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A widely accepted theory is that life originated from the hydrothermal environment in the primordial ocean. Nevertheless, the low desorption temperature from inorganic substrates and the fragileness of hydrogen‐bonded nucleobases do not support the required thermal stability in such an environment. Herein, we report the super‐robust complexes of xanthine, one of the precursors for the primitive nucleic acids, with Na. We demonstrate that the well‐defined xanthine–Na complexes can only form when the temperature is ≥430 K, and the complexes keep adsorbed even at ≈720 K, presenting as the most thermally stable organic polymer ever reported on Au(111). This work not only justifies the necessity of high‐temperature, Na‐rich environment for the prebiotic biosynthesis but also reveals the robustness of the xanthine–Na complexes upon the harsh environment. Moreover, the complexes can induce significant electron transfer with the metal as inert as Au and hence lift the Au atoms up. [ABSTRACT FROM AUTHOR]

The development of eco‐friendly and low cost catalysts is challenging. Here, heterostructures of Bi2S3 quantum dots (QDs) doped onto ultrathin BiOCl nanosheets were synthesized by a facile hydrothermal method to exploit efficient photosensitizers with appropriate electronic states to enhance the transfer of electrons. The obtained Bi2S3−BiOCl showed highly efficient photocatalytic ability for selective oxidation of aromatic alcohols to aldehydes. More oxygen vacancies are formed on the exposed 001 facet of the ultrathin BiOCl, which can effectively trap electrons and form.O2− radicals. The cooperation between the BiOCl and the Bi2S3 QDs effectively separates photogenerated electron‐hole pairs at the heterointerface and facilitates the cooperative actions of.O2− radicals and holes, which brings about a desirable photocatalytic efficiency for the selective oxidation of aromatic alcohols. This work highlights the synergistic effect of semiconductor QDs and two‐dimensional materials on selective conversion processes and provides a new design paradigm using noble metal‐free heteromaterials with high photocatalytic activity. This opens new possibilities for photocatalyst design using heteromaterials with high photocatalytic activity. [ABSTRACT FROM AUTHOR]

• Initial set cathode potentials determine the electron transfer behavior of biocathode. • Biocathodes developed at > –0.8 V mainly possessed a direct electron transfer manner. • Biocathodes developed at < –0.8 V mainly possessed an indirect electron transfer pathway. Microbial electrosynthesis is an innovative technology capable of producing biofuels (particularly CH 4) via CO 2 reduction. Electron-uptaking from biocathode by microorganisms is the key step in the process of microbial electrosynthesis. However, the lack of understanding of electron transfer behaviors and their affecting factors largely limit the development of microbial electrosynthesis. Herein, we investigated the effects of initial startup cathode potentials (–0.7, –0.8, –0.9, –1.0 and –1.1 V vs. Ag/AgCl) on the electron transfer behaviors of biocathodes. The cyclic voltammetry (CV) showed typical sigmoidal catalytic currents corresponding to the CO 2 reduction on the biocathodes started up at –0.7 and –0.8 V, but not on the other biocathodes. The CH 4 production rate, Faradaic efficiency, scanning electron microscopy (SEM), and microbial community were also investigated. All the results indicated that the startup cathode potentials determine the electron transfer behaviors of biocathode: the biocathodes started up at –0.7 and –0.8 V mainly possessed a direct electron transfer manner, while the biocathodes started up at –0.9, –1.0 and –1.1 V mainly possessed an indirect electron transfer pathway. This study provides a guidance for the development of CH 4 -producing biocathodes with a desired electron transfer behavior. [ABSTRACT FROM AUTHOR]

[Display omitted] • Sb 2 S 3 nanowires/rGO composite was prepared by a simple self-assembly method with 3D interconnected structure. • The 3D-rGO framework effectively alleviates volume change and improves conductivity of Sb 2 S 3. • Sb 2 S 3 nanowires/rGO exhibits an outstanding capacity and long-term cycling stability when used as LIBs anode. The three-dimensional Sb 2 S 3 nanowires/reduced graphene oxide (SBSWs/rGO) was prepared as an anode for lithium storage by self-assembling SBSWs on 3D rGO framework. SBSWs/rGO shows the perfect rate capability (505 mAh g−1 at 3 A g−1) and long cycle stability (697 mAh g−1 after 100 cycles at 100 mA g−1). The 3D rGO framework has good structural stability, which can provide a free space towards shortening lithium ions diffusion paths and accommodating the volume change of SBSWs. The rGO sheets with high electrical conductivity promote electron transfer in composites to improve rate performances. [ABSTRACT FROM AUTHOR]

Novel SubPc-Br/Ag 3 PO 4 photocatalysts for pollutants degradation were fabricated via a facile impregnation method. The SubPc-Br/Ag 3 PO 4 showed significant improvement of photocatalytic activities compared to that of pristine Ag 3 PO 4 and the 4 wt% SubPc-Br/Ag 3 PO 4 sample exhibited the highest efficiency. The enhancement of photocatalytic performance was mainly induced by the sensitized effect of SubPc-Br, providing both accelerated charge separation and extended absorption region. This work may offer insights for developing the promising photocatalysts in the application of environmental remediation. • The obtained composites exhibited higher photocatalytic efficiency in degrading organic pollutants compared to pure Ag 3 PO 4. • The SubPc-Br/Ag 3 PO 4 photocatalysts showed an enhanced cycling stability. • This work paves the way to a new class of aromatic macrocyclic sensitizer. Ag 3 PO 4 has been proven to be an efficient photocatalyst to degrade organic pollutants in aqueous phase, which makes it a promising candidate for constructing an environmental purification system. In this study, novel series of subphthalocyanine-Br sensitized Ag 3 PO 4 (SubPc-Br/Ag 3 PO 4) photocatalysts with broadband light responsive ability were fabricated for the first time by coating SubPc-Br microcrystals onto the surface of Ag 3 PO 4 bulk polyhedron. The obtained SubPc-Br/Ag 3 PO 4 composites exhibited significant enhancement of photocatalytic efficiency in degrading bromophenol blue (BB) and methyl orange (MO) under both the visible-light and ultraviolet-light. It was shown that the weight percentage of SubPc-Br had a remarkable impact on the photocatalytic activities of the substrates and the 4 wt% SubPc-Br/Ag 3 PO 4 composite displayed the most superior photocatalytic efficiency. The improved photocatalytic performance of SubPc-Br/Ag 3 PO 4 photocatalysts could be mainly attributed to the sensitization, which broadened the absorption region and then improved the separation of photogenerated electron-hole pairs of Ag 3 PO 4. Moreover, photo-induced electrons transfer between SubPc-Br and Ag 3 PO 4 particles also decreased the possibility of Ag+ reduction, generating an enhanced cycling stability of SubPc-Br/Ag 3 PO 4 photocatalysts. [ABSTRACT FROM AUTHOR]

The Co@BN core–shell structure boosts dye-sensitized photocatalysis under shell by confined effect and improvement of the tandem electron transfer. • High EY-sensitized photocatalytic hydrogen evolution activity was achieved. • Enhanced adsorption of EY and Co/BN Schottky junction promotes the electron transfer. • The confined space was a nanoreactor boosting the reduction of H+ to H 2 under shell. • The magnetic recyclability makes Co@BN favorable for its practical application. The Co@BN core–shell nanostructure of Co core and boron nitride (BN) shell was prepared through a facile one-step thermal treatment. The as-prepared Co@BN nanocomposites exhibited excellent dye-sensitized photocatalytic hydrogen evolution activity (13.78 mmol h−1 g−1) with visible light and the apparent quantum yield was 1.15%. The enhanced adsorption of EY on the BN shell and the Co/BN Schottky junction facilitate the tandem transfer of photo-generated carriers to the Co surface. Moreover, the core–shell interface serves as a nanoreactor boosting the reduction of H+ to H 2 on the Co surface. Additionally, the magnetic recyclability makes Co@BN favorable for its practical application. This work extends the application of the "photocatalysis under shell" and has potential in dye-sensitized solar cell. [ABSTRACT FROM AUTHOR]

[Display omitted] • A multi-scale Ga 2 O 3 @rGO is synthesized by hydrothermal and freeze-drying strategies. • Ga 2 O 3 @rGO exhibited outstanding rate capability and long-life cyclic property. • rGO can provide a porous space to alleviate the Ga 2 O 3 change of Li anode. Ga 2 O 3 has been used as an anode for lithium batteries due to its high theoretical capacity. However, limited electronic conductivity and severe volume expansion limit its application. Herein, to circumvent these issues, we proposed to design multiscale interface of Ga 2 O 3 @rGO. It was synthesized to achieve superior multiplicative performance (218 mAh g−1 at 5.0 A g−1) and cycling performance (428.7 mAh g−1 after 100 cycles at 100 mAh g−1). These findings suggest that the nanoscale morphology of Ga 2 O 3 and nanographene work together to promote electron transfer, ultimately enhancing the cycling stability of the composites. [ABSTRACT FROM AUTHOR]

[Display omitted] • SubPc-3/Ag 3 PO 4 direct S -scheme supramolecular semiconductors were successfully fabricated. • Photocatalytic performance of SubPc-3/Ag 3 PO 4 for organic pollutants improved obviously. • Experimental and theoretical demonstrated the electron transfer mechanism between SubPc-3 and Ag 3 PO 4. • Photodegradation pathways were proposed based on DFT and experimental results. This study demonstrates the successful construction of a hybrid van der Waals heterostructure (vdWH) consisting of 3D supramolecular networks and 2D semiconductor Ag 3 PO 4 , using hydrogen-bonded 3D networks H 12 SubPcB-OPh 2 OH self-assembled onto Ag 3 PO 4. The resulting organic/inorganic vdWH exhibits significantly enhanced photocatalytic degradation efficiency for oxytetracycline (OTC) and tetracycline (TC) under visible light irradiation, with apparent rate constants 1.8 and 1.5 times higher than those of pristine Ag 3 PO 4 , respectively. Moreover, after five photocatalytic cycles, the photocatalytic activity of vdWH was still much higher than that of pristine Ag 3 PO 4. Molecular dynamics simulations indicate that the SubPc-3 supramolecular assembly is more prone to forming a 3D hydrogen bonding network rather than a 1D columnar stacking. In-situ irradiated X-ray photoelectron spectroscopy analyses and theoretical calculations confirm that the charge transfers between H 12 SubPcB-OPh 2 OH and Ag 3 PO 4 are consistent with the S-scheme mechanism. This work provides a promising strategy for designing and fabricating efficient and stable supramolecular self-assembled semiconductor-based photocatalysts. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs), featuring semiconductor-like behavior, are promising for the photocatalytic reduction of CO 2. While their practical application is hindered by the disadvantages of low charge migration efficiency and fast electron-hole pair complexation. In this paper, a simple solvothermal method was used to load NH 2 -UiO-66 onto the surface of MIL-101(Cr) to form a nano type II heterojunction double MOFs composite of NH 2 -UiO-66 @MIL-101. The results show that the heterostructure of NH 2 -UiO-66 @MIL-101 promotes the separation of photogenerated electron-hole pairs and accelerates the interfacial photogenerated electron transfer under light, and the NH 2 -UiO-66 @MIL-101 type II heterojunction exhibits higher activity for photocatalytic reduction of CO 2 compared with pure MIL-101(Cr) and NH 2 -UiO-66. In addition, the possible photocatalytic mechanism was further elucidated to demonstrate the increased photocatalytic activity of NH 2 -UiO-66 @MIL-101. This study provides effective insights for designing efficient MOFs photocatalysts for CO 2 reduction to enhance the photocatalytic activity for environmental protection and governance. [Display omitted] [ABSTRACT FROM AUTHOR]

Microbial electrosynthesis is a biocathode-driven device for chemicals production from carbon dioxide reduction and has been a promising carbon-consuming technology to alleviate the greenhouse effect and acquire the renewable energy. However, previous studies primarily focused on the effect of the operating parameters on the biocathode with an indirect electron transfer (IDET) pathway instead of a direct electron transfer (DET) pathway for CO 2 reduction. In this work, we aim to study the effect of the operating parameters, including temperature, inorganic carbon source, and initial pH value, on the biocathode with a DET pathway for CO 2 reduction to CH 4. The CH 4 -producing biocathodes showed the respective optimum performance at the condition of 35 °C temperature, 4 g L−1 bicarbonate concentration, and pH 7.5 catholyte. This work provides an important guidance for the operation and development of microbial electrosynthesis for CO 2 reduction to chemicals. • Effects of temperature, inorganic carbon source, and pH value were studied. • 35 °C, 4 g L−1 bicarbonate, and pH 7.5 were the optimum operating parameters. • The Faradaic efficiencies for CH 4 production at all conditions exceeded 90%. [ABSTRACT FROM AUTHOR]

[Display omitted] • S-scheme hydrogen-bonded SubPc-2/Ag 3 PO 4 heterojunction was successfully fabricated. • SubPc-2/Ag 3 PO 4 exhibits efficient and stable photocatalytic degradation of PPCPs. • Theoretical and experimental results prove the S-scheme electron transport mechanism. • Photodegradation pathways were proposed based on DFT and HPLC-MS results. Controllable fine-tuning of heterojunction interfaces at the atomic level represents a promising strategy for enhancing semiconductor photocatalytic performance. Herien, we propose a strategy to introduce hydrogen-bonded electron channels at the heterojunction interface to achieve rapid interfacial electron transfer. This S-scheme hydrogen-bonded supramolecular self-assembled H 12 SubPcB-OPhCH 2 COOH/Ag 3 PO 4 semiconductor heterojunction exhibits efficient and stable photocatalytic degradation of a wide range of pharmaceuticals and personal care products. Experimental results and theoretical simulations demonstrate that the interface O-H⋅⋅⋅O hydrogen bond at the heterojunction generates an internal electric field, which provides the driving force for accelerated S-scheme charge transfer and enhanced redox properties. Furthermore, the combination of TDDFT calculations and synchronous illumination XPS has revealed that hydrogen bonding acts as a suction electron pump in the excited state, transferring electrons from Ag 3 PO 4 to SubPc-2. These findings suggest that hydrogen-bonded supramolecular semiconductor can be used to develop high-performance photocatalytic materials for environmental remediation. [ABSTRACT FROM AUTHOR]

• PCCN v were synthesized with (NH 4) 3 PO 4 and Agar by one-step process. • Electron-localized heptazine units was delocalized by CP in PCCN v. • In-plane CP and interlayers' C N interaction boosted carriers' separation. • PCCN v exhibited superior photodegradation efficiency for alkanes. • Catalytic mechanism, reaction path and toxicities were investigated. The electron localized heptazine units make it difficult to separate photoinduced electeron-hole pairs for graphitic carbon nitride (g-C 3 N 4), which limits the application prospect of graphitic-like carbon nitride. Changing inherent N-(C) 3 bridging mode of in-plane heptazine units and built more electron channel could be a reasonable strategy. Herein, "carbon patches" were introduced to stitch heptazine units, high speed electron transfer path were thus constructed due to delocalized p orbital electron in "carbon patches" as a result. Simultaneously, interlayers' high speed electron transfer channel was also constructed by distorted molecular layer because of presence of large electronegative interstitial phosphorus atoms. Such photoinduced electron-holes' spatial separation in-plane and interlayers were built concurrently and confirmed by XANES and DFT calculation for the first time. The resulted PCCN v series photocatalysts exhibited superior photon absorption capability, excellent charge carriers' separation kinetics, good O 2 molecule adsorption as well as activation capability, the resulted abundant reactive radicals contributed to petroleum hydrocarbons photocatalytic degradation significantly. This work shed light on efficient separation of photoinduced excition for carbon nitride in photocatalysis, simultaneously presented a promising candidate non-metal photocatalytic environmental material for marine oil spill remediation. [ABSTRACT FROM AUTHOR]

• "Electron Bridge" effect of surface oxygen vacancies (SOVs) in Pd/BMO-SOVs was firstly proposed. • "Electron Bridge" effect of SOVs can transfer photogenerated electrons from Bi 2 MoO 6-x to Pd. • SOVs promote photoinduced carriers' separation and utilization efficiency of Pd active sites. • Pd/BMO-SOVs exhibited superior photocatalytic activity for blue LED driven selective oxidation. The recombination of photogenerated carriers seriously restricts their utilization efficiency in photocatalysis. Herein, surface oxygen vacancies (SOVs) were constructed in Pd-Bi 2 MoO 6 interface to bridge ultra-low loading Pd cluster and Bi 2 MoO 6 semiconductor (Pd/BMO-SOVs). It was found SOVs in Pd/Bi 2 MoO 6-x serve as "Electron Bridge" to bridge ultra-low loading Pd cluster and Bi 2 MoO 6-x , thus tremendously enhance utilization efficiency of photoexcited carriers and ultra-low loading Pd active sites for blue LED driven selective oxidation reaction. The Pd(0.05)/Bi 2 MoO 6 -SOVs exhibited 57.8 % conversion for selection oxidation of benzyl which are 6.5, 3.3 and 2.1 times higher than pristine Bi 2 MoO 6 , Bi 2 MoO 6-x and Pd(0.05)/Bi 2 MoO 6. Combined with theoretical calculations, SOVs was proposed as "Electron Bridge" to transfer photogenerated electrons from Bi 2 MoO 6-x to ultra-low loading Pd clusters, thus greatly boosting separation and utilization efficiency of photogenerated electron-hole pairs. [ABSTRACT FROM AUTHOR]