averaged electron density difference and Bader charge, the unproductive CO2 efficiency might be due to the insufficient interfacial electron transfer from TiO2 to CTF-AB. Given that the ΔG (-3.22 eV) of CHO intermediate generation is lower than that of CO desorption (-1.23 eV), the reaction tends to further generate CH4 other than yielding CO. This study could shed fresh light over the reasonable design of effective photocatalytic heterostructures.

Cost benefit analysis of reducing speed limits in Athens to 30 Km/h

The objective of this research is to investigate public acceptance and socio-economic feasibility of reducing speed limit from 50 km/h to 30 km/h in certain parts of the road network of Athens, Greece. A questionnaire was developed based on the method of stated preference for various hypothetical scenarios of time, fuel consumption and the probability of road crash to investigate road user preferences towards the reduction of speed limit and identify the most important influencing factors preferences. A total of 408 respondents were asked to choose among three alternative proposals: a) Reduce the speed limit to 30 km/h throughout the urban network except on major arteries, b) Reduce the speed limit to 30 km/h throughout the urban network and c) No Reduction (do nothing). For the analysis, two binomial logistic regression models and two multinomial logistic regression models were developed. The results indicate that increase in travel time, the importance of speed in causing a crash, the number of crashes the user has been involved in, the respondent’s driving habits are the main determinants of the users’ preferences. Furthermore, a Cost Benefit Analysis (CBA) was conducted to understand the sustainability implications of the implementation of lower speed limits (i.e., 50 to 30 km/h). In terms of socio-economic impacts, the CBA considered safety-related metrics, namely the number of road casualties of all severity levels, and environmental-related metrics, namely reductions in CO2, NOx, PM levels as well as in road user surplus metrics namely travel time increase and fuel consumption reduction. Costs considered in the analysis result from increased time spent on the road. Consequently, the investment and the operational costs along with the socio-economic impact are estimated and monetized, up to the year 2030. The positive Net Present Value (NPV) and the high Internal Rate of Return (IRR), i.e. 64.5 %, obtained as well as the sensitivity analysis results, indicate the feasibility of this policy over time. Therefore, speed limit reductions are economically viable and so, should be encouraged.

Photothermal Synergistic Effect Induces Bimetallic Cooperation to Modulate Product Selectivity of CO2 Reduction on Different CeO2 Crystal Facets

AbstractProduct selectivity of solar‐driven CO2 reduction and H2O oxidation reactions has been successfully controlled by tuning the spatial distance between Pt/Au bimetallic active sites on different crystal facets of CeO2 catalysts. The replacement depth of Ce atoms by monatomic Pt determines the distance between bimetallic sites, while Au clusters are deposited on the surface. This space configuration creates a favourable microenvironment for the migration of active hydrogen species (*H). The *H is generated via the activation of H2O on monatomic Pt sites and migrate towards Au clusters with a strong capacity for CO2 adsorption. Under concentrated solar irradiation, selectivity of the (100) facet towards CO is 100 %, and the selectivity of the (110) and (111) facets towards CH4 is 33.5 % and 97.6 %, respectively. Notably, the CH4 yield on the (111) facet is as high as 369.4 μmol/g/h, and the solar‐to‐chemical energy efficiency of 0.23 % is 33.8 times higher than that under non‐concentrated solar irradiation. The impacts of high‐density flux photon and thermal effects on carriers and *H migration at the microscale are comprehensively discussed. This study provides a new avenue for tuning the spatial distance between active sites to achieve optimal product selectivity.

Structural and Reservoir Characteristics of Potential Carbon Dioxide Storage Sites in the Northern South Yellow Sea Basin, Offshore Eastern China

The geological storage of carbon dioxide (CO2) in offshore saline aquifers stands as a primary option for reducing CO2 emissions in coastal regions. China’s coastal regions, particularly Shandong and Jiangsu provinces, face significant challenges in CO2 reduction. Therefore, evaluating the feasibility of CO2 geological storage in the adjacent seas is critical. To assess the suitability of a CO2 storage site, understanding its structural and reservoir characteristics is essential to mitigate injection and storage risks. In this study, we analyzed the structural characteristics and potential traps of the Yantai Depression in the South Yellow Sea Basin based on seismic data interpretation. We further conducted well logging analysis and post-stack seismic inversion to obtain lithological data, including acoustic impedance and sandstone content percentages from the Cenozoic Funing Formation, Dainan–Sanduo Formation, and Yancheng Formation. Our findings highlight that the Yantai Depression in the South Yellow Sea Basin exhibits diverse structural traps and favorable reservoir–caprock combinations, suggesting promising geological conditions for CO2 storage. This area emerges as a suitable candidate for implementing CO2 geological storage initiatives.

Switching of electrochemical selectivity due to plasmonic field-induced dissociation

Electrochemical reactivity is known to be dictated by the structure and composition of the electrocatalyst-electrolyte interface. Here, we show that optically generated electric fields at this interface can influence electrochemical reactivity insofar as to completely switch reaction selectivity. We study an electrocatalyst composed of gold-copper alloy nanoparticles known to be active toward the reduction of CO2 to CO. However, under the action of highly localized electric fields generated by plasmonic excitation of the gold-copper alloy nanoparticles, water splitting becomes favored at the expense of CO2 reduction. Real-time time-dependent density functional tight binding calculations indicate that optically generated electric fields promote transient-hole-transfer-driven dissociation of the O─H bond of water preferentially over transient-electron-driven dissociation of the C─O bond of CO2. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.

Ag Nanoparticles-Confined Doped within Triazine-Based Covalent Organic Frameworks for Syngas Production from Electrocatalytic Reduction of CO2.

Electrocatalytic CO2 reduction reaction (CO2RR) emerges as a promising avenue to mitigate carbon emissions, enabling the capture and conversion of CO2 into high-value products such as syngas with CO/H2. One of the crucial aspects lies in the tailored development of durable and efficient electrocatalysts for the CO2RR. Covalent organic frameworks (COFs) possess unique characteristics that render them attractive candidates for catalytic applications. However, the relationship between structure and performance still requires further exploration; especially, most COFs with such properties are limited to COFs containing specific groups such as phthalocyanine or porphyrin groups. Here, we custom-synthesize two azine-linked nitrogen-rich COFs constructed from triazine building blocks, which are doped with ultrafine and highly dispersed Ag nanoparticles (Ag@TFPT-HZ and Ag@TPT-HZ). Thus-obtained COFs can serve as electrocatalysts for the CO2RR, and a comprehensive investigation has been conducted to uncover the intricate structure-performance relationship within these materials. Notably, Ag@TFPT-HZ exhibits superior CO selectivity in the electrocatalytic CO2RR, achieving a FECO of 81% and a partial current density of 7.65 mA·cm-2 at the potential of -1.0 V (vs reversible hydrogen electrode (RHE)). In addition, Ag@TPT-HZ as an electrocatalyst can continuously produce syngas with a CO/H2 molar ratio of 1:1, an ideal condition for methanol synthesis. The observed distinct performance between these two COFs is attributed to the presence of O atoms in TFPT-HZ. These O atoms facilitate a higher loading capacity of Ag nanoparticles (11 wt %) and generate a greater number of active sites, thereby enhancing electrochemical activity and promoting faster reaction kinetics. Therefore, two tailor-made two-dimensional (2D) nitrogen-rich COFs with various active sites as electrocatalysts can exhibit different outstanding electrocatalytic performances for CO2RR and possess high cycling stability (>50 h). This work offers valuable insights into the design and synthesis of electrocatalysts, particularly in elucidating the intricate relationship between their structure and performance.

Photoirradiation-enhanced behavior via morphological manipulation of CoFe2O4/g-C3N4 heterojunction for supercapacitor and CO2 reduction

Regulating the morphology of graphitic carbon nitride (g-C3N4, CN) and constructing CoFe2O4/g-C3N4 (CFO/CN) heterojunctions were adopted in the photocatalytic energy storage and photocatalytic CO2 reduction (PCR). CFO/CNS had outstanding light response ability, while CFO/CNT possessed excellent charge transfer ability. Consequently, CFO/CNT electrode exhibited the highest specific capacitance without light, CFO/CNS electrode showed the most obvious photo-enhanced capacitance behavior with an increase by 21.05 % under light. This was ascribed to the generation and separation of photo-generated carriers, promoting oxidation/reduction reactions. And in PCR, the electron consumption rates of four CFO/CN heterojunctions were CFO/CNT > CFO/BCN > CFO/MCN > CFO/CNS. CFO/CNT presented the highest photocatalytic activity, attributing to the strong redox ability and photo-enhanced electron transfer. This strategy of utilizing CFO/CN heterojunctions to construct photo-enhanced supercapacitor electrodes and photocatalytic CO2 reduction catalysts provided new ideas for energy conversion and storage.

Zirconium-doped ultrathin copper nanowires for C1 and C2+ products in electrochemical CO2 reduction reaction

Cu-based nanostructures have garnered significant attention in the field of electrochemical carbon dioxide reduction (eCO2R), due to their significant activity and ability to produce a variety of value-added hydrocarbons and oxygenates. Current research efforts focus on steering eCO2R towards the formation of multi-carbon (C2+) products and elucidating the complex mechanisms of C-C coupling. One promising approach involves transition metals into Cu nanostructures. This study computationally investigates the impact of trace Zr atom doping on Cu nanostructures, specifically at the interfaces of (100) and (110) surfaces of ultrathin Cu nanowires. Our findings reveal that Zr dopants are energetically favourable and facilitate charge transfer to adjacent Cu atoms, thereby reducing the activation barriers for C-C coupling and enhancing the formation of C1 and C2 hydrocarbons. Additionally, the Zr-O interaction weakens the C-O bond, promoting C-O bond cleavage. The formation of C3 products, and the selectivity between hydrocarbons and oxygenates, are influenced by the hydrogenation sequence on different carbon atoms.

Stabilizing In/InN intermediates by electron-deficient carbon for improved CO2 electroreduction to CO

Monitoring and stabilizing the reconstructed active material under operational conditions is crucial for the rational design of electrocatalysts. Herein, we developed a novel hinged structure composited by the electron-deficient carbon and InN nanorods (InN@C) for preserving the high-active In/InN interfaces under electrochemical CO2 reduction process. The electron-deficient carbon, caused by the interfacial rectifying effect, prevents active site annihilation and deep self-reduction of In/InN, leading to synergistic improvements in catalytic activity and long-term stability. Mechanistic studies show that an interfacial dipole between the electron-deficient carbon layer and In/InN promotes CO2 activation and strengthens In−N bonds, inhibiting the deep self-reduction of In/InN. As a result, we achieved remarkable long-term stability of 150 hours, with a Faradaic efficiency of 92 % and a current density of ∼ 40 mA cm−2 at − 0.8 V versus the reversible hydrogen electrode. This study offers a practical approach to preserve the high-active intermediates for synergistically improving the catalytic activity and long-term stability of transition metal compound electrocatalysts.

Simultaneous electrochemical upgrading of polyethylene terephthalate plastic and carbon dioxide into valuable chemicals

The natural environment is gravely threatened by plastic made of polyethylene terephthalate (PET) and CO2 pollution, which not only damage the environment but also waste a significant amount of carbon energy. Here, an electrocatalytic waste upgrading method to convert PET waste plastic and CO2 wastes into formate at the anode and cathode simultaneously. The anodic Mn/CoOOH electrocatalyst achieves high Faradaic efficiency (FE) of 96.7 % for formate production via PET hydrolysate oxidation and the cathodic oxygen vacancy rich Bi2O2CO3 (OV-rich BOC) electrocatalyst achieves high FE of 97.5 % for formate production via CO2 reduction. The constructed Mn/CoOOH||OV-rich BOC integrated system gets a total FEformate of 184.6 % at 150 mA cm−2 by combining integrated two half-reactions, along with outstanding stability for 100 h with a cell voltage of 2.2 V. More importantly, the oxidation and reduction intermediate (*CH2OH and *OCHO) were detection by quasi-in-situ electron paramagnetic resonance (EPR) and operando attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), which contribute to the understanding of reaction pathways. Techno-economic analysis shows that the final product potassium diformate can get profit instead of format acid, which points out the direction of practical application. Based on this study, electrocatalytic PET plastic valorization coupled with CO2 reduction can be a practical and cost-effective way to achieve the production of valuable chemicals.

Synthesis of isolated ZnO nanorods on introducing g-C3N4 for improved photoelectrocatalytic methanol production by CO2 reduction

The photoelectrocatalytic (PEC) CO2 reduction into fuels has been developed as a prospective approach to resolve the environmental and energy concerns. Herein, a composite catalyst comprising ZnO nanorods dispersed on the g-C3N4 surface (g-C3N4/ZnO) was successfully obtained by simple ZnO seed layer formation and then hydrothermal processes. The synthesized and characterized g-C3N4/ZnO catalytic composite showed 2.8 times enhanced photocurrent density at −1 V applied potential than the bare g-C3N4. The g-C3N4/ZnO catalyst exhibited 2.86 times enhanced the PEC CO2 reduction to methanol than the prepared bare ZnO catalyst. The catalyst’s enhanced the PEC CO2 reduction performance was ascribed to the high surface area, and higher generation and lower recombination of e−/h+ pairs. For the first time, this study showed the enhanced methanol production by the PEC reduction of CO2 over the prepared g-C3N4/ZnO catalytic composite.

Bismuth-based photocatalysts enhanced by sulfur/oxygen vacancies for the selective reduction of carbon dioxide into methane

Reducing carbon dioxide (CO2) into methane (CH4) through photocatalysis technology can effectively decrease carbon emissions and ease the energy crisis. However, the low photocatalytic efficiency and high electron-hole recombination rates still hinder the large-scale utilization of photocatalysis. Vacancy engineering can reduce electron-hole pair complexation, however, the effects of oxygen (O) and sulfur (S) vacancies on the CO2 reduction properties of bismuth (Bi)-based photocatalysts are unclear. This study prepared different Bi-based photocatalysts, including α-Bi2O3, α-Bi2O3-X, Bi2S3, and Bi2S3-X. The introduction of vacancies was found to greatly increase the specific surface areas, effectively reduce electron-hole recombination, decrease charge transfer resistance, and enhance electron transfer, leading to enhanced CH4 production. Comparatively, Bi2S3-X has substantially demonstrated a superior efficiency in the photocatalytic conversion of CO2 to CH4 compared to Bi2S3, while α-Bi2O3-X exhibited slightly higher than α-Bi2O3. There are more S vacancies in Bi2S3-X (x=0.581) than O vacancies in α-Bi2O3-X (x=0.329), leading to its superior photocatalytic activity, with CO and CH4 production rates of 3.706 μmol·g−1·h−1 and 7.697 μmol·g−1·h−1, respectively. Moreover, the CH4 selectivity of Bi2S3-X reaches 67.50 %, which is 1.67 times that of α-Bi2O3-X. Therefore, Bi2S3-X holds great promise as a photocatalyst for CO2 reduction. This work proves that in Bi-based photocatalyst, S vacancy is more effective than O vacancy in enhancing the selective reduction of CO2 to CH4, offering a pathway for achieving selective CO2 reduction to CH4.

Experimental study on effect of use of oxyhydrogen blends with traditional fuels in spark engines for better performance

The utilization of oxyhydrogen as a supplementary fuel in internal combustion engines has garnered significant attention due to its potential to enhance engine performance and reduce emissions. This study investigates the effects of oxyhydrogen addition on the performance, emissions, and thermodynamic efficiencies of a spark-ignition engine fueled by gasoline, propane, and methane. The engine drives a commercial stationary power generator. The results demonstrate that oxyhydrogen addition leads to a consistent reduction in CO2 and hydrocarbon emissions across all fuel types, with the most substantial reduction observed in gasoline, decreasing from 2413 g/kg to 1709 g/kg (a 29 % reduction) with 20 % oxyhydrogen addition. However, NOx emissions tend to increase, particularly pronounced in gasoline, where they escalate from 9.5 g/kg fuel with no oxyhydrogen to 24.6 g/kg fuel for the same case (a 159 % increase). The power output exhibits varying degrees of improvement depending on the fuel type and oxyhydrogen concentration. Oxyhydrogen has compensated for the power reduction when propane and methane are used as the base fuel. The energy and exergy efficiencies consistently improve with increasing oxyhydrogen addition, with the most significant improvement observed in propane, where the energy efficiency increases from 30.0 % to 37.3 % with and addition of 20 % oxyhydrogen.

Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural

Co3O4 possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co3O4 on OH− and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co3O4 with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH− species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co3O4 at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.