Shear Stress Triggers Ultrathin-Nanosheet Carbon Nitride Assembly for Photocatalytic H2O2 Production Coupled with Selective Alcohol Oxidation.

Coupled photocatalysis without cocatalysts can maximize the utilization of photons and atoms, which puts forward higher demands on photocatalysts. Polymeric carbon nitride (CN) has become the most promising photocatalyst, but still suffers from major drawbacks of insufficient catalytic sites and low quantum efficiency. Herein, we report a fluid shear stress-assisted molecular assembly to prepare ultrathin-nanosheet-assembled acanthosphere-like CN (ASCN) with nitrogen vacancy (Nv) and carbonyl modification. Shear stress breaks the stacking interactions between layers and cuts the stacked structure into ultrathin layers, which are further reassembled into acanthosphere bundles driven by "centrifugal force". Benefitted greatly from the ultrathin nature that provides more exposed active sites and improves charge carrier separation, ASCN-3 exhibits a 20-fold higher activity than the bulk counterpart toward oxygen reduction to H2O2 coupled with 4-methoxybenzyl alcohol (4-MBA) oxidation to anisaldehyde (AA), with significantly increased turnover frequency (TOF) values (TOF: 1.69 h-1 for H2O2 and 1.02 h-1 for AA). Significantly, ASCN-3 exhibits 95.8% conversion for 4-MBA oxidation with nearly 100% selectivity. High apparent quantum yields of 11.7% and 9.3% at 420 nm are achieved for H2O2 photosynthesis and 4-MBA oxidation. Mechanism studies suggest that carbonyl induces holes concentrated at the neighboring melem unit to directly oxidize the Cα-H bond of 4-MBA to produce carbon radicals, and Nv as oxygen adsorption active site traps electrons to form a superoxide radical that further combines with the shed protons into H2O2. This work presents a simple physical method to break the layered stack of CN for creating hierarchical assembly for coupled photocatalysis.

Decrypting the Electron-Withdrawing Effect of Au-Decorated Bi2 O3 for Efficient CO2 -to-Formate Electroreduction.

Although the electron-withdrawing effect of gold (Au) is highlighted in catalytic reactions, its enhancement mechanism for electron transport, especially in the electrochemical process, is still unclear. Herein, Au-decorated Bi2 O3 (Au-Bi2 O3 ) is proposed as a proof-of-concept to investigate the electron-withdrawing effect in the electrocatalytic CO2 reduction reaction (eCO2 RR) process. Evidence from in situ Raman spectra and in situ XRD tests reveals that, compared to Bi2 O3 , Bi species in Au-Bi2 O3 can be reduced to metallic Bi more rapidly and more easily driven by the electron-withdrawing effect of Au. The XPS tests after eCO2 RR further validates the transformation from Bi3+ to Bi0 in Au-Bi2 O3 is more complete. Meanwhile, in the in situ Fourier transform infrared (FTIR) spectra, the key intermediates (CO2 *- and OCHO*- ) appear at the more positive potential, indicating that metallic Bi is favorable for eCO2 RR due to the lower energy barrier as corroborated by density function theory (DFT) calculations. Au don't directly participate in the conversion from CO2 to formate as the reaction sites, but utilize the electron-withdrawing effect to motivate Bi-sites to deliver higher catalytic activity and higher selectivity to formate at a lower applied potential. This study not only has an insight into the electron-withdrawing effect of Au on the eCO2 RR process, but also develops a new perspective for engineering electron-withdrawing effect in electrocatalysts for high-efficient CO2 -to-formate conversion.

Potential Dominates Structural Recombination of Single Atom Mn Sites for Promoting Oxygen Reduction Reaction.

Single atom sites (SAS) often undergo structural recombination in oxygen reduction reaction (ORR), while the effect of valence state and reconstruction on active centers needs to be investigated thoroughly. Herein, the Mn-SAS catalyst with uniform and precise Mn-N4 configuration is rationally designed. We utilize operando synchrotron radiation to track the dynamic evolution of active centers during ORR. Under the applied potential, the structural evolution of Mn-N4 into Mn-N3 C and further into Mn-N2 C2 configurations is clarified. Simultaneously, the valence states of Mn are increased from +3.0 to +3.8 and then decreased to +3.2. When the potential is removed, the catalyst returned to its initial Mn+3.0 -N4 configuration. Such successive evolutions optimize the electronic and geometric structures of active centers as evidenced by theory calculations. The evolved Mn+3.8 -N3 C and Mn+3.2 -N2 C2 configurations respectively adjust the O2 adsorption and reduce the energy barrier of rate-determining step. Thus, it can achieve an onset potential of 0.99 V, superior stability over 10,000 cycles, and a high turnover frequency of 1.59 s-1 at 0.85 VRHE. Our present work provides new insights into the construction of well-defined SAS catalysts by regulating the valence states and configurations of active centers.

Mo-Ni-based Heterojunction with Fine-customized d-Band Centers for Hydrogen Production Coupled with Benzylamine Electrooxidation in Low Alkaline Medium.

Benzylamine electrooxidation reaction (BAOR) is a promising route to produce value-added, easy-separated benzonitrile, and effectively hoist H2 production. However, achieving excellent performance in low alkaline medium is a huge challenge. The performance is intimately correlated with effective coupling of HER and BAOR, which can be achieved by manipulating the d-electron structure of catalyst to regulate the active species from water. Herein, we constructed a biphasic Mo0.8 Ni0.2 N-Ni3 N heterojunction for enhanced bifunctional performance toward HER coupled with BAOR by customizing the d-band centers. Experimental and theoretical calculations indicate that charge transfer in the heterojunction causes the upshift of the d-band centers, which one side facilitates to decrease water activation energy and optimize H* adsorption on Mo0.8 Ni0.2 N for promoting HER activity, the other side favors to more easily produce and adsorb OH* from water for forming NiOOH on Ni3 N and optimizing adsorption energy of benzylamine, thus catalyzing BAOR effectively. Accordingly, it shows an industrial current density of 220 mA cm-2 at 1.59 V and high Faradaic efficiencies (>99 %) for H2 production and converting benzylamine to benzonitrile in 0.1 M KOH/0.5 M Na2 SO4 . This work guides the design of excellent bifunctional electrocatalysts for the scalable production of green hydrogen and value-added products.

Atomically Dispersed Fe-N3 C Sites Induce Asymmetric Electron Structures to Afford Superior Oxygen Reduction Activity.

Introducing heteroatoms into atomically dispersed Fe-N4 sites with symmetric electron distribution can adjust the imperfect oxygenated adsorption-activation and promote oxygen reduction reaction (ORR) activity. However, the relevant design synthesis and deeply understanding the electrocatalytic mechanism of such an asymmetric structure by introducing Fe-C coordination remains challenging. Herein, the structural stability of Fe-Nx Cy (x = 0 ≈ 4, y = 4-x) is first theoretically predicted and indicates that the energy of Fe-N4 in the two most stable structures is greater than that of Fe-N3 C. Subsequently, Fe-N4 and Fe-N3 C configurations are controlled synthesized by adjusting pyrolytic temperature. The Fe-N3 C-based electrocatalyst displays a boosted ORR activity with a half-wave potential of 0.91 V and superior long-term stability, outperforming Fe-N4 , Pt/C, and state-of-the-art noble metal-free electrocatalysts. Density functional theory calculations unveil that Fe-N3 C is much more favorable for electron delocalization than Fe-N4 . Furthermore, the residual Zn atom derived from ZIF-8 would give its d-orbit electron to the Fe atom, so the synergy between Fe-N3 C and Zn-N4 makes an enhanced ORR activity.

Vanadium-Incorporated CoP2 with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting.

A proton exchange membrane water electrolyzer (PEMWE) in acidic medium is a hopeful scenario for hydrogen production using renewable energy, but the grand challenge lies in substituting noble-metal catalysts. Herein, a robust electrocatalyst of V-CoP2 porous nanowires arranged on a carbon cloth is successfully fabricated by incorporating vanadium into the CoP2 lattice. Structural characterizations and theoretical analysis indicate that lattice expansion of CoP2 caused by V incorporation results in the upshift of the d-band center, which is conducive to hydrogen adsorption for boosting the hydrogen evolution reaction (HER). Besides, V promotes surface reconstruction to generate a thicker Co3 O4 layer with an oxygen vacancy that enhances acid-corrosion resistance and optimizes the adsorption of water and oxygen-containing species, thus improving activity and stability toward the oxygen evolution reaction (OER). Accordingly, it presents a superior acidic overall water splitting activity (1.47 V@10 mA cm-2 ) to Pt-C/CC||RuO2 /CC (1.59 V@10 mA cm-2 ), and remarkable stability. This work proposes a new route to design efficient non-noble metal electrocatalysts for PEMWE.

Reconstruction of Highly Dense Cu-N4 Active Sites in Electrocatalytic Oxygen Reduction Characterized by Operando Synchrotron Radiation.

The emerging star of single atomic site (SAS) catalyst has been regarded as the most promising Pt-substituted electrocatalyst for oxygen reduction reaction (ORR) in anion-exchange membrane fuel cells (AEMFCs). However, the metal loading in SAS directly affects the whole device performance. Herein, we report a dual nitrogen source coordinated strategy to realize high dense Cu-N4 SAS with a metal loading of 5.61 wt% supported on 3D N-doped carbon nanotubes/graphene structure wherein simultaneously performs superior ORR activity and stability in alkaline media. When applied in H2 /O2 AEMFC, it could reach an open-circuit voltage of 0.90 V and a peak power density of 324 mW cm-2 . Operando synchrotron radiation analyses identify the reconstruction from initial Cu-N4 to Cu-N4 /Cu-nanoclusters (NC) and the subsequent Cu-N3 /Cu-NC under working conditions, which gradually regulate the d-band center of central metal and balance the Gibbs free energy of *OOH and *O intermediates, benefiting to ORR activity.

Structural Design Strategy and Active Site Regulation of High-Efficient Bifunctional Oxygen Reaction Electrocatalysts for Zn-Air Battery.

Zinc-air batteries (ZABs) exhibit high energy density as well as flexibility, safety, and portability, thereby fulfilling the requirements of power batteries and consumer batteries. However, the limited efficiency and stability are still the significant challenge. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are two crucial cathode reactions in ZABs. Development of bifunctional ORR/OER catalysts with high efficiency and well stability is critical to improve the performance of ZABs. In this review, the ORR and OER mechanisms are first explained. Further, the design principles of ORR/OER electrocatalysts are discussed in terms of atomic adjustment mechanism and structural design in conjunction with the latest reported in situ characterization techniques, which provide useful insights on the ORR/OER mechanisms of the catalyst. The improvement in the energy efficiency, stability, and environmental adaptability of the new hybrid ZAB by the inclusion of additional reaction, including the introduction of transition-metal redox couples in the cathode and the addition of modifiers in the electrolyte to change the OER pathway, is also summarized. Finally, current challenges and future research directions are presented.

Operando Cooperated Catalytic Mechanism of Atomically Dispersed Cu-N4 and Zn-N4 for Promoting Oxygen Reduction Reaction.

Dual-metal single-atom catalysts exhibit superior performance for oxygen reduction reaction (ORR), however, the synergistic catalytic mechanism is not deeply understood. Herein, we report a dual-metal single-atom catalyst consisted of Cu-N4 and Zn-N4 on the N-doped carbon support (Cu/Zn-NC). It exhibits high-efficiency ORR activity with an Eonset of 0.98 V and an E1/2 of 0.83 V, excellent stability (no degradation after 10 000 cycles), surpassing state-of-the-art Pt/C and great mass of Pt-free single atom catalysts. Operando XANES demonstrates that the Cu-N4 as active center experiences the change from atomic dispersion to cluster with the cooperation of Zn-N4 during ORR process, and then turns to single atom state again after reaction. DFT calculation further indicates that the adjustment effect of Zn on the d-orbital electron distribution of Cu could benefit to the stretch and cleavage of O-O on Cu active center, speeding up the process of rate determining step of OOH*.

Ultrathin Porous Carbon Nitride Bundles with an Adjustable Energy Band Structure toward Simultaneous Solar Photocatalytic Water Splitting and Selective Phenylcarbinol Oxidation.

Actiniae-like carbon nitride (ACN) bundles were synthesized by the pyrolysis of an asymmetric supramolecular precursor prepared from L-arginine (L-Arg) and melamine. ACN has adjustable band gaps (2.25 eV-2.75 eV) and hollow microtubes with ultrathin pore walls, which enrich reaction sites, improve visible-light absorption and enhance charge separation. In the presence of phenylcarbinol, ACN exhibited excellent water-splitting ability (95.3 µmol h-1 ) and in the meanwhile phenylcarbinol was selectively oxidized to benzaldehyde (conversion of 90.9 %, selectivity of 99.7 %) under solar irradiation. For the concurrent reactions, 2 D isotope labeling, separation, and detection were conducted to confirm that the proton source of released hydrogen is water. The mechanism of water splitting and phenylcarbinol oxidation was also investigated.

Two-Dimensional Porous Molybdenum Phosphide/Nitride Heterojunction Nanosheets for pH-Universal Hydrogen Evolution Reaction.

Herein, we present a new strategy for the synthesis of 2D porous MoP/Mo2 N heterojunction nanosheets based on the pyrolysis of 2D [PMo12 O40 ]3- -melamine (PMo12 -MA) nanosheet precursor from a polyethylene glycol (PEG)-mediated assembly route. The heterostructure nanosheets are ca. 20 nm thick and have plentiful pores (<5 nm). These structure features offer advantages to promote the HER activity, including the favorable water dissociation kinetics around heterojunction as confirmed by theoretical calculations, large accessible surface of 2D nanosheets, and enhanced mass-transport ability by pores. Consequently, the 2D porous MoP/Mo2 N heterojunction nanosheets exhibit excellent HER activity with low overpotentials of 89, 91 and 89 mV to achieve a current density of 10 mA cm-2 in alkaline, neutral and acidic electrolytes, respectively. The HER performance is superior to the commercial Pt/C at a current density >55 mA cm-2 in neutral medium and >190 mA cm-2 in alkaline medium.

Molecule Self-Assembly Synthesis of Porous Few-Layer Carbon Nitride for Highly Efficient Photoredox Catalysis.

Polymeric carbon nitride (C3N4) has emerged as the most promising candidate for metal-free photocatalysts but is plagued by low activity due to the poor quantum efficiency and low specific surface area. Exfoliation of bulk crystals into ultrathin nanosheets has proven to be an effective and widely used strategy for enabling high photocatalytic performances; however, this process is complicated, time-consuming, and costly. Here, we report a simple bottom-up method to synthesize porous few-layer C3N4, which involves molecule self-assembly into layered precursors, alcohol molecules intercalation, and subsequent thermal-induced exfoliation and polycondensation. The as-prepared few-layer C3N4 expose more active sites and greatly enhance the separation of charge carriers, thus exhibiting a 26-fold higher hydrogen evolution activity than bulk counterpart. Furthermore, we find that both the high activity and selectivity for the oxidative coupling of amines to imines can be obtained under visible light that surpass those of other metal-free photocatalysts so far.

NiSe-Ni0.85 Se Heterostructure Nanoflake Arrays on Carbon Paper as Efficient Electrocatalysts for Overall Water Splitting.

Fabricating cost-effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni0.85 Se/CP, and NiSe-Ni0.85 Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe-Ni0.85 Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single-phase NiSe/CP and Ni0.85 Se/CP. A current density of 10 mA cm-2 at 1.62 V and a high stability can be obtained by using NiSe-Ni0.85 Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH- can be more easily adsorbed on NiSe-Ni0.85 Se than on NiSe and Ni0.85 Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases.

High-Efficient, Stable Electrocatalytic Hydrogen Evolution in Acid Media by Amorphous Fex P Coating Fe2 N Supported on Reduced Graphene Oxide.

Development of efficient and durable non-Pt catalysts for hydrogen evolution reaction (HER) in acid media is highly desirable. Iron nitride has emerged as a promising catalyst for its cost-effective nature, but the corresponding acidic stability must be promoted. Herein, phosphorus-decorated Fe2 N and reduced graphene oxide (P-Fe2 N/rGO) composite are designed and synthesized. X-ray photoelectron spectroscopy and X-ray absorption fine structure (XAFS) show that a thin layer amorphous iron phosphide is coated on the surface of Fe2 N nanoparticles, which could be responsible for the well resistance of chemical corrosion in acidic media. Meanwhile, the P-decoration could tune the electronic state and coordination environment of iron atom as evidenced by XAFS, resulting in dramatically enhanced electrocatalytic activity of P-Fe2 N/rGO. Density functional theory calculations reveal that both the P-connected N atoms and the Fe atoms in P-Fe2 N/rGO catalyst are the main active sites for H* adsorption. The hydrogen-binding free energy |ΔGH* | value is close to zero for P-Fe2 N/rGO, suggesting a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, P-Fe2 N/rGO catalyst could achieve a low ηonset of 22.4 mV, a small Tafel plot of 48.7 mV dec-1 , and remarkable stability for HER in acid electrolyte.

A Stable Bifunctional Catalyst for Rechargeable Zinc-Air Batteries: Iron-Cobalt Nanoparticles Embedded in a Nitrogen-Doped 3D Carbon Matrix.

Low-cost, efficient bifunctional electrocatalysts are needed to mediate the oxygen reduction and oxygen evolution reactions (ORR/OER) in Zn-air batteries. Such catalysts should offer binary active sites and an ability to transfer oxygen-based species and electrons. A 3D catalyst, composed of nanoparticles of CoFe alloy embedded in N-doped carbon nanotubes tangled with reduced graphene oxide, was developed, which presents appreciable ORR/OER activity when applied in a Zn-air battery. A high open-circuit voltage of 1.43 V, a stable discharge voltage of 1.22 V, a high energy efficiency of 60.1 %, and excellent stability after 1 600 cycles at 10 mA cm-2 are demonstrated. An all-solid-state battery had an outstanding lifetime and high cell efficiency even upon bending. In situ X-ray absorption spectroscopy revealed that OOH* and O* intermediates induce variations in the Fe-Fe and Co-Co bond lengths, respectively, suggesting that Fe and Co species are crucial to the ORR/OER processes.

Constructing B and N separately co-doped carbon nanocapsules-wrapped Fe/Fe3C for oxygen reduction reaction with high current density.

The exploration of low-cost and highly efficient non-platinum electrocatalysts for the oxygen reduction reaction (ORR) is vital for renewable systems. Herein, we report a novel non-platinum electrocatalyst consisting of B and N separately co-doped graphitic carbon encapsulated Fe/Fe3C nanoparticles (BNGFe), which were synthesized from a facile method by adopting melamine, iron nitrate and boric acid as the precursors. In this synthesis, the N atoms in melamine first bond with the iron ions in iron nitrate, which could prevent the formation of BN covalent bonds during the subsequent pyrolysed process, resulting in the formation of effective B and N separately co-doped graphitic carbon encapsulated on the Fe/Fe3C nanoparticles. The synthetic BNGFe catalyst shows outstanding catalytic performance for ORR with an onset potential of 0.98 V (vs. RHE) and a high limiting diffusion current density, which could be comparable to the state-of-the-art commercial Pt/C catalyst in alkaline electrolyte.

Phosphorus-Doped Carbon Nitride Tubes with a Layered Micro-nanostructure for Enhanced Visible-Light Photocatalytic Hydrogen Evolution.

Phosphorus-doped hexagonal tubular carbon nitride (P-TCN) with the layered stacking structure was obtained from a hexagonal rod-like single crystal supramolecular precursor (monoclinic, C2/m). The production process of P-TCN involves two steps: 1) the precursor was prepared by self-assembly of melamine with cyanuric acid from in situ hydrolysis of melamine under phosphorous acid-assisted hydrothermal conditions; 2) the pyrolysis was initiated at the center of precursor under heating, thus giving the hexagonal P-TCN. The tubular structure favors the enhancement of light scattering and active sites. Meanwhile, the introduction of phosphorus leads to a narrow band gap and increased electric conductivity. Thus, the P-TCN exhibited a high hydrogen evolution rate of 67 µmol h(-1) (0.1 g catalyst, λ >420 nm) in the presence of sacrificial agents, and an apparent quantum efficiency of 5.68 % at 420 nm, which is better than most of bulk g-C3 N4 reported.

Small-Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro-oxidation.

The anchoring of small-sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H4 [SiO4 (W3 O9 )4 ] (SiW12 ) and CNTs modified with polyethylenimine (PEI-CNTs) was ground to dryness. Small-sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH3 . Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small-sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro-oxidation reaction. The mass activity of Pt-WN/CNTs-G-70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg(-1) Pt , better that those of commercial Pt/C (340 mA mg(-1) Pt ) and Pt/CNTs (162 mA mg(-1) Pt ). The Pt-WN/CNTs-G also displayed good CO tolerance. In contrast, Pt-WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg(-1) Pt , verifying the key role of grinding treatment in the preparation of WN/CNTs with good co-catalytic effect.

Three-dimensional Fe2 N@C microspheres grown on reduced graphite oxide for lithium-ion batteries and the Li storage mechanism.

Nanostructured iron compounds as lithium-ion-battery anode material have attracted considerable attention with respect to improved electrochemical energy storage and excellent specific capacity, so lots of iron-based composites have been developed. Herein, a novel composite composed of three-dimensional Fe2 N@C microspheres grown on reduced graphite oxide (denoted as Fe2 N@C-RGO) has been synthesized through a simple and effective technique assisted by a hydrothermal and subsequent heating treatment process. As the anode material for lithium-ion batteries, the synthetic Fe2 N@C-RGO displayed excellent Li(+) -ion storage performance with a considerable initial capacity of 847 mAh g(-1) , a superior cycle stability (a specific discharge capacity of 760 mAh g(-1) remained after the 100th cycle), and an improved rate-capability performance compared with those of the pure Fe2 N and Fe2 N-RGO nanostructures. The good performance should be attributed to the existence of RGO layers that can facilitate to enhance the conductivity and shorten the lithium-ion diffusion path; in addition, the carbon layer on the surface of Fe2 N can avert the structure decay caused by the volume change during the lithiation/delithiation process. Moreover, in situ X-ray absorption fine-structure analysis demonstrated that the excellent performance can be attributed to the lack of any obvious change in the coordination geometry of Fe2 N@C-RGO during the charge/discharge processes.