Low H2O2 consumption Fenton-like catalysts for pollutant cleavage based on the construction of a dual reaction center.

High energy consumption has seriously hindered the development of Fenton-like reactions for the removal of refractory organic pollutants in water. To solve this problem, we designed a novel Fenton-like catalyst (Cu-PAN3) by coprecipitation and carbon thermal reduction. The catalyst exhibits excellent Fenton-like catalytic activity and stability for the degradation of various pollutants with low H2O2 consumption. The experimental results indicate that the dual reaction centers (DRCs) are composed of Cu-N-C and Cu-O-C bridges between copper and graphene-like carbon, which form electron-poor/rich centers on the catalyst surface. H2O2 is mainly reduced at electron-rich Cu centers to free radicals for pollutant degradation. Meanwhile, pollutants can be oxidized by donating electrons to the electron-poor C centers of the catalyst, which inhibits the ineffective decomposition of H2O2 at the electron-poor centers. This therefore significantly reduces the consumption of H2O2 and reduces energy consumption.

Simultaneous Emerging Contaminant Removal and H2O2 Generation Through Electron Transfer Carrier Effect of Bi─O─Ce Bond Bridge Without External Energy Consumption.

Conventional advanced oxidation processes (AOPs) require significant external energy consumption to eliminate emerging contaminants (ECs) with stable structures. Herein, a catalyst consisting of nanocube BiCeO particles (BCO-NCs) prepared by an impregnation-hydrothermal process is reported for the first time, which is used for removing ECs without light/electricity or any other external energy input in water and simultaneous in situ generation of H2O2. A series of characterizations and experiments reveal that dual reaction centers (DRC) which are similar to the valence band/conducting band structure are formed on the surface of BCO-NCs. Under natural conditions without any external energy consumption, the BCO-NCs self-purification system can remove more than 80% of ECs within 30 min, and complete removal of ECs within 30 min in the presence of abundant electron acceptors, the corresponding second-order kinetic constant is increased to 3.62 times. It is found that O2 can capture electrons from ECs through the Bi─O─Ce bond bridge during the reaction process, leading to the in situ production of H2O2. This work will be a key advance in reducing energy consumption for deep wastewater treatment and generating important chemical raw materials.

Water self-purification via electron donation effect of emerging contaminants arousing oxygen activation over ordered carbon-enhanced CoFe quantum dots.

The release of emerging contaminants (ECs) into aquatic environments poses a significant risk to global water security. Advanced oxidation processes (AOPs), while effective in removing ECs, are often resource and energy-intensive. Here, we introduce a novel catalyst, CoFe quantum dots embedded in graphene nanowires (CoFeQds@GN-Nws), synthesized through anaerobic polymerization. It uniquely features electron-rich and electron-poor micro-regions on its surface, enabling a self-purification mechanism in wastewater. This is achieved by harnessing the internal energy of wastewater, particularly the bonding energy of pollutants and dissolved oxygen (DO). It demonstrates exceptional efficiency in removing ECs at ambient temperature and pressure without the need for external oxidants, achieving a removal rate of nearly 100.0%. The catalyst's structure-activity relationship reveals that CoFe quantum dots facilitate an unbalanced electron distribution, forming these micro-regions. This leads to a continuous electron-donation effect, where pollutants are effectively cleaved or oxidized. Concurrently, DO is activated into superoxide anions (O2•-), synergistically aiding in pollutant removal. This approach reduces resource and energy demands typically associated with AOPs, marking a sustainable advancement in wastewater treatment technologies.

Salinity-mediated water self-purification via bond network distorting of H2O molecules on DRC-surface.

High salinity has plagued wastewater treatment for a long time by hindering pollutant removal, thereby becoming a global challenge for water pollution control that is difficult to overcome even with massive energy consumption. Herein, we propose a novel process for rapid salinity-mediated water self-purification in a dual-reaction-centers (DRC) system with cation-π structures. In this process, local hydrogen bond networks of H2O molecules can be distorted through the mediation of salinity, thereby opening the channels for the preferential contact of pollutants on the DRC interface. As the result, the elimination rate of pollutants increased approximately 32-fold at high salinity (100 mM) without any external energy consumption. Our findings provide a novel technology for high-efficiency and low-consumption water self-purification, which is of great significance in environmental remediation and even fine chemical industry.

Twistedly hydrophobic basis with suitable aromatic metrics in covalent organic networks govern micropollutant decontamination.

The pre-designable structure and unique architectures of covalent organic frameworks (COFs) render them attractive as active and porous medium for water crisis. However, the effect of functional basis with different metrics on the regulation of interfacial behavior in advanced oxidation decontamination remains a significant challenge. In this study, we pre-design and fabricate different molecular interfaces by creating ordered π skeletons, incorporating different pore sizes, and engineering hydrophilic or hydrophobic channels. These synergically break through the adsorption energy barrier and promote inner-surface renewal, achieving a high removal rate for typical antibiotic contaminants (like levofloxacin) by BTT-DATP-COF, compared with BTT-DADP-COF and BTT-DAB-COF. The experimental and theoretical calculations reveal that such functional basis engineering enable the hole-driven levofloxacin oxidation at the interface of BTT fragments to occur, accompanying with electron-mediated oxygen reduction on terphenyl motif to active radicals, endowing it facilitate the balanced extraction of holes and electrons.

Synergetic effects of catalyst-surface dual-electric centers and microbes for efficient removal of ciprofloxacin in water.

Antibiotics and antibiotic resistance genes (ARGs) are still a problem in biological treatment. Herein, we propose a synergetic strategy between microbes and dual-electric centers catalysts (CCN/Cu-Al2O3/ceramsite) for Ciprofloxacin (CIP)-contained (5 mg/L) water treatment in an up-flow biological filter. CIP was cleaved into small molecules by the catalyst, bringing a 57.6% removal and reducing 10.5% ARG. The characterization results verified that a Cu-π electrostatic force occurs on the catalyst surface, forming electron-rich areas around Cu and electron-poor areas at the carbon-doped g-C3N4 (CCN) aromatic ring. Thus, the electrons of adsorbed CIP were delocalized and then captured by the adsorbed extracellular polymeric substance at the electron-rich areas. Therefore, the synergetic process weakened the stress of CIP on bacteria and reduced ARG accumulation. It also enriched more electro-active bacteria on the surface of CCN/Cu-Al2O3/ceramsite, promoting the expression of extracellular electron transfer-related genes and reconstructing the energy metabolism mode. This result provides an opportunity for refractory antibiotic treatment in the biological process.

Resourcelized conversion of poultry feces to ordered carbon with electron poor/rich microregions for water purification induced by peroxymonosulfate.

For the sustainable reutilization of poultry feces (PF) to reduce environmental pollution, we present a novel approach for converting PF into a highly effective catalyst, consisting of trace copper (Cu) and sulfur (S) linked with ordered graphitized carbon (CS/CPF) for wastewater purification. Raman and EPR results verified that the disorderly organic matters in PF are transformed into orderly graphene structures that complexed with Cu to form large numbers of electron-poor/rich microregions on CS/CPF surface. The electrons from electron-rich organic pollutants can be directly captured by dissolved oxygen (DO) to produce abundant reactive oxygen species due to the enhanced electron polarization via the construction of Cu-S-C bond bridge on CS/CPF surface, which greatly enhance the removal efficiency of pollutants. CS/CPF achieves 100% removal for 2,4-dichlorophenoxyacetic acid (2,4-D) in just 10 min after adding trace peroxymonosulfate (PMS), keeping efficient catalytic activity after continuous reactions for 240 h. This strategy offers a practical and sustainable solution for the efficient resource recovery of poultry feces.

Self-purification of actual wastewater via microbial-synergy driving of catalyst-surface microelectronic field: A pilot-scale study.

High energy consumption is impedimental for eliminating refractory organics in wastewater by current technologies. Herein, we develop an efficient self-purification process for actual non-biodegradable dyeing wastewater at pilot scale, using N-doped graphene-like (CN) complexed Cu-Al2O3 supported Al2O3 ceramics (HCLL-S8-M) fixed-bed reactor without additional input. About 36% chemical oxygen demand removal was achieved within 20 min empty bed retention time and maintained stability for almost one year. The HCLL-S8-M structure feature and its interface on microbial community structure, functions, and metabolic pathways were analyzed by density-functional theory calculation, X-ray photoelectron spectroscopy, multiomics analysis of metagenome, macrotranscriptome and macroproteome. On the surface of HCLL-S8-M, a strong microelectronic field (MEF) was formed by the electron-rich/poor area due to Cu-π interaction from the complexation between phenolic hydroxy of CN and Cu species, driving the electrons of the adsorbed dye pollutants to the microorganisms through extracellular polymeric substance and the direct transfer of extracellular electrons, causing their degradation into CO2 and intermediates, which was degraded partly via intracellular metabolism. The lower energy feeding for the microbiome produced less adenosine triphosphate, resulting in little sludge throughout reaction. The MEF from electronic polarization is greatly potential to develop low-energy wastewater treatment technology.

Resourcelized conversion of livestock manure to porous cage microsphere for eliminating emerging contaminants under peroxymonosulfate trigger.

Pollution and resource waste caused by the improper disposal of livestock manure, and the threat from the release of emerging contaminants (ECs), are global challenges. Herein, we address the both problems simultaneously by the resourcelized conversion of chicken manure into porous Co@CM cage microspheres (CCM-CMSs) for ECs degradation through the graphitization process and Co-doping modification step. CCM-CMSs exhibit excellent performance for ECs degradation and actual wastewater purification under peroxymonosulfate (PMS) initiation, and show adaptability to complex water environments. The ultra-high activity can maintain after continuous operation over 2160 cycles. The formation of C-O-Co bond bridge structure on the catalyst surface caused an unbalanced electron distribution, which allows PMS to trigger the sustainable electron donation of ECs and electron gain of dissolved oxygen processes, becoming the key to the excellent performance of CCM-CMSs. This process significantly reduces the resource and energy consumption of the catalyst throughout the life cycle of production and application.

Enhanced purification of kitchen-oil wastewater driven synergistically by surface microelectric fields and microorganisms.

The stable structure and toxic effect of refractory organic pollutants in wastewater lead to the problem of high energy consumption in water treatment technology. Herein, we propose a synergistic purification of refractory wastewater driven by microorganisms and surface microelectric fields (SMEF) over a dual-reaction-center (DRC) catalyst HCLL-S8-M prepared by an in situ growth method of carbon nitride on the Cu-Al2O3 surface. Characterization techniques demonstrate the successful construction of SMEF with strong electrostatic force over HCLL-S8-M based on cation-π interactions between metal copper ions and carbon nitride rings. With the catalyst as the core filler, an innovative fixed bed bioreactor is constructed to purify the actual kitchen-oil wastewater. The removal efficiency of the wastewater even with a very low biodegradability (BOD5/COD = 0.33) can reach 60% after passing through this bioreactor. An innovative reaction mechanism is revealed for the first time that under the condition of a small amount of biodegradable organic matter, the SMEF induces the enrichment of electric active microorganisms (Desulfobulbus and Geobacter) in the wastewater, accelerates the interspecies electron transfer of intertrophic metabolism with the biodegradable bacteria through the extracellular electron transfer mechanism such as cytochrome C and self-secreted electron shuttle. The electrons of the refractory organic pollutants adsorbed on the surface of the catalyst are delocalized by the SMEF, which can be directly utilized by microorganisms through EPS conduction. The SMEF generated by electron polarization can maximize the utilization of pollutants and microorganisms in wastewater and further enhance degradation without adding any external energy, which is of great significance to the development of water self-purification technology.

Water Self-Purification with Zero External Consumption by Livestock Manure Resource Utilization.

Improper disposal of waste biomass and an increasing number of emerging contaminants (ECs) in water environment are universal threats to the global environment. Here, we creatively propose a sustainable strategy for the direct resource transformation of livestock manure (LM) into an innovative catalyst (Fe-CCM) for water self-purification with zero external consumption. ECs can be rapidly degraded in this self-purification system at ambient temperature and atmospheric pressure, without any external oxidants or energy input, accompanied by H2O and dissolved oxygen (DO) activation. The performance of the self-purification system is not affected by various types of salinity in the wastewater, and the corresponding second-order kinetic constant is improved 7 times. The enhanced water self-purification mechanism reveales that intermolecular forces between anions and pollutants reinforce electron exchange between pollutants and metal sites on the catalyst, further inducing the utilization of the intrinsic energy of contaminants, H2O, and DO through the interfacial reaction. This work provides new insights into the rapid removal of ECs in complicated water systems with zero external consumption and is expected to advance the resource utilization of livestock waste.

Graphitized Cu-ß-cyclodextrin polymer driving an efficient dual-reaction-center Fenton-like process by utilizing electrons of pollutants for water purification.

Excessive consumption of energy and resources is a major challenge in wastewater treatment. Here, a novel heterogeneous Fenton-like catalyst consisting of Cu-doped graphene-like catalysts (Cu-GCD NSs) was first synthesized by an enhanced carbothermal reduction of ß-cyclodextrin (ß-CD). The catalyst exhibits excellent Fenton-like catalytic activity for the degradation of various pollutants under neutral conditions, accompanied by low H2O2 consumption. The results of structural characterization and theoretical calculations confirmed that the dual reaction centers (DRCs) were constructed on Cu-GCD NSs surface through C-O-Cu bonds supported on zero-valent copper species, which play a significant role in the high-performance Fenton-like reaction. The pollutants that served as electron donors were decomposed in the electron-poor carbon centers, whereas H2O2 and dissolved oxygen obtained these electrons in the electron-rich Cu centers through C-O-Cu bonds, thereby producing more active species. This study demonstrates that the electrons of pollutants can be efficiently utilized in Fenton-like reactions by DRCs on the catalyst surface, which provides an effective strategy to improve Fenton-like reactivity and reduce H2O2 consumption.

Sustainable micro-activation of dissolved oxygen driving pollutant conversion on Mo-enhanced zinc sulfide surface in natural conditions.

The activation of inert oxygen (O2) often consumes enormous amounts of energy and resources, which is a global challenge in the field of environmental remediation and fuel cells. Organic pollutants are abundant in electrons and are promising alternative electron donors. Herein, we implement sustainable microactivation of dissolved oxygen (DO) by using the electrons and adsorption energy of pollutants by creating a nonequilibrium microsurface on nanoparticle-integrated molybdenum (Mo) lattice-doped zinc sulfide (ZnS) composites (MZS-1). Organic pollutants were quickly removed by DO microactivation in the MZS-1 system under natural conditions without any additional energy or electron donor. The turnover frequency (TOF, per Mo atom basis) is 5 orders of magnitude higher than those of homogeneous systems. Structural and electronic characterization technologies reveal the change in the crystalline phase (Zn-S-Mo) and the activation of π-electrons on six-membered rings of ZnS after Mo doping, which results in the formation of a nonequilibrium microsurface on MZS-1. This is the key for the strong interfacial interaction and directional electron transfer from pollutants to MZS-1 through the delocalized π-π conjugation effect and from MZS-1 to DO via Zn-S-Mo, as demonstrated by electron paramagnetic resonance (EPR) techniques and density functional theory (DFT) calculations. This process achieves the efficient use of pollutants and the low-energy activation of O2 through the construction of a nonequilibrium microsurface, which shows new significance for water treatment.

Preferential Destruction of Micropollutants in Water through a Self-Purification Process with Dissolved Organic Carbon Polar Complexation.

Removing micropollutants in real water is a scientific challenge due to primary dissolved organic carbon (DOC) and high energy consumption of current technologies. Herein, we develop a self-purification process for the preferential destruction of various micropollutants in municipal wastewater, raw drinking water, and ultrapure water with humic acid (HA) driven by the surface microelectronic field of Fe0-FeyCz/Fex-GZIF-8-rGO without any additional input. It was verified that a strongly polar complex consisting of an electron-rich HA/DOC area and an electron-poor micropollutant area was formed between HA/DOC and micropollutants, promoting more electrons of micropollutants in the adsorbed complex to delocalizing to electron-rich Fe species area and be trapped by O2, which resulted in their surface cleavage and hydrolyzation preferentially. The higher micropollutant degradation efficiency observed in real wastewaters was due to the greater complex polarity of DOC. Moreover, the electron transfer process ensured the stability of the surface microelectronic field and continuous water purification. Our findings provide a new insight into low-energy combined-micropollution water treatment.

Peroxymonosulfate as inducer driving interfacial electron donation of pollutants over oxygen-rich carbon-nitrogen graphene-like nanosheets for water treatment.

Herein, a novel metal-free catalyst consisting of multiporous oxygen-rich carbon-nitrogen graphene-like nanosheets (OLAA-CN NSs) is first developed through a staged temperature-programmed calcination of l-ascorbic acid (LAA)-modified dicyandiamide precursor. It is found that the oxygen species from l-ascorbic acid (OLAA) are introduced into the graphene-like basic matrix and replace partial N atoms to form the COC-R structure, leading to the non-uniform distribution of electrons on the catalyst surface, and the formation of electron-rich centers around the COC microareas according to a series of characterization techniques. As a result, OLAA-CN NSs exhibits excellent performance for refractory pollutant removal in the presence of peroxymonosulfate (PMS) and dissolved oxygen. Some pollutants with complex structures are even completely degraded within only 1 min. The interface reaction mechanism is further revealed that PMS mainly acts as an active inducer to drive the electron donation of pollutants over OLAA-CN NSs. These electrons are finally utilized by dissolved oxygen to generate reactive oxygen species (ROS) through the interface process. This reaction system results in pollutants that can either be cleaved directly by surface oxidation process or degraded by the attack of the generated ROS, such as singlet oxygen (1O2) and superoxide radicals (O2•-), through oxygen activation, which significantly reduces the resource and energy consumption in advanced wastewater treatment by harnessing the energy of pollutants and dissolved oxygen in the water.

Enhanced Fenton-like process via interfacial electron donating of pollutants over in situ Cobalt-doped graphitic carbon nitride.

The heterogeneous Fenton process suffers from low efficiency because of the low electron transfer cycle rate of Fe3+/Fe2+, which often consumes enormous amounts of hydrogen peroxide (H2O2) or other energy. Herein, we report a novel Co-based Fenton-like catalyst (in-situ-Co-g-C3N4) synthesized via the surface complexation method, in which Co species were modified in situ into the framework of the graphitic carbon nitride (g-C3N4) substrate through C-O-Co chemical bonding. The catalyst exhibited higher Fenton-like catalytic activity than pure g-C3N4 in the degradation of various pollutants under neutral conditions, as evidenced by the approximately 150-fold higher Fenton-like reaction rate constant of in-situ-Co-g-C3N4 than that of g-C3N4. Density functional theory (DFT) calculations and a series of experimental and characterization analyses revealed the interfacial reaction mechanism between H2O2, pollutants and in-situ-Co-g-C3N4. During the Fenton-like reaction, the electron-poor C center on the aromatic ring of g-C3N4 could capture the electrons deprived from pollutants, and subsequently deliver them to around the electron-rich Co center to efficiently reduce H2O2 to hydroxyl radicals (•OH), enabling H2O2 to be used efficiently for the degradation of pollutants. This study provides a strategy for improving Fenton-like degradation efficiency by effectively utilizing the energy of organic pollutants.

Cation-π induced surface cleavage of organic pollutants with ⋠OH formation from H2O for water treatment.

High energy consumption is impedimental for eliminating refractory organic pollutants in water by applying advanced oxidation processes (AOPs). Herein, we develop a novel process for destructing these organics in chemical conjuncted Fe0-FeyCz/Fex, graphited ZIF-8, and rGO air-saturated aqueous suspension without additional energy. In this process, a strong Fe-π interaction occurs on the composite surface, causing the surface potential energy ∼310.97 to 663.96 kJ/mol. The electrons for the adsorbed group of pollutants are found to delocalize to around the iron species and could be trapped by O2 in aqueous suspension, producing ⋅OH, H, and adsorbed organic cation radicals, which are hydrolyzed or hydrogenated to intermediate. The target pollutants undergo surface cleavage and convert H2O to ⋅OH, consuming chemical adsorption energy (∼2.852-9.793 kJ/mol), much lower than that of AOPs. Our findings provide a novel technology for water purification and bring new insights into pollutant oxidation chemistry.

H2O2 inducing dissolved oxygen activation and electron donation of pollutants over Fe-ZnS quantum dots through surface electron-poor/rich microregion construction for water treatment.

In common advanced oxidation processes, excess reagents and energy are often added to the reaction system to maintain the continuity of the reaction. These additions result in a large waste of resources and energy, which has become a bottleneck in the development of water treatment technology. In this study, we propose a new strategy to solve this problem based on a novel dual-reaction-center (DRC) Fe-ZnS quantum dots (Fe-ZnS QDs) catalyst that forms a non-equilibrium surface with an electron-polarized distribution. Through experimental and theoretical studies, it was verified that the activation of trace amounts of H2O2 could break the energy barrier for pollutants to transfer electrons. The dissolved oxygen (DO) in the reaction system could be activated by gaining energy on the surface of the Fe-ZnS QDs catalyst, and was converted to 1O2 to attack organic pollution. In addition, the pollutants themselves supplied electrons to H2O2 through the surface of the Fe-ZnS QDs catalyst to generate more •OH radicals for pollutant degradation, thus providing two fast paths for pollutant degradation. The system could drive the reaction through a trace amount of H2O2, thereby activating DO to generate 1O2 while effectively using the energy of pollutants. Therefore, the proposed system offers a new direction for the development of environmentally-friendly catalysts and greatly reduces the consumption of resources and energy.