Tuning Surface Potential Polarization to Enhance N2 Affinity for Ammonia Electrosynthesis.

Electrocatalytic N2 reduction reaction (NRR) to synthesize ammonia is a sustainable reaction that is expected to replace Haber Bosch process. Laminated Bi2WO6 has great potential as an NRR electrocatalyst, however, the effective activity requires that the inert substrate is fully activated. Here, for the first time, success is achieved in activating the Bi2WO6 basal planes with NRR activity through Ti doping. The introduction of Ti successfully tunes the surface potential distribution and enhances the N2 adsorption. The subsequently strong hybrid coupling of d(Ti)-p(N) orbitals fills the electronic state of N2 antibonding molecular orbital, which greatly weakens the bonding strength of N≡N bonds. Further, in situ synchrotron radiation-based Fourier transform infrared (SR-FTIR) spectrum and theoretical calculations show that surface potential polarization enhances the adsorption of HNN* by Bi-Ti dual-metal sites, which is beneficial for the subsequent activation hydrogenation process. The Ti-Bi2WO6 nanosheets achieve 11.44% Faradaic efficiency (-0.2 V vs. RHE), a NH3 yield rate of 23.14 µg mg-1 h-1 (15N calibration), and satisfactory stability in 0.1 M HCl environment. The mutual assistance of theory and experiment can help understand and develop of excellent two-dimensional (2D) materials for the NRR.

Selective NOx- Electroreduction to Ammonia on Isolated Ru Sites.

Nitrate and nitrite (NOx-) are widespread contaminants in industrial wastewater and groundwater. Sustainable ammonia (NH3) production via NOx- electroreduction provides a prospective alternative to the energy-intensive industrialized Haber-Bosch process. However, selectively regulating the reaction pathway, which involves complicated electron/proton transfer, toward NH3 generation relies on the robust catalyst. A specific consideration in designing selective NOx--to-NH3 catalysts should meet the criteria to suppress competing hydrogen evolution and avoid the presence of neighboring active sites that are in favor of adverse N-N coupling. Nevertheless, efforts in this regard are still inadequate. Herein, we demonstrate that isolated ruthenium sites can selectively reduce NOx- into NH3, with maximal Faradaic efficiencies of 97.8% (NO2- reduction) and 72.8% (NO3- reduction) at -0.6 and -0.4 V, respectively. Density functional theory calculations simulated the reaction mechanisms and identified the *NO → *NOH as the potential rate-limiting step for NOx--to-NH3 conversion on single-atom Ru sites.

Size-Dependent Nickel-Based Electrocatalysts for Selective CO2 Reduction.

Closing the anthropogenic carbon cycle by converting CO2 into reusable chemicals is an attractive solution to mitigate rising concentrations of CO2 in the atmosphere. Herein, we prepared Ni metal catalysts ranging in size from single atoms to over 100 nm and distributed them across N-doped carbon substrates which were obtained from converted zeolitic imidazolate frameworks (ZIF). The results show variance in CO2 reduction performance with variance in Ni metal size. Ni single atoms demonstrate a superior Faradaic efficiency (FE) for CO selectivity (ca. 97 % at -0.8 V vs. RHE), while results for 4.1 nm Ni nanoparticles are slightly lower (ca. 93 %). Further increase the Ni particle size to 37.2 nm allows the H2 evolution reaction (HER) to compete with the CO2 reduction reaction (CO2 RR). The FE towards CO production decreases to under 30 % and HER efficiency increase to over 70 %. These results show a size-dependent CO2 reduction for various sizes of Ni metal catalysts.

Photo/Bio-Electrochemical Systems for Environmental Remediation and Energy Harvesting.

Water and energy systems are interdependent: water is utilized in each stage of energy production, and energy is required to extract, treat, and deliver water for many uses. However, energy and water systems are usually developed and managed independently. In the quest to develop environmentally friendly and energy-efficient solutions for water and energy issues, photoelectrochemical (PEC) energy conversion and microbial electrochemical (MEC) systems show profound potential for addressing environmental remediation problems and harvesting energy simultaneously. Herein, PEC, MEC, and their variant hybrid systems toward energy conversion and environmental remediation are summarized and discussed.

Active Electron Density Modulation of Co3 O4 -Based Catalysts Enhances their Oxygen Evolution Performance.

Despite the fact that many strategies have been developed to improve the efficiency of the oxygen evolution reaction (OER), the precise modulation of the surface electronic properties of catalysts to improve their catalytic activity is still challenging. Herein, we demonstrate that the surface active electron density of Co3 O4 can be effectively regulated by an argon-ion irradiation method. X-ray photoelectron and synchrotron x-ray absorption spectroscopy, UV photoelectron spectrometry, and DFT calculations show that the surface active electron density band center of Co3 O4 has been upshifted, leading to a significantly enhanced absorption capability of the oxo group. The optimized Co3 O4 -based catalysts exhibit an excellent overpotential of 260 mV at 10 mA cm-2 and Tafel slope of 54 mV dec-1 , superior to the capability of the benchmark RuO2 , representing one of the best Co-based OER catalysts. This approach could guide the future rational design and discovery of ideal electrocatalysts.

Anionic Dopant Delocalization through p-Band Modulation to Endow Metal Oxides with Enhanced Visible-Light Photoactivity.

An N-doped TiO2 model reveals a conceptually different mechanism for activating the N dopant based on delocalized orbital hybridization through O vacancy incorporation. Synchrotron-based X-ray absorption spectroscopy, time-resolved fluorescence, and DFT studies revealed that O vacancy incorporation can effectively stimulate the delocalization of N impurity states through p-band orbital modulation, which leads to a significant enhancement in photocarrier lifetime. Consequently, this effect also results in a remarkable increase in the incident photon-to-electron conversion efficiency in the range of 400-550 nm compared to that of conventional N-incorporated TiO2 (15 % versus 1 % at 450 nm). This work reveals the fundamental necessity of orbital modulation in the band engineering of metal oxides for driving solar water splitting and beyond.

Co2P Nanoparticles Wrapped in Amorphous Porous Carbon as an Efficient and Stable Catalyst for Water Oxidation.

Exploring highly active, enduringly stable, and low-cost oxygen evolution reaction catalysts continues to be a dominant challenge to commercialize renewable electrochemical water-splitting technology. High-active and earth-abundant cobalt phosphides are recently considered as promising candidates. However, the poor inherent electron transfer efficiency and instability hinder its further development. In this work, a novel approach was demonstrated to effectively synthesize Co2P nanoparticles wrapped in amorphous porous carbon framework (Co2P/C). Benefiting from extremely high specific surface area of porous carbon, plenty of active sites were adequately exposed. Meanwhile, unique anchoring structure between Co2P nanoparticles and amorphous carbon outerwear insured high charge transfer efficiency and superior stability of Co2P/C. Due to these favorable properties, low overpotential of 281 mV at 10 mA cm-2 and Tafel slope of 69 mV dec-1 were achieved in resultant Co2P/C catalyst. More significantly, it only exhibited a negligible overpotential increase after 30 h stability test, and these performances entirely preceded commercial RuO2 benchmark. In summary, we proposed a simple and feasible strategy to prepare metal phosphides wrapped with amorphous porous carbon outerwear for efficient and durable electrochemical water oxidation.

Significantly enhanced visible light response in single TiO2 nanowire by nitrogen ion implantation.

The metal-oxide semiconductor TiO2 shows enormous potential in the field of photoelectric detection; however, UV-light absorption only restricts its widespread application. It is considered that nitrogen doping can improve the visible light absorption of TiO2, but the effect of traditional chemical doping is far from being used for visible light detection. Herein, we dramatically broadened the absorption spectrum of the TiO2 nanowire (NW) by nitrogen ion implantation and apply the N-doped single TiO2 NW to visible light detection for the first time. Moreover, this novel strategy effectively modifies the surface states and thus regulates the height of Schottky barriers at the metal/semiconductor interface, which is crucial to realizing high responsivity and a fast response rate. Under the illumination of a laser with a wavelength of 457 nm, our fabricated photodetector exhibits favorable responsivity (8 A W-1) and a short response time (0.5 s). These results indicate that ion implantation is a promising method in exploring the visible light detection of TiO2.