Three-Dimensional Porous Indium Single-Atom Catalysts with Improved Accessibility for CO2 Reduction to Formate.

Single-atom catalysts (SACs) present substantial potential in electrocatalytic CO2 reduction reactions; however, inferior accessibility of single-atom sites to CO2 limits the overall CO2RR performances. Herein, we propose to improve the accessibility between In sites and CO2 through the construction of a three-dimensional (3D) porous indium single-atom catalyst (In1/NC-3D). The NaCl template-mediated synthesis strategy generates the unique 3D porous nanostructure of In1/NC-3D. Multiple characterizations validate that In1/NC-3D exhibits increased exposure of active sites and enhanced CO2 transport/adsorption capacity compared to the bulk In1/NC, thus improving accessibility of active sites to CO2. As a result, the In1/NC-3D presents superior CO2RR performance to the bulk In1/NC, with a partial current density of formate of 67.24 mA cm-2 at -1.41 V, relative to a reversible hydrogen electrode (vs RHE). The CO2RR performances with high formate selectivity at a large current density also outperform most reported In-based SACs. Importantly, the In1/NC-3D is demonstrated to maintain an FEformate of >82% at -66.83 mA·cm-2 over 21 h. This work highlights the design of a 3D porous single-atom catalyst for efficient CO2RR, promoting the development of advanced catalysts toward advanced energy conversion.

A review of the phosphorus removal of polyphosphate-accumulating organisms in natural and engineered systems.

Increasing eutrophication has led to a continuous deterioration of many aquatic ecosystems. Polyphosphate-accumulating organisms (PAOs) can provide insight into the human response to this challenge, as they initiate enhanced biological phosphorus removal (EBPR) through cyclical anaerobic phosphorus release and aerobic phosphorus uptake. Although the limiting environmental factors for PAO growth and phosphorus removal have been widely discussed, there remains a gap in the knowledge surrounding the differences in the type and phosphorus removal efficiencies of natural and engineered PAO systems. Furthermore, due to the limitations of PAOs in conventional wastewater treatment environments, there is an urgent need to find functional PAOs in extreme environments for better wastewater treatment. Therefore, it is necessary to explore the effects of extreme conditions on the phosphorus removal efficiency of PAOs as well as the types, sources, and characteristics of PAOs. In this paper, we summarize the response mechanisms of PAOs, denitrifying polyphosphate-accumulating organisms (D-PAOs), aerobic denitrifying polyphosphate-accumulating organisms (AD-PAOs), and sulfur-related PAOs (S-PAOs). The mechanism of nitrogen and phosphorus removal in PAOs is related to the coupling cycles of carbon, nitrogen, phosphorus, and sulfur. The genera of PAOs differ in natural and engineered systems, but PAOs have more diversity in aquatic environments and soils. Recent studies on the impact of several parameters (e.g., temperature, carbon source, pH, and dissolved oxygen) and extracellular polymer substances on the phosphorus removal efficiency of PAOs in natural and engineered systems are further discussed. Most of the PAOs screened under extreme conditions still had high phosphorus removal efficiencies (>80.0 %). These results provide a reference for searching for PAOs with different adaptations to achieve better wastewater treatment.

Mn Single-Atom Tuning Fe-N-C Catalyst Enables Highly Efficient and Durable Oxygen Electrocatalysis and Zinc-Air Batteries.

Fe-N-C catalyst is one of most promising candidates for oxygen electrocatalysis reaction in zinc-air batteries (ZABs), but achieving sustained high activity is still a challenging issue. Herein, we demonstrate that introducing Mn single atoms into Fe-N-C (Mn1@Fe-N-C/CNTs) enables the realization of highly efficient and durable oxygen electrocatalysis performance and application in ZABs. Multiple characterizations confirm that Mn1@Fe-N-C/CNTs is equipped with Mn-N2O2 and Fe-N4 sites and Fe nanoparticles. The Mn-N2O2 sites not only tune the electron structure of Fe-Nx sites to enhance intrinsic activity, but also scavenge the attack of radicals from Fe-Nx sites for improvement in ORR durability. As a result, Mn1@Fe-N-C/CNTs exhibits enhanced ORR performance to traditional Fe-N-C catalysts with high E1/2 of 0.89 V vs reversible hydrogen electrode (RHE) and maintains ORR activity after 15 000 CV. Impressively, Mn1@Fe-N-C/CNTs also presents excellent OER activity and the difference (ΔE) between E1/2 of ORR and OER potential at 10 mA cm-2 (Ej10) is only 0.59 V, outperforming most reported catalysts. In addition, the maintainable bifunctional activity of Mn1@Fe-N-C/CNTs is demonstrated in ZABs with almost unchanged cycle voltage efficiency up to 200 h. This work highlights the critical role of Mn single atoms in enhancing ORR activity and stability, promoting the development of advanced catalysts.

Highly Hydrophilic and Defective Carbon Nitride for Enhanced Photocatalytic Hydrogen Evolution.

Graphitic carbon nitride (g-C3N4), as a kind of nonmetallic low-cost photocatalyst, has great potential in photocatalytic hydrogen (H2) evolution, but its poor hydrophilicity and nonwetting extremely limit its H2 evolution efficiency. Herein, highly hydrophilic and defective g-C3N4 photocatalysts (NH3-CN-P as a representative example) have been fabricated on the basis of the strategy of joint phosphorus doping and ammonia stripping. The dopant of phosphorus prefers to occupy the C atoms bonded to -NH2 groups in the g-C3N4 skeleton, which is conducive to the formation of N defects caused by the effects of electronegativity and charge balance. Moreover, ammonia stripping plays a dual role in exposing plentiful two-dimensional defective planar structure and implanting the hydrophilic groups on the surface. As expected, the photocatalytic H2 evolution property of NH3-CN-P reaches 11.31 mmol g-1 h-1, with an apparent quantum yield of 17.9% at 420 nm, outperforming the majority of the reported g-C3N4-based photocatalysts.

Modulating the Cu2O Photoelectrode/Electrolyte Interface with Bilayer Surfactant Simulating Cell Membranes for Boosting Photoelectrochemical CO2 Reduction.

The low solubility of CO2 molecules and the competition of the hydrogen evolution reaction (HER) in aqueous electrolytes pose significant challenges to the current photoelectrochemical (PEC) CO2 reduction reaction. In this study, inspired by the bilayer phospholipid molecular structure of cell membranes, we developed a Cu2O/Sn photocathode that was modified with the bilayer surfactant DHAB for achieving high CO2 permeability and suppressed HER. The Cu2O/Sn/DHAB photocathode stabilizes the *OCHO intermediate and facilitates the production of HCOOH. Our findings show that the Faradaic efficiency (FE) of HCOOH by the Cu2O/Sn/DHAB photoelectrode is 83.3%, significantly higher than that achieved with the Cu2O photoelectrode (FEHCOOH = 30.1%). Furthermore, the FEH2 produced by the Cu2O/Sn/DHAB photoelectrode is only 2.95% at -0.6 V vs RHE. The generation rate of HCOOH by the Cu2O/Sn/DHAB photoelectrode reaches 1.52 mmol·cm-2·h-1·L-1 at -0.7 V vs RHE. Our study provides a novel approach for the design of efficient photocathodes for CO2 reduction.

Enhanced Electron Confinement of p-Block Indium Site in Extended Macrocyclic Conjugation Boosting Oxygen Reduction to Hydrogen Peroxide.

The electrocatalytic oxygen reduction reaction via a two-electron pathway (2e- ORR) is a promising route for hydrogen peroxide (H2O2) production. However, the strong electron interaction between the metal site and oxygen-containing intermediates usually generates 4-electron ORR, limiting H2O2 selectivity. Here, combining theoretical and experimental studies, we propose to enhance the electron confinement of the indium (In) center in an extended macrocyclic conjugation system toward high-efficiency H2O2 production. The extended macrocyclic conjugation in indium polyphthalocyanine (InPPc) evokes the attenuated transfer electron ability of the In center and weakens the interaction between the s orbital of In and the p obital of OOH*, favoring protonation of OOH* to H2O2. Experimentally, the prepared InPPc catalyst exhibits a noticeable H2O2 selectivity above 90% in 0.1-0.6 V vs RHE, outperforming the counterpart InPc. Importantly, the InPPc displays a high average H2O2 production rate of 23.77 mg/cm2/h in a flow cell. This study proposes a novel strategy to engineer molecular catalysts and provides new insights into the ORR mechanism.

Synergistic impacts of Fe/Fe3C and Fe-Nx on high-efficiency microwave-absorbing properties of Fe/Fe3C@NC composites.

The construction of multi-component composites has become an attractive strategy for high-performance microwave absorption through balancing the magnetic and dielectric loss. However, the influences of different components on absorption performance are ambiguous, which has inevitably hampered the widespread applications of microwave absorbents. Herein, we rationally designed the multi-component absorbers of N-doped carbon composited with Fe/Fe3C nanoparticles, and systematically investigated the impacts of Fe/Fe3C nanoparticles and Fe-Nxmoieties on the microwave-absorbing capacities. It is found that the coexisitence of Fe/Fe3C and Fe-Nxis indispensable to realize the strong microwave absorption ability by simultaneously enhancing the dielectric and magnetic loss in the frequency range of 2-18 GHz. As expected, our optimal absorber dispersed in paraffin with a filler loading of 15 wt% exhibits the minimum reflection loss (RLmin) value of -49 dB and the maximum effective absorption bandwidth (BWeff) value of 4.2 GHz at a low thickness. Our work specifies the importance and influence of the coexistence between the Fe-Nxconfigurations and Fe/Fe3C nanoparticles in the carbon-based composites for the superior microwave absorption and inspires the future fabrication of extraordinary materials in the electromagnetic field.

Hydrophobic surface efficiently boosting Cu2O nanowires photoelectrochemical CO2 reduction activity.

The limited mass transfer of CO2 and the competitive hydrogen evolution reaction (HER) during photoelectrochemical (PEC) CO2 reduction usually result in low CO2 reduction activity. Here, we constructed a Cu2O/Sn/PTFE photocathode with a hydrophobic surface based on Cu2O by physical vapor deposition and a dipping method. The CO faradaic efficiency (FE) increased from 34.5% (Cu2O) to 95.1% (Cu2O/Sn/PTFE) at -0.7 V vs. RHE, and the FEH2 decreased from 27.9% (Cu2O) to 3.8% (Cu2O/Sn/PTFE). The introduction of the hydrophobic layer enhances the local CO2 concentration on the electrode surface and effectively isolates H+ from the aqueous electrolyte, thereby enhancing the CO2 reduction activity.

Regulating the N-Coordination Structure of Fe-Fe Dual Sites as the Electrocatalyst for the O2 Reduction Reaction in Metal-Air Batteries.

Iron-nitrogen coordinated catalysts are regarded as efficient catalysts for the oxygen (O2) reduction reaction (ORR), wherein the coordination environment of Fe sites is critical to the catalytic activity. Herein, we explored the effect of the nitrogen-coordination structure of dual-atomic Fe2 sites (i.e., Fe2-N6-C and Fe2-N4-C) on the performance of the ORR. The half-wave potential (E1/2) of Fe2-N6-C is 0.880 V vs RHE, outperforming that of the tetracoordinate Fe2-N4-C (0.851 V) and commercial Pt/C (0.850 V) in alkaline electrolytes. The Fe2-N6-C-based zinc-air battery delivers a maximum power density of (258.6 mW/cm2) and superior durability under 10 mA/cm2. Theoretical calculations unveil that the moieties of Fe2-N6 profits the d-electron rearrangement of the Fe2 sites. The electronic and geometrical structure of Fe2-N6 promotes the O2 molecules adsorbed on the Fe2 site and reduces the dissociation energy barrier of O2, benefiting fracture of O-O bonds and acceleration of the transformation of O2 to *OOH (the first step of the ORR process). Such exploration of modulating the local N-coordination environment of Fe2 dimers paves an in-depth insight to design and optimize dual-atomic catalysts.

Plasmonic Ag-decorated Cu2O nanowires for boosting photoelectrochemical CO2 reduction to multi-carbon products.

The generation of multi-carbon products on the Cu2O photocathode remains a great challenge. Herein, effective charge separation and surface catalytic reaction are achieved for photoelectrochemical CO2 reduction through plasmon metal (Ag) decoration on Cu2O nanowires. The Cu2O/Ag composite photocathode achieves a 47.7% faradaic efficiency for CH3COOH and the generation rate is 212.7 µmol cm-2 h-1 under illumination, which is about five times that in dark (44.4 µmol cm-2 h-1) at -0.7 V vs. RHE.

Highly efficient and stable indium single-atom catalysts for electrocatalytic reduction of CO2 to formate.

Indium single-atom catalysts display a large total current density (38.94 to 81.08 mA cm-2) over an extensive potential window (-0.91 to -1.41 V vs. RHE) for electrocatalytic CO2 reduction to formate with high selectivity (85.2% faradaic efficiency at -1.31 V).

Accelerating CO2 Electroreduction to Multicarbon Products via Synergistic Electric-Thermal Field on Copper Nanoneedles.

Electrochemical CO2 reduction is a promising way to mitigate CO2 emissions and close the anthropogenic carbon cycle. Among products from CO2RR, multicarbon chemicals, such as ethylene and ethanol with high energy density, are more valuable. However, the selectivity and reaction rate of C2 production are unsatisfactory due to the sluggish thermodynamics and kinetics of C-C coupling. The electric field and thermal field have been studied and utilized to promote catalytic reactions, as they can regulate the thermodynamic and kinetic barriers of reactions. Either raising the potential or heating the electrolyte can enhance C-C coupling, but these come at the cost of increasing side reactions, such as the hydrogen evolution reaction. Here, we present a generic strategy to enhance the local electric field and temperature simultaneously and dramatically improve the electric-thermal synergy desired in electrocatalysis. A conformal coating of ∼5 nm of polytetrafluoroethylene significantly improves the catalytic ability of copper nanoneedles (∼7-fold electric field and ∼40 K temperature enhancement at the tips compared with bare copper nanoneedles experimentally), resulting in an improved C2 Faradaic efficiency of over 86% at a partial current density of more than 250 mA cm-2 and a record-high C2 turnover frequency of 11.5 ± 0.3 s-1 Cu site-1. Combined with its low cost and scalability, the electric-thermal strategy for a state-of-the-art catalyst not only offers new insight into improving activity and selectivity of value-added C2 products as we demonstrated but also inspires advances in efficiency and/or selectivity of other valuable electro-/photocatalysis such as hydrogen evolution, nitrogen reduction, and hydrogen peroxide electrosynthesis.

Tuning Active Species in N-Doped Carbon with Fe/Fe3C Nanoparticles for Efficient Oxygen Reduction Reaction.

Transition metal-nitrogen-carbon (M-N-C) catalysts (M = Fe, Co, etc.) are the most promising substituents of Pt-based catalysts for oxygen reduction reaction (ORR). However, the insufficient active species in catalysts inevitably hamper their widespread applications. Herein, we report the regulation of the active species in the catalysts of multicomponent N-doped carbon with Fe/Fe3C nanoparticles by polydopamine (PDA) coating. It is found that the PDA is conducive to increasing the pyridinic, graphitic, and total N content in the carbon matrix. Benefiting from the chelating effects, the PDA further profits the formation of Fe-Nx structures and the implantation of Fe/Fe3C nanoparticles in the matrix during the pyrolysis. As expected, the resultant catalysts exhibit over 15 times mass activity toward ORR than nitrogen-doped carbon. Moreover, our developed catalysts show long-term stability as well as high methanol tolerance, which is superior to that of the commercial Pt/C electrode. This work provides a new avenue to explore a wider range of high-performance ORR electrocatalysts by regulating the active species.

Machine Learning in Screening High Performance Electrocatalysts for CO2 Reduction.

Converting CO2 into carbon-based fuels is promising for relieving the greenhouse gas effect and the energy crisis. However, the selectivity and efficiency of current electrocatalysts for CO2 reductions are still not satisfactory. In this paper, the development of machine learning methods in screening CO2 reduction electrocatalysts over the recent years is reviewed. Through high-throughput calculation of some key descriptors such as adsorption energies, d-band center, and coordination number by well-constructed machine learning models, the catalytic activity, optimal composition, active sites, and CO2 reduction reaction pathway over various possible materials can be predicted and understood. Machine learning is now realized as a fast and low-cost method to effectively explore high performance electrocatalysts for CO2 reduction.

Atomically Dispersed s-Block Magnesium Sites for Electroreduction of CO2 to CO.

Atomically dispersed transition metal sites have been extensively studied for CO2 electroreduction reaction (CO2 RR) to CO due to their robust CO2 activation ability. However, the strong hybridization between directionally localized d orbits and CO vastly limits CO desorption and thus the activities of atomically dispersed transition metal sites. In contrast, s-block metal sites possess nondirectionally delocalized 3s orbits and hence weak CO adsorption ability, providing a promising way to solve the suffered CO desorption issue. Herein, we constructed atomically dispersed magnesium atoms embedded in graphitic carbon nitride (Mg-C3 N4 ) through a facile heat treatment for CO2 RR. Theoretical calculations show that the CO desorption on Mg sites is easier than that on Fe and Co sites. This theoretical prediction is demonstrated by experimental CO temperature program desorption and in situ attenuated total reflection infrared spectroscopy. As a result, Mg-C3 N4 exhibits a high turnover frequency of ≈18 000 per hour in H-cell and a large current density of -300 mA cm-2 in flow cell, under a high CO Faradaic efficiency ≥90 % in KHCO3 electrolyte. This work sheds a new light on s-block metal sites for efficient CO2 RR to CO.

Dual Inorganic Sacrificial Template Synthesis of Hierarchically Porous Carbon with Specific N Sites for Efficient Oxygen Reduction.

It is still a challenge to achieve efficiently controlled preparation of functional oxygen reduction reaction (ORR) carbon electrocatalysts with multi-preferred structures (hierarchically porous networks and specific carbon-nitrogen bonds) from carbohydrate-containing small molecules via simple one-step pyrolysis. Based on the step-by-step spontaneous gas-foaming strategy, we successfully prepare 3D hierarchically porous networks with tunable N sites (NP/NG ≈ 1:1) by pyrolyzing diverse carbohydrates (glucose, maltose, and cyclodextrin) using nonmetal-metal dual inorganic sacrificial templates. In situ evaporation templates can simplify the procedure of the experiments and avoid the active site loss compared with traditional hard templates. Crucially, dual inorganic sacrificial templates can induce abundant defects and microscopic pore structures (the specific surface area increased from 922.403 to 1898.792 m2·g-1) and tunable N sites compared with single nonmetal sacrificial templates. The regulatory mechanism of dual inorganic templates on N sites (NP/NG ≈ 1:1) is independent of the polymeric state of carbohydrate precursors or even the carbonization condition of the pyrolysis process. A series of carbon materials prepared by this strategy all have ORR-preferred structures and exhibit low ORR overpotentials compared with Pt/C. For instance, the Zn-air battery with ßCD-DSC-950-1 exhibits an open-circuit potential of 1.51 V and a peak power density of 180.89 mW·cm-2, higher than those of Pt/C (1.47 V, 174.94 mW·cm-2). In general, the conversion of carbohydrate-containing small molecules to functional carbon materials provides a new strategy for the development of carbonaceous electrocatalysts.

Efficient three-phase electrocatalytic CO2 reduction to formate on superhydrophobic Bi-C interfaces.

Bi-C catalysts with the three-phase interfaces of CO2 (gas), electrolyte (liquid) and catalyst (solid) exhibit a remarkable electrocatalytic CO2 reduction (ECR) to formate selectivity (above 95% faradaic efficiency) with a high current (100 mA cm-2) in a broad potential range.

Defect-Induced Ce-Doped Bi2WO6 for Efficient Electrocatalytic N2 Reduction.

Electrochemical nitrogen reduction reaction (NRR) is a promising method for synthesizing ammonia (NH3). However, due to the extremely strong N≡N bond and the competing hydrogen evolution reaction (HER), the electrochemical NRR process remains a great challenge in achieving a high NH3 yielding rate and a high Faradaic efficiency (FE). Recently, either Bi-based or W-based catalysts have been used in N2 fixation due to lower HER activity. To further promote N2 activation, we develop a simple protocol to introduce and adjust the crystal defects in the host lattice of Bi2WO6 nanoflowers via adjusting the amount of Ce dopant (denoted as xCe-Bi2WO6, where x represents the designed mole percentage of Ce). At -0.20 V versus the reversible hydrogen electrode (RHE), 10%Ce-Bi2WO6 manifests a high NH3 yielding rate (22.5 µg h-1 mg-1cat.), a high FE (15.9%), and excellent electrochemical and structure durability. Its performance is better than most previously reported Bi-based and W-based electrocatalysts for NRR in aqueous solutions. According to density functional theory (DFT) calculations, the introduction of crystal defects into Bi2WO6 can strengthen the adsorption and activation of N2, thus leading to a significant increase in NRR activity.

Hydroxyl/amino and Fe(III) co-grafted graphite carbon nitride for photocatalytic removal of volatile organic compounds.

Hydroxyl/amino and Fe(III) co-grafted graphite carbon nitride (CN) is fabricated via alkaline hydrothermal treatment and followed by an impregnation adsorption process. In this unique fabrication, hydroxyl and amino groups enriched on the surface play a vital role in improving the adsorption capacity for volatile organic compounds (VOCs), while the grafted amorphous Fe(III) clusters could dominantly regulate the path of molecular oxygen activation via photo-Fenton reaction, and change the selectivity of intermediate reactive oxygen species (ROS) with the assistant of the rich surficial hydroxyl groups. Meanwhile, both the grafted functional groups and Fe(III) clusters can serve as photogenerated charge acceptors for collaboratively accelerating carriers' separation. Besides, the Fe(III)-mediated interfacial charge transfer effect (IFCT) also could extend visible light absorption and boost carriers' generation. Benefiting from the virtues of the complementary and synergy of the grafted hydroxyl/amino and Fe(III), the dual-functionalized CN is qualified as an efficient photocatalyst for removal of VOCs, which exhibits 22 and 18 times isopropanol (IPA) adsorption capacity and CO2 production than of pristine CN during photocatalytic IPA removal, respectively. Moreover, this work provides a new strategy of surficial group-cluster bifunctionalization for systematically improving sustainable solar-to-chemical energy conversion towards VOCs mineralization.

An "on-off-super on" photoelectrochemical sensor based on quenching by Cu-induced surface exciton trapping and signal amplification of copper sulfide/porous carbon nitride heterojunction.

In this work, we report an "on-off-super on" photoelectrochemical sensor for probing hydrogen sulfide due to its toxicity in water environment by using porous carbon nitride as photoelectric transducers. Synthesized by an alkaline-assisted hydrothermal method, the porous carbon nitride photoanode exhibited a remarkable photocurrent on the initial "on" state. Cu2+ immobilized on the surfaces of porous carbon nitride could significantly decrease the charge transfer efficiency and quench the photoelectrochemical signal in the "off" state. In addition, the introduction of S2- ions could eliminate the influence of Cu-induced surface exciton trapping and amplify the photoelectrochemical signal due to the formation of carbon nitride/copper sulfide heterojunction, thus leading to the achievement of the ''super on'' state and subsequently detection of hydrogen sulfide. More importantly, this photoelectrochemical sensor shows the excellent performance for probing hydrogen sulfide in terms of stability, selectivity, sensitivity and fabrication cost. Enabled by a unique "on-off-super on" strategy, it could serve as a reference for developing the new class of photoelectrochemical sensor.