Tandem Fields Facilitating Directional Carrier Migration in Van der Waals Heterojunction for Efficient Overall Piezo-Synthesis of H2O2.

Piezo-synthesis of H2O2 utilizing sustainable mechanical energy as well as earth-abundant water and oxygen is a green, cost-effective, and promising approach. However, achieving simultaneous two-electron water oxidation reaction (2e- WOR) and two-electron oxygen reduction reaction (2e- ORR) faces huge challenges due to insufficient synergistic active sites and slow/messy carrier transfer. Herein, a novel 2D/2D van der Waals heterojunction consisting of BiOIO3 and carbon nitride (BIO/CN) is elaborately designed for highly efficient overall H2O2 piezo-synthesis. Theoretical/experimental results reveal that a Z-scheme electron transfer is formed and facilitated by the tandem interfacial electric field and the bulk piezo-polarization field. On this basis, the carriers are efficiently separated while the oxidation/reduction capacity is preserved, thus providing the strong driving force for the 2e- WOR and 2e- ORR on BIO and CN, respectively. Furthermore, the kinetic and thermodynamic processes of WOR and ORR for H2O2 synthesis improve remarkably. Therefore, BIO/CN exhibits an excellent H2O2 yield of 259.8 µM within 30 min in pure water and air atmosphere (without any sacrificial agents and aeration). This study provides a new idea on strategically controlling electron transfer toward high-efficiency H2O2 piezo-synthesis and expands the avenue for developing effective environmental purification materials.

In situ single iron atom doping on Bi2WO6 monolayers triggers efficient photo-fenton reaction.

Developing an efficient photocatalytic system for hydrogen peroxide (H2O2) activation in Fenton-like processes holds significant promise for advancing water purification technologies. However, challenges such as high carrier recombination rates, limited active sites, and suboptimal H2O2 activation efficiency impede optimal performance. Here we show that single-iron-atom dispersed Bi2WO6 monolayers (SIAD-BWOM), designed through a facile hydrothermal approach, can offer abundant active sites for H2O2 activation. The SIAD-BWOM catalyst demonstrates superior photo-Fenton degradation capabilities, particularly for the persistent pesticide dinotefuran (DNF), showcasing its potential in addressing recalcitrant organic pollutants. We reveal that the incorporation of iron atoms in place of tungsten within the electron-rich [WO4]2- layers significantly facilitates electron transfer processes and boosts the Fe(II)/Fe(III) cycle efficiency. Complementary experimental investigations and theoretical analyses further elucidate how the atomically dispersed iron induces lattice strain in the Bi2WO6 monolayer, thereby modulating the d-band center of iron to improve H2O2 adsorption and activation. Our research provides a practical framework for developing advanced photo-Fenton catalysts, which can be used to treat emerging and refractory organic pollutants more effectively.

Triggering Dual Two-electron Pathway for H2 O2 Generation by Multiple [Bi-O]n Interlayers in Ultrathin Bi12 O17 Cl2 towards Efficient Piezo-self-Fenton Catalysis.

Piezo-self-Fenton system (PESF) has been emerging as a promising water treatment technology but suffering from unsatisfied H2 O2 production efficiency. Herein, we rationally design a Bi12 O17 Cl2 piezo-catalyst with multiple [Bi-O]n interlayers towards highly efficient H2 O2 production. The introduction of [Bi3 O4.25 ] layers initiates dual two-electron pathway for H2 O2 generation by altering the interlayer properties. It is found that the additional [Bi3 O4.25 ] layers not only enhance the polarization electric field but also serve as active sites for triggering dual pathways of two-electron O2 reduction and H2 O oxidation reaction for H2 O2 production. Therefore, the Bi12 O17 Cl2 exhibits an ultrahigh rate of H2 O2 generation (7.76 mM h-1 g-1 ) in pure water. Based on the adequate H2 O2 yield, a PESF was constructed for acetaminophen (ACE) degradation with an apparent rate constant of 0.023 min-1 . This work not only presents a potential strategy of tuning the activity of bismuth based piezo-catalysts but also provides a good example on the construction of highly efficient PESF for environmental remediation by using natural mechanical energy.

Environmental energy enhanced solar-driven evaporator with spontaneous internal convection for highly efficient water purification.

Solar-driven interfacial evaporation for water purification is limited by the structural design of the solar evaporator and, more importantly, by the inability to separate the water from volatile organic compounds (VOCs) present in the water source. Here, we report a three-dimensional (3D) bifunctional evaporator based on N-doped carbon (CoNC/CF), which enables the separation of fresh water from VOCs by activating PMS during the evaporation process with a VOC removal rate of 99%. There is abundant van der Waals interaction between peroxymonosulfate (PMS) and CoNC/CF, and pyrrolic N is confirmed as the active site for binding phenol, thus contributing to the separation of phenol from water. With the advantageous features of sufficient light absorption, adequate water storage capacity, and spontaneous internal convection flow on its top surface, the 3D evaporator achieves a high evaporation rate under one sun (1 kW/m2) at 3.16 kg/m2/h. More notably, through careful structural design, additional energy from the environment and water can be utilized. With such a high evaporation rate and satisfactory purification performance, this work is expected to provide a promising platform for wastewater treatment.

Multi-heteroatom-doping promotes molecular oxygen activation on polymeric carbon nitride for simultaneous generation of H2O2 and degradation of oxcarbazepine.

Simultaneously realizing the efficient generation of H2O2 and degradation of pollutants is of great significance for environmental remediation. However, most polymeric semiconductors only show moderate performance in molecular oxygen (O2) activation due to the sluggish electron-hole pair dissociation and charge transfer dynamics. Herein, we develop a simple thermal shrinkage strategy to construct multi-heteroatom-doped polymeric carbon nitride (K, P, O-CNx). The resultant K, P, O-CNx not only improves the separation efficiency of charge carriers, but also improves the adsorption/activation capacity of O2. K, P, O-CNx significantly increases the production of H2O2 and the degradation activity of oxcarbazepine (OXC) under visible light. K, P, O-CN5 shows a high H2O2 production rate (1858 µM h-1 g-1) in water under visible light, far surpassing that of pure PCN. The apparent rate constant for OXC degradation by K, P, O-CN5 increases to 0.0491 min-1, which is 8.47 times that of PCN. Density functional theory (DFT) calculations show that the adsorption energy of O2 near phosphorus atoms in K, P, O-CNx is the highest. This work provides a new idea for the efficient degradation of pollutants and generation of H2O2 at the same time.

n→π* Electron Transitions and Directional Charge Migration Synergistically Promoting O2 Activation and Holes Utilization on Carbon Nitride for Efficiently Photocatalytic Degradation of Organic Contaminants.

Stimulating electron transitions and promoting exciton dissociation are crucial for improving the photocatalytic performance of polymeric carbon nitride (CN) yet still challenging. Herein, a novel CN with C dopant and asymmetric structure (CC-UCN2 ) is ingeniously synthesized. The obtained CC-UCN2 not only reinforces the intrinsic π→π* electron transitions, but also successfully awakens additional n→π* electron transitions. Besides, charge centers dislocation caused by symmetry breaking induces a spontaneous polarized electric field, effectively breaking the constraints of Coulomb electrostatic interaction between electrons and holes and driving their directional migration. Along with the spatial separation of reduction and oxidation sites, CC-UCN2 shows exceptional O2 activation and holes oxidation efficiency, thus exhibits a high degradation rate constant (0.201 min-1 ) and mineralization rate (80.1%) for bisphenol A (BPA)(far outperforming pristine and other modified CNs). This work proposes a novel perspective for developing high-efficiency photocatalysts and comprehending the underlying mechanism of O2 activation and holes oxidation for pollutant degradation.

Highly Efficient FeIII -initiated Self-cycled Fenton System in Piezo-catalytic Process for Organic Pollutants Degradation.

Piezo-catalytic self-Fenton (PSF) system has been emerging as a promising technique for wastewater treatment, while the competing O2 reductive hydrogen peroxide (H2 O2 ) production and FeIII reduction seriously limited the reaction kinetics. Here, we develop a two-electron water oxidative H2 O2 production (WOR-H2 O2 ) coupled with FeIII reduction over a FeIII /BiOIO3 piezo-catalyst for highly efficient PSF. It is found that the presence of FeIII can simultaneously initiate the WOR-H2 O2 and reduction of FeIII to FeII , thereby enabling a rapid reaction kinetics towards subsequent Fenton reaction of H2 O2 /FeII . The FeIII initiating PSF system offers exceptional self-recyclable degradation of pollutants with a degradation rate constant for sulfamethoxazole (SMZ) over 3.5 times as that of the classic FeII -PSF system. This study offers a new perspective for constructing efficient PSF systems and shatters the preconceived notion of FeIII in the Fenton reaction.

Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D-π-A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation.

Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor-π-acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN-5B2T D-π-A OCPs). The resultant PCN-5B2T D-π-A OCPs extended the π-conjugate structure and introduced abundant micro-, meso-, and macro-pores, which greatly promoted intramolecular charge transfer, light absorption, and mass transport and thus significantly enhanced the photocatalytic performance in pollutant degradation. The apparent rate constant of the optimized PCN-5B2T D-π-A OCP for 2-mercaptobenzothiazole (2-MBT) removal is ∼10 times higher than that of the pure PCN. Density functional theory calculations reveal that the photogenerated electrons in PCN-5B2T D-π-A OCPs are much easier to transfer from the donor tertiary amine group to the benzene π-bridge and then to the acceptor imine group, while 2-MBT is more easily adsorbed on π-bridge and reacts with the photogenerated holes. A Fukui function calculation on the intermediates of 2-MBT predicted the real-time changing of actual reaction sites during the entire degradation process. Additionally, computational fluid dynamics further verified the rapid mass transport in holey PCN-5B2T D-π-A OCPs. These results demonstrate a novel concept toward highly efficient photocatalysis for environmental remediation by improving both intramolecular charge transfer and mass transport.

Highly efficient removal of organic contaminant with wide concentration range by a novel self-cleaning hydrogel: Mechanism, degradation pathway and DFT calculation.

A novel carbon nitride based self-cleaning hydrogel photocatalyst (KI-PCN gel, potassium and iodine co-doped carbon nitride confined in alginate) has been successfully constructed by a facile method. Fabricated photocatalyst showed enhanced synergistic adsorption-photocatalytic degradation property on a high concentration of methylene blue (HMB) because of enhanced carrier separation efficiency and improved light adsorption capacity of KI-PCN. As expected, the KI-PCN gel showed the highest apparent rate constant value (Kapp =0.0310 min-1), which was about 38.8 and 5.8 times as that of blank hydrogel (Kapp=0.0008 min-1) and PCN gel (Kapp=0.0053 min-1), respectively. Meanwhile, KI-PCN gel can continuously adsorb low concentration of MB (LMB), and the MB-adsorbed KI-PCN gel can self-clean under light irradiation. The bench-scale experiments simulating real river showed that KI-PCN gel can effectively and continuously remove LMB (0.1-20 ppm), indicating the possibility for the removal of contaminants in natural rivers. Furthermore, the possible degradation pathways were proposed by combining the density functional calculations (DFT) and intermediates identified by liquid chromatography-mass spectrometry (LC-MS). This work proposed a new perspective to acquire a novel self-cleaning and easily recyclable photocatalyst for treatment of wide concentration range organic wastewater as well as remediation of natural waterbody.

Regulating directional transfer of electrons on polymeric g-C3N5 for highly efficient photocatalytic H2O2 production.

Graphite carbon nitride (g-C3N5) has been widely used in various photocatalytic reactions due to its higher thermodynamic stability and better electronic properties compared to g-C3N4. However, it is still challenging to endow g-C3N5 with high performance on photocatalytic hydrogen peroxide (H2O2) production. Herein, potassium and iodine are co-doped into g-C3N5 (g-C3N5-K, I) for photocatalytic production of H2O2 with high efficiency. As expected, the photocatalytic H2O2 production rate over the g-C3N5-K, I (2933.4 µM h-1) reaches to 84.22 times as that of g-C3N5. The excellent photocatalytic H2O2 production activity is mainly ascribed to the co-doping of K and I, which significantly improves the capacity of oxygen (O2) adsorption, selectivity of two-electrons oxygen reduction reaction (2e- ORR) and separation efficiency of charge carriers. The density functional theory (DFT) calculations reveal that O2 molecules are more conducive to being adsorbed on g-C3N5-K, I. Besides, the result of excited states further indicates that photo-generated electrons can be directionally driven to the adsorbed O2 molecules, which are effectively activated to form H2O2. The findings will contribute to new insights in designing and synthesizing g-C3N5 based photocatalysts for the H2O2 production.

Understanding the mechanism of interfacial interaction enhancing photodegradation rate of pollutants at molecular level: Intermolecular π-π interactions favor electrons delivery.

Uncovering the interaction between photocatalyst and reaction substrate as well as subsequent electron transfer process is critical to achieve high-performance photodegradation of pollutants. Herein, based on the reduced density gradient (RDG) method, we visualize the simulation of the π-π interactions between photocatalyst (g-C3N4) and pollutant molecule (flumequine, FLU). Results revealed that π-π interactions between g-C3N4 and FLU favor electrons delivery, resulting in enhanced charge separation efficiency and direct hole oxidation of FLU. Moreover, it is found that the charge transfer rate is determined by the valence band (VB) level of g-C3N4 and EHOMO of FLU, of which the deeper VB position of g-C3N4 favors faster charge transfer, leading to further enhancement in photocatalytic degradation rate of FLU. Additionally, the possible degradation pathways of FLU were proposed by theoretical calculation and the determined intermediates. Our work afforded a new insight into pollutants degradation and the rational design of highly efficient photocatalysts.

Iodide-Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High-Performance Quasi-Homogeneous Photocatalytic H2 O2 Production.

Polymeric carbon nitride (PCN) as a class of two-electron oxygen reduction reaction (2 e- ORR) photocatalyst has attracted much attention for H2 O2 production. However, the low activity and inferior selectivity of 2 e- ORR greatly restrict the H2 O2 production efficiency. Herein, we develop a new strategy to synthesize hydrophilic, fragmented PCN photocatalyst by the terminating polymerization (TP-PCN) effect of iodide ions. The obtained TP-PCN with abundant edge active sites (AEASs), which can form quasi-homogeneous photocatalytic system, exhibits superior H2 O2 generation rate (3265.4 µM h-1 ), far surpassing PCN and other PCN-based photocatalysts. DFT calculations further indicate that TP-PCN is more favorable for electron transiting from ß spin-orbital to the π* orbitals of O2 , which optimizes O2 activation and reduces the energy barrier of H2 O2 formation. This work provides a new concept for designing functional photocatalysts and understanding the mechanism of O2 activation in ORR for H2 O2 production.

Confinement of ultrasmall CoFe2O4 nanoparticles in hierarchical ZnIn2S4 microspheres with enhanced interfacial charge separation for photocatalytic H2 evolution.

The charge carriers' separation efficiency, light absorption capacity and microstructure of photocatalysts are important factors affecting the photocatalytic performance. Herein, we prepared the hierarchical ZnIn2S4 (ZIS) microspheres-confined CoFe2O4 nanoparticles (CFO NPs) p-n junction (CFO/ZIS) with enhanced charge carriers' separation and extensive visible light response. Surprisingly, the 1% CFO/ZIS exhibits the optimal photocatalytic H2 evolution (PHE) activity, which is about over 3.7 times higher than pure ZIS. Furthermore, the apparent quantum yield (AQY) of the1% CFO/ZIS reaches 5.0% at 420 nm. In addition, the effects of various sacrificial reagent on the PHE were investigated in depth. And the formed photocatalytic reaction path of p-n junction effectively prevents the photocorrosion of ZIS. Hence, the photocatalytic activity and crystalline structure of 1% CFO/ZIS have no obvious change after five photocatalytic cycles, which shows that the photocatalyst possesses excellent chemical stability. Moreover, the as-prepared p-n junction shows outstanding photocatalytic performance for the degradation of 2-mercaptobenzothiazole (MBT). According to a series of experiments and characterizations, a possible photocatalytic mechanism for the CFO/ZIS p-n junction was proposed.

Enhanced light utilization efficiency and fast charge transfer for excellent CO2 photoreduction activity by constructing defect structures in carbon nitride.

Defect structure is one of the crucial factors for enhancing the catalytic activities of photocatalysts. However, rational design and construction of defect structures in catalysts to meet the aim of enhancing photocatalytic performance in a simple and cost-effective way is still a challenge. In this contribution, we report a strategy to construct defect structures in graphitic carbon nitride (g-CN) by simple copolymerizing of urea with polyethyleneimine (PEI). Among the prepared catalysts, u-0.05PEI presents the best photocatalytic activity for CO2 reduction, with CO and CH4 yields of 32.86 and 1.68 µmol g-1 in 4 h, which is about 3.2 and 2.5 times higher than that of g-CN, respectively. Characterization results show that both C and N defects are formed in the newly prepared catalysts. The C defects on the surface of u-xPEI result in the formation of more amino groups which are beneficial for CO2 adsorption. Meanwhile, the N defects inside the samples lead to the generation of midgap states between the valance band and conduction band of u-xPEI. The midgap states greatly enlarge the light absorption extent, and enable the use of light with energy lower than the intrinsic absorption of g-CN in the photoreduction of CO2. As confirmed by DRS, EPR, PL analysis, the excellent catalytic activity of u-0.05PEI is mainly attributed to the remarkably improved light utilization efficiency and fast charge transfer. Moreover, the reaction is performed in water without any additive or organic solvent, which makes it environmentally friendly.

Precursor-reforming strategy induced g-C3N4 microtubes with spatial anisotropic charge separation established by conquering hydrogen bond for enhanced photocatalytic H2-production performance.

Precursor-reforming strategy induced graphitic carbon nitride (g-C3N4) with different morphologies for enhanced photocatalytic hydrogen (H2) evolution activity is highly desirable. Herein, g-C3N4 microtubes (mg-C3N4) with adjustable closure degree of microtube orifice and spatial anisotropic charge separation are established by conquering hydrogen bond during thermally exfoliate precursor. Compared to the bulk g-C3N4 (bg-C3N4) and ultrathin g-C3N4 (ug-C3N4), the tubular structure endows mg-C3N4 with spatial anisotropic charge separation that accelerates transfer of charge carriers. As expected, the photocatalytic H2 evolution (PHE) activity of mg-C3N4 has been obviously enhanced. Particularly, the mg-C3N4-24 shows the best PHE activity (957.9 µmol h-1 g-1), which is over 18.72 and 3.77 times higher than the bg-C3N4 and ug-C3N4, respectively. In addition, selective photo-deposition experiment results reveal a charge carriers migration behavior that photoproduction electrons migrate to the outer shell and holes prefer to move onto the inner shell of mg-C3N4, thus achieving efficient spatial anisotropic charge separation. We firmly believe that the work presents significant advancement for the design of other materials by precursor-reforming strategy.

Yeast-derived carbon sphere as a bridge of charge carriers towards to enhanced photocatalytic activity of 2D/2D Cu2WS4/g-C3N4 heterojunction.

It is very challenging to fabricate novel, high-efficiency photocatalysts with an enhanced visible light absorption capacity, high charge carrier separation efficiency, and large specific surface area. For this purpose, a yeast-derived carbon (YC) sphere was added as a charge carrier bridge to the 2D-2D Cu2WS4/g-C3N4 heterojunction through a facile hydrothermal method. The YC sphere, as a bridge for electrons, is not only advantageous in inhibiting rapid recombination by electrons, but also remarkably enhances the visible light absorption capacity. Moreover, the YC sphere can also increase the specific surface area and surface roughness, which can enhance the adsorption of pollutant molecules and provide abundant active sites for photocatalytic reactions. The g-C3N4/YC/Cu2WS4 heterojunction showed the best photocatalytic activity for reducing hexavalent chromium Cr(VI) and decomposing tetracycline (TC) under visible light. Meanwhile, the acute toxicity of Daphnia magna (D. magna) gradually decreases with the conversion of Cr(VI) to Cr(III) in solution. In addition, the possible intermediate products and the photocatalytic reaction mechanism are revealed in depth. This work provides a general example for improving the photocatalytic activity of 2D-2D based heterojunctions by introducing a biomass material.

A visible-light-driven Z-scheme CdS/Bi12GeO20 heterostructure with enhanced photocatalytic degradation of various organics and the reduction of aqueous Cr(VI).

A series of Z-scheme CdS/Bi12GeO20 heterostructures were successfully obtained by a simple hydrothermal method. The Z-scheme CdS/Bi12GeO20 heterostructures show outstanding photocatalytic performance for degrading the various organic pollutants of the waste water, and for the reduction of aqueous Cr(VI) under visible light. For degradation of 2-Mercaptobenzothiazole (MBT), the Z-scheme 30CdS/Bi12GeO20 heterostructure exhibits the superior rate constant, which is about 22.67 and 4.6 times higher than that of the pure Bi12GeO20 and CdS, respectively. Meanwhile, as we expected, the Z-scheme 30CdS/Bi12GeO20 heterostructure also displays the enhanced photocatalytic performance for degradation of Levofloxacin (LEV), Ciprofloxacin (CIP), Tetracycline (TC) and reduction of aqueous Cr(VI). The enhancement of photocatalytic performance is attributed to the high redox capacity and the strong interfacial interaction between CdS and Bi12GeO20, which can effectively improve the separation of photo-induced electron-hole pairs. Additionally, the photocatalytic mechanism over the Z-scheme CdS/Bi12GeO20 heterostructure is provided. The research work may provide a promising approach to fabricate other Z-scheme heterostructures with efficient photocatalytic performance.

Visible-light-driven Ag/Bi3O4Cl nanocomposite photocatalyst with enhanced photocatalytic activity for degradation of tetracycline.

In this study, a novel Ag/Bi3O4Cl photocatalyst has been synthesized by a facile photodeposition process. Its photocatalytic performance was evaluated from the degradation of tetracycline (TC) under visible light irradiation (λ > 420 nm). The 1.0 wt% Ag/Bi3O4Cl photocatalyst could significantly enhance the degradation of TC compared with pure Bi3O4Cl, with the degradation level reaching 94.2% in 120 minutes. The enhancement of photocatalytic activity could be attributed to the synergetic effect of the photogenerated electrons (e-) of Bi3O4Cl and the surface plasmon resonance (SPR) caused by Ag nanoparticles, which could improve the absorption capacity of visible light and facilitate the separation of photogenerated electron-hole pairs. In addition, electron spin resonance (ESR) analysis and trapping experiments demonstrated that the superoxide radicals (˙O2-), hydroxyl radicals (˙OH) and holes (h+) played crucial roles in the photocatalytic process of TC degradation. The present work provides a promising approach for the development of highly efficient photocatalysts to address current environmental pollution, energy issues and other related areas.

Composition dependent magnetic and ferroelectric properties of hydrothermally synthesized GdFe1-xCrxO3 (0.1 ≤ x ≤ 0.9) perovskites.

The hydrothermal synthesis and magnetic, dielectric and ferroelectric property characterization of ABO3-perovskite GdFe1-xCrxO3 (0 < x < 1) are reported. The mineralizer KOH plays a critical role in the perovskite structure of the sample. The Fe/Cr ratio of the final crystal is controlled by the alkalinity in the initial reaction mixtures. The lattice parameters and magnetic ordering transition temperature have a close relationship with the Fe/Cr ratio. The temperature dependent magnetic properties of GdFe1-xCrxO3 (0 < x < 1) samples show a close relationship with substituent ratios of Cr3+. The occurrence of ferromagnetic behavior in all of the as-prepared samples comes from the coexistence of canted-antiferromagnetism due to the double exchange effect of Fe-O-Fe and Cr-O-Cr and ferromagnetism due to superexchange interaction of Fe-O-Cr. A large spontaneous polarization was observed in GdFe1-xCrxO3 at room temperature, exhibiting a clear ferroelectric hysteresis loop, which indicates the ferroelectric behavior in this system. This work not only provides an effective route to the controllable synthesis of B-site doped REFe1-xCrxO3 perovskite structure materials, but also presents a comprehensive study of the tunable effect of ionic doping on ferroelectric properties.