Release Of Electrons Research Articles

Sequential Aerial Oxidation and Atom‐Economical C‐3 Chalcogenation of Indolines Facilitated by Potassium tert‐Butoxide

AbstractAn operationally straightforward and highly efficient potassium tert‐butoxide facilitated protocol for the C‐3 chalcogenation of indolines under catalyst and additive‐free conditions has been established under ambient temperature. The salient features of the process include the development of transition metal‐free, oxidant‐free and iodine‐free, atom‐economic and cost‐effective reaction conditions at room temperature in DMSO as solvent for regioselective generation of 3‐chalcogenyl indoles in high yields. The mechanistic interpretation through controlled experiments and analysis of intermediates suggests the prevalence of the ionic pathway. The reaction is scalable to gram‐scale without a significant decrease in product yield, indicating its potential for large‐scale applications. This protocol offers a practical and environment friendly approach to accessing a diverse range of 3‐arylthioindoles and 3‐arylselenylindoles withstanding electron releasing and withdrawing substituents in good to excellent yields. Interestingly, the biological evaluation of the 3‐arylselenylindole products exhibited significant activity against breast cancer and triple‐negative breast cancer cell lines MCF‐7, and MDA‐MB 231. These results indicate the derivatives to be potent candidates for further SAR study.

Reducing Stoichiometric Excess of Base to Catalytic Amount: Revisiting Staudinger Reaction for -lactam Synthesis

Background: -lactams have been primarily utilized as a leading class of effective antibiotics. They have been found to show activity against various diseases, prompting the scientific community to prioritise innovative protocols for their synthesis. The general and well-known synthetic strategy involves the classical Staudinger reaction exhibiting [2+2] cycloaddition reaction. However, the protocol utilizes stoichiometric excess of base for efficient product formation. Objective: A smarter and more acceptable approach for the synthesis of -lactams would be to reduce the excess base to a catalytic amount, furnishing a catalytic version of the Staudinger reaction. The modified version can eliminate the hazards arising out of excess use of the base, ultimately promoting the environmentally benign approach. Methods: With this hypothesis, a base-catalyzed approach in dimethyl formamide (DMF) towards the synthesis of -lactam via Staudinger reaction has been endorsed under moderate reaction conditions. Results: The scope of the substrates was explored with both electron-withdrawing and electronreleasing substitutions in the formation of -lactam. The reduction of the base amount from stoichiometric to catalytic amount was justified by the involvement of DMF in generating the basic condition for the reaction. Conclusion: It was hypothesized that the decomposition of DMF under the base-catalysed reaction condition can generate dimethylamine, which produces the required basic environment. conclusion: A base-catalysed approach in dimethyl formamide (DMF) towards the synthesis of β-lactam via Staudinger reaction has been endorsed under moderate reaction conditions. The substrates scope was explored with both electron withdrawing and electron releasing substitutions in the formation of β-lactam. The reduction of base amount from stoichiometric to catalytic was justified by the involvement of DMF in generating the basic condition for the reaction. It was hypothesized that the decomposition of DMF under the base catalysed reaction condition can generate dimethylamine which produces the required basic environment.

Time, temperature and concentration resolved Yb3+ luminescence study in co-sputtered Cu2-xGaxS2 (0.1 < x < 1.6) thin films with a Cu–Ga composition gradient

The broad class of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials when doped with Yb3+ are interesting for thin film based luminescent solar concentrator (LSC's) application. In this work the strong and broad absorption properties of co-sputtered CuGaS2 (CGS) thin films combined with the luminescent properties of Yb are reported. Energy-dispersive x-ray spectroscopy (EDS), x-ray diffraction, transmission, excitation, and temperature dependent emission as well as radiative lifetime measurements are performed on thin films with varying Cu:Ga ratios and Yb3+ concentrations. It is found that Yb3+ emission can be broadly sensitized by the host in the range of 200–600 nm. A lower Cu:Ga ratio, crystallinity and post annealing in air provides a positive impact on the sensitization of Yb3+ emission. The temperature dependent time integrated decay curves show a clear thermal energy barrier of about 0.2 eV. Because the exponential tail, with a lifetime of 110 μs, is constant with temperature, we conclude that the barrier is connected to the thermal release of electrons trapped at the Yb2+ ground state. The low energy transfer efficiency from the host to the Yb dopant is attributed to efficient non-radiative electron-hole pair recombination. The prospects and design criteria of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials for LSC applications is the further subject of the discussion.

Multiple confinement-limited activation and defect effect co-triggered the ultra-long lifetime of carbon dots

The luminescence process of carbon dots (CDs) is typically influenced by spin-forbidden transition, triplet exciton quenching, and non-radiative transition. Thus, it faces great challenges to achieve efficient and ultra-long lifetime afterglow for CDs. The commonly employed strategy to obtain efficient afterglow performance of CDs is to encapsulate CDs into a rigid matrix to protect the afterglow signal from quenching. Generally, the ultra-long lifetime and excellent luminescent properties of inorganic RTP (room temperature phosphorescence) nanomaterials attribute to the slow release of electrons trapped in defect states of the surfaces. This capture-release mechanism has advanced afterglow lifetime of CDs towards longer levels via the design of defect states. Anchoring CDs onto a rigid matrix can preserve the rigid structure for the restrictive effect, and also can create structural defects. Herein, as-prepared RHCDs@SiO2 composite can exhibit an ultra-long afterglow lifetime of 7.76 s, which is the highest value achieved for CDs in silica matrix to date. This composite is also successfully applied in anti-counterfeiting and cell imaging fields. The synergistic multiple confinement effect and defect effect from the composite provides a universal strategy to design and achieve the ultra-long afterglow lifetime of CDs.

Cooperation of rhamnolipid and thermophilic bacteria modifies proteinic structure, microbial community, and metabolic traits for efficient solubilization and acidogenesis of mariculture solid wastes

Anaerobic fermentation combined with thermophilic bacteria (TB) pretreatment is a promising method to realize effective waste management and carbon resource recovery. However, undesirable properties of high-strength mariculture solid wastes (MSW) such as high solids concentration, excessive salinity and poor bioavailability limited the overall solubilization and acidogenic efficiency. This study innovatively introduced rhamnolipid (RL) to alleviate this adverse effect, and unveiled its cooperation with TB on enhancing organic matter dissolution and volatile fatty acids (VFAs) production. The results showed that VFAs yield from pretreated MSW was improved by 9.4-15.1 folds with enriched acetate (81.4%-94.4%) in the TB+RL groups. The co-pretreatment of RL and TB disintegrated substrate structure for efficient release of electron shuttles and biodegradable organics. This was because introducing RL reconstructed solid-liquid interfacial charge and molecular arrangement, improved thermophilic enzyme activity, and reduced apoptosis and necrosis cells of TB. Substrate bioavailability was further improved with proteinic structure shifted from α-helix and β-sheet to random coil and aggregated strands, and amide II and carboxyl groups interacted with RL molecules. These changes induced the selective enrichment of hydrolytic and acidogenic bacteria, and the upregulated expression of encoding genes responsible for transmembrane transport, protein hydrolysis, carbohydrate metabolism and acetate biosynthesis. This study provides a new strategy to overcome the bottlenecks of acidogenesis from high-strengthen organic wastes and deciphers the underlying mechanism.

Mechanochemical Thioglycolate Modification of Microscale Zero‐Valent Iron for Superior Heavy Metal Removal

Microscale zero‐valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron‐withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)‐sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG‐modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g−1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG‐modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

Mechanochemical Thioglycolate Modification of Microscale Zero-Valent Iron for Superior Heavy Metal Removal.

Microscale zero-valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron-withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)-sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG-modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g-1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG-modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

MoS2/CuS/g-C3N4 double S-scheme with charge storage ability for efficient photocatalytic H2 production

The photocatalytic H2 production technology exhibits promising potential in addressing the challenges of environmental pollution and energy crisis. In this work, CuS particles decorated MoS2 seaweed spheres (MoS2/CuS) were synthesized through a hydrothermal method, then they are loaded on the surface of g-C3N4 nanosheets using a solvent evaporation strategy to form MoS2/CuS/g-C3N4 double S-scheme heterojunction. The investigation reveals the H2 production rate of 25 wt% MoS2/CuS/g-C3N4 can reach up to 1438 μmol·g-1·h-1, which is 14.8-fold of g-C3N4 (97 μmol·g-1·h-1). Further studies indicate that the introduction of MoS2/CuS can broaden the light absorption range, increase electrochemical specific surface area, reduce the activation energy for H2 production and increase hydrophilicity of the composite. Especially, CuS can suppress carrier recombination effectively through its electron storage and release ability. Based on the experimental and theoretical analysis of band structures, the charge transfer in MoS2/CuS/g-C3N4 shares optimized double S-scheme charge transfer pathways with a dual reduction site, leading to an enhanced H2 evolution kinetics. This work offers valuable insights for the advancement of novel double S-scheme heterojunctions, showcasing their potential in energy storage and photothermal enhancement effects.

Stabilization of Cu2O catalyst via strong electronic interaction for selective electrocatalytic CO2 reduction to ethanol

While cuprous oxide (Cu2O) remains the most efficient and viable electrocatalyst for the electrochemical conversion of CO2 to ethanol, its reduction to Cu during the catalytic CO2RR process poses a barrier to its industrial application. To address this challenge, we have reported a highly stable Cu2O-based catalyst by introducing pseudo-capacitive NiCo2O4 intermediate layers. The current densities observed on the surface of the prepared NF@NiCo2O4@Cu2O remained consistent over a 15-hour stability test, demonstrating excellent durability that exceeds that of the NF@Cu2O electrode by more than 200 %. Experimental characterization and DFT analysis indicate that the exceptional stability is primarily attributed to the pseudo-capacitive NiCo2O4 interlayer with cyclic charge–discharge properties, where NiCo2O4 can capture and eliminate accumulated reduced electrons around Cu2O under strong electronic interactions and release electrons through catalytic reduction to produce hydrogen. Furthermore, the NiCo2O4@Cu2O (111) heterostructure significantly reduces the Gibbs free energy (ΔG) required for C-C coupling of *CO intermediates compared to Cu2O (111). This mechanism establishes a cyclic charge–discharge process in order to prevent reduction of Cu2O into copper monomers. As a result, NF@NiCo2O4@Cu2O demonstrates a C2H5OH faradaic efficiency of 56.9 % at −0.5 V vs. RHE, surpassing many other Cu-based catalytic electrodes. This work provides new insights into studying strong electronic interaction structures to eliminate electron enrichment at the catalytic site for stabilizing catalysts and also offers an effective strategy for designing catalysts that maintain long-term stability in industrial applications.

Sunlight‐Activated Eu2+‐Doped Red Persistent Luminescence Material for Night‐Vision Signage, Anti‐Counterfeiting and Location Detection

AbstractPersistent luminescence materials have been widely studied due to their excellent optical properties. However, they can only be activated by UV light; in other words, the charging method for these phosphors is limited. In fact, materials that can continuously emit light when exposed to sunlight are highly sought after for their potential to reduce energy consumption. Warm‐colored persistent luminescence materials are particularly useful for information storage, security marking, and preventing counterfeiting. Nevertheless, creating effective warm‐color persistent luminescence materials that are activated by sunlight remains a challenging task. To address this issue, novel daylight‐activated red persistent luminescence materials, Gd3‐xCax‐0.02GaO6:0.02Eu2+ (x = 0.3 ‐ 0.7) are explored. The material can be effectively activated by sunlight under all weather conditions, as well as by bright light from indoor lamps, mobile phone screens, and any form of visible light. Moreover, it possesses excellent water resistance. The process of electron trapping and release within the material is investigated through thermoluminescence experiments, photoluminescence spectra, and persistent luminescence spectra. Importantly, this phosphor has been demonstrated for various applications, including night vision marking, anti‐counterfeiting, optical information storage, and positioning, among others.

Hydrogen reduction and baking process of Pb-silicate microchannel plate and their performance studies

Microchannel plate (MCP) are honeycomb structures consisting of numerous parallel, hollow micro glass fiber channels renowned for their exceptional secondary electron multiplication. This paper investigates changes in MCP properties under hydrogen reduction temperatures ranging from 300 °C to 500 °C. The findings reveal that higher temperatures reduce surface metal oxides, which then accumulate within and darken the microchannels, affecting electron transport. Bulk resistance decreases before increasing, while gain increases and then decreases. At 350 °C, lead oxide begins to reduce to its conductive state, enhancing electron multiplication. However, increased temperatures cause clustering and roughening of the inner channel walls, which diminishes the efficiency of secondary electron release. These alterations are associated with the reduction dynamics of lead ions and temperature-induced microstructural changes. As the hydrogen reduction temperature increases, internal stresses shift outward, and the uniformity of gain varies, reaching its peak at 400 °C. Additionally, an aluminum oxide film enhances resistance to baking and ensures consistent bulk resistance. This study elucidates the relationship between MCP performance and reduction temperature, providing valuable insights for design improvement.

Metal-enhanced carbon-nitrogen material for selective detection of hazardous gases: Insights from interface electronic states

In this study, utilizing density functional theory, the C3N1 monolayer modified by Ir, Pd, Pt, and Rh atoms (Ir/Pd/Pt/Rh-C2N1) was chosen for selective adsorption of C2H2 amidst multiple gases (H2O, C2H2, and C4H10O2). According to the results of cohesive energy and ab initio molecular dynamics simulations, it is indicated that precious metal atoms can be stably anchored on the monolayer while enhancing the conductivity of the material The analysis of the electrostatic potential and work function determined the highly active sites and electron release capacity. In addition, the adsorption energy and distance disclosed the gas-solid interface structure of multiple gases on the Ir/Pd/Pt/Rh-C2N1 monolayer. Importantly, C2H2 exhibits strong responses to p-type semiconductor Pt-C2N1 and n-type semiconductor Ir-C2N1, respectively. Crystal Orbital Hamilton Population reveals the difference in adsorption energy due to modifications involving four precious metals. Interestingly, for the first time, the density of states calculation reveals that under the coexistence of multiple gases, the Pt/Ir-C2N1 monolayer effectively eliminates the interference of other gases and has a unique response only to C2H2. In real situations, with the basis of Gibbs free energy and Einstein's law of diffusion, it was determined that Pt-C2N1 and Ir-C2N1 showed excellent hydrophobicity, a wider temperature range, and a low diffusion activation energy barrier. In summary, Pt-C2N1 and Ir-C2N1 detect C2H2 without interference, maintaining fundamental principles, responsiveness, stability, and versatility unaffected by external factors.

Electron Release via Internal Polarization Fields for Optimal S-H Bonding States.

Transition metal dichalcogenides (TMDs) have received considerable attention as promising electrocatalysts for the hydrogen evolution reaction (HER), yet their potential is often constrained by the inertness of the basal planes arising from their poor hydrogen adsorption ability. Here, the relationship between the electronic structure of the WS2 basal plane and HER activity is systemically analyzed to establish a clear insight. The valance state of the sulfur atoms on the basal plane has been tuned to enhance hydrogen adsorption through sequential engineering processes, including direct phase transition and heterostructure that induces work function-difference-induced unidirectional electron transfer. Additionally, an innovative synthetic approach, harnessing the built-in internal polarization field at the W-graphene heterointerface, triggers the in-situ formation of sulfur vacancies in the bottom WSx (x < 2) layers. The resultant modulation of the valance state of the sulfur atom stabilizes the W-S bond, while destabilizing the S-H bond. The electronic structural changes are further amplified by the release and transfer of surplus electrons via sulfur vacancies, filling the valance state of W and S atoms. Consequently, this work provides a comprehensive understanding of the interplay between the electronic structure of the WS2 basal plane and the HER activity, focusing on optimizing S-H bonding state.

Exploring the post-illumination behavior of 1D/2D-NiMoO4/Bi2O2CO3 heterostructure photocatalyst: Insights into the photocatalytic 'memory effect'

Photocatalysts with a "memory" effect can regain their activity after light is removed. We developed a novel NiMoO4/Bi2O2CO3 hybrid photocatalyst through a simple hydrothermal process. This memory effect results from the trapping and release of photogenerated electrons, facilitated by the NiMoO4/Bi2O2CO3 hybrid's compatible band structures and internal electrostatic field, which enhance electron transfer. This photocatalyst effectively removes Rhodamine B (RhB), with a 34 % increase in oxidation after sunlight exposure. The optimized NiMoO4/Bi2O2CO3 composite achieves 84 % photocatalytic degradation of RhB (kapp = 0.0196 min−1) under visible light in 90 min, proving effective for water pollutant removal both during and after light exposure.

Theoretical Design of New Grafted Molecules d-Glucosamine-Oxyresveratrol-Essential Amino Acids: DFT Evaluation of the Structure-Antioxidant Activity.

In the pursuit of innovative high-performance materials suitable for antioxidant applications, the density functional theory was employed to design a series of compounds derived from small biodegradable organic molecules. This study involved grafting the negatively charged unit d-glucosamine (GleN) and essential amino acids onto the 3 and 4' carbons of the backbone of trans-2,4,3',5'-tetrahydroxystilbene (trans-OXY), respectively. The aim was to prevent trans-OXY degradation into the cis region and enhance its electronic and antioxidant properties. Theoretical calculations using DFT/PW91/TZP in water revealed that the designed biomolecules (GleN-OXY-AA) outperformed both free OXY units and essential amino acids in terms of antioxidant efficacy, as indicated by the bond dissociation energy (BDE) findings. Notably, GleN-OXY-Ile and GleN-OXY-Trp compounds exhibited an average BDE of 66.355 kcal/mol, translating to 1.82 times the activity of t-OXY and 1.55 times the action of ascorbic acid (Vit C). AIM analysis demonstrated that the proposed biomaterials favored the formation of quasi-rings through intramolecular H···O hydrogen bonds, promoting π-electron delocalization and stabilization of radical, cationic, and anionic forms. Quantum calculations revealed the release of hydrogen atoms or electrons from sites of reduced electronegativity, visually identified by MEP maps and estimated by Hirshfeld atomic charges.

Probing the Operation of Quantum-Dot Light-Emitting Diodes Using Electrically Pumped Transient Absorption Spectroscopy.

The quantum-dot light-emitting diode (QLED) is a new generation light emission source that holds great promise for display and lighting applications. Understanding the dynamics of electrons and holes in QLEDs during their operation is crucial for future QLED optimization, but a time-resolved technology capable of characterizing electrons is still lacking. To tackle this challenge, we develop a unique electrically pumped transient absorption (E-TA) spectroscopy to probe the density of electrons in the QD layer with a nanosecond time resolution. The E-TA result provides a comprehensive understanding of the electron dynamics in QLEDs by quantifying the electron injection time after external voltage on, electron release time after external voltage off, and equilibrated electron density (Ne) in the QD layer during device operation. By combining E-TA technology with time-resolved electroluminescence and transient current measurements, we present a comprehensive overview of the dynamics of both electrons and holes in a QLED during operation.

Co-doping Sm3+ transforms Y2Ge2O7:Pr3+ into a novel orange-reddish long afterglow phosphor

Red long afterglow phosphors have significant implications for the realization of multicolor long-afterglow phosphors, but their insufficient luminescence intensity and afterglow duration still cannot meet the demands of practical applications. In this study, a novel orange-red phosphor, Y2Ge2O7:Pr3+, was synthesized for the first time. This phosphor not only exhibits exceptional thermal resistance but also shows a marked enhancement in long-afterglow performance upon co-doping with Sm3+. Remarkably, an orange-red afterglow can still be distinctly observed with the naked eye even 5 min after the removal of the excitation source in darkness. Further investigations involving thermoluminescence spectrum tests and the construction of an independent host-referred binding energy (HRBE) diagram reveal that the introduction of Sm3+ effectively mitigates the trap depth (1.02 eV) of the Y2Ge2O7:Pr3+ phosphor and significantly augments the quantity of electrons in shallow traps. This modification facilitates the effective release of electrons under room temperature conditions by the improved phosphor, thereby actualizing the long-afterglow luminescence phenomenon. Additionally, our findings indicate that a trap depth within the range of 0.60–0.80 eV is the optimal range for releasing electrons at room temperature. This research offers a crucial reference for future endeavors aimed at enhancing the performance of long-afterglow phosphors.

Influence of riboflavin on the corrosion of X80 pipeline steel by Sulfate reducing bacteria

The sulfate reducing bacteria(SRB) is commonly attached to the surface of buried pipeline steel, and the electron shuttle in the corrosion medium can promote the release of electrons from iron oxidation through the bacterial cell wall into the cytoplasm to accelerate the corrosion of anode iron. This study investigated the impact of riboflavin (RF) as an endogenous electron shuttle on the corrosion behavior of X80 pipeline steel in SRB system. The findings indicated that while the type of corrosion products remains unchanged in samples under SRB+10 mg l−1 RF system, there was an expansion in both area and depth of corrosion pits on the sample surface, resulting in a corrosion loss rate approximately 3 times higher than that observed in SRB system. Furthermore, the polarization resistance (Rp) value of the sample in SRB system is about 2 ∼ 5 times that of the sample in SRB+10 mg l−1 RF system. Additionally, the corrosion current density of X80 pipeline steel samples soaked in SRB and SRB +10 mg l−1 RF system for 14 days is 9.31 × 10-6 A·cm−2 and 1.28 × 10−5 A·cm−2, and the addition of 10 mg l−1 RF increases the corrosion current density of SRB system by about 37.49%. These results indicated that the reaction resistance of SRB-induced MIC in X80 pipeline steel was significantly reduced due to the presence of RF.

Study on regeneration mechanism of composite adsorbent by Mg-MOF-74-based modified biochar

In this paper, composite adsorbent was prepared from biochar and Mg-MOF-74 by in-situ growth method to investigate regeneration mechanism. The effects of O2 and temperature on regeneration characteristics were investigated by CO2 adsorption properties and characterization techniques, and the optimal regeneration conditions were determined. Regeneration mechanism of adsorbent was revealed by adsorption kinetics and elemental valence analysis. The related wave function parameters were calculated based on DFT to reveal the repair mechanism of the failed oxidation sites from the microscopic level. The mechanism of CO2 adsorption by the repaired oxidation sites was explored based on the regenerated adsorption configuration. It was found that the regeneration performance of the adsorbent exhibited a trend of increasing and then decreasing with the increase of O2 concentration and temperature, and the optimal regeneration conditions were determined to be 5 % O2 concentration and 200 °C. At optimal regeneration conditions, a synergistic interaction between O2 and poly-metals was generated to enhance the adsorbent polarity. O2 also reacted with the adsorbent in a redox reaction to produce new oxygen-containing functional groups and cause pore expansion, the mass transfer and diffusion was enhanced. The oxidation site adsorbed O2 to undergo electron rearrangement and release the adsorbed CO2. Due to the nature of common orbital hybridization between metals, the metals underwent conjugation and synergistic effects with O2 to form tetrahedral co-coordination structures with lower energies. The electron density and electric field effects of the system were enhanced. The former enhanced interaction with CO2 to form carbonate. The latter increased the activity of the neighboring N atom, which in turn generated a stable ring structure with carbonate, and CO2 adsorption was enhanced.

Rational design of graphene biohydrogel as a modular platform for highly efficient starch‐to‐bioelectricity

AbstractChemical‐to‐bioelectricity by using different biocatalysts was considered as a next‐generation green power source. However, bioelectricity production using macromolecular substrate usually encountered low Coulombic efficiency (CE) and power density due to inefficient electron releasing and sluggish electron collection. Here, a rationally engineered biocascade (including depolymerization module, fermentation module, and electro‐respiration module) embedded in highly conductive 3D graphene hydrogel (electron collection module) was designed and fabricated as a modular platform to simultaneously improve the substrate degradation, enhance the electron releasing and reinforce the electron collection. As a result, this modular platform enabled a ~15‐fold improvement on power density and reached the highest CE (46.3%) and power density (780 mW/m2) ever reported for bioelectricity production from starch (a model macromolecular substrate). This work demonstrated a promising approach for rationally harvesting bioelectricity with complicated substrates, which would open up a new avenue for practical applications.