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Owing to rich-redox chemistry, metal-N4-molecular catalysts have been found as promising electrocatalysts for oxygen reduction reaction (ORR), however, de-metalation of the metal atom from N4-cavity in the electrolyte limits their activity and endurance. Herein, a MnN4-macrocyclic complex was prepared and characterized via various techniques. The results of analytical and theoretical studies suggest that the MnN4-macrocyclic complex has saddle-shaped geometry. Further, this complex was incorporated with black carbon (MnN4@CB) and studied for electrocatalytic ORR in alkaline media. The MnN4@CB composite displayed comparable ORR formal potential (−0.14 V vs Ag/AgCl) to the traditional 20% Pt/C catalyst (−0.13 V vs Ag/AgCl) and remarkable methanol tolerance. Theoretical studies revealed that the highest occupied molecular orbital (HOMO) of MnN4 has almost the same energy as the π∗ orbital of an O2 molecule, resulting in optimal coupling between HOMO and π∗ orbital, leading to efficient ORR. The charge distribution and 2D Fourier optimization of the MnN4-complex suggested that the N-donor atoms increased the electron density on Mn-atom, and transferred into the π∗ orbital of O2, weakening the O–O bond during ORR. In addition to developing low-cost ORR electrocatalysts, this work will contribute to defining their activity descriptors.

In this work, we designed a novel Bi2MoO6/Bi2MoO6-x homojunction photocatalyst and successfully fabricated by a facile solvothermal-calcination approach. Experimental characterizations indicated that the formation of Bi2MoO6/Bi2MoO6-x homojunction was caused by controlling oxygen vacancies formation. Such Bi2MoO6/Bi2MoO6-x homojunction exhibits about 240 times higher photocatalytic activity towards phenol degradation as compared with pure Bi2MoO6 under visible light irradiation. Similarly, for a co-existed phenol and Cr(VI) model system, Bi2MoO6/Bi2MoO6-x-catalyzed the photodegradation of phenol and the reduction of Cr(VI) simultaneously occur, and Bi2MoO6/Bi2MoO6-x homojunction also displays a superior photocatalytic activity, that is 4 and 8 times higher than pure Bi2MoO6, respectively. The remarkably boosted photocatalytic activity could be attributed primarily to the highly efficient separation of photogenerated electrons/holes due to the homojunction and the synergistic effect between phenol oxidation and Cr(VI) reduction. Thus, the present insight provides an effective strategy for designing and preparing highly active photocatalysts with the incorporation of oxygen vacancies modulation and applying for environmental remediation.

Ammonia (NH3) plays a significant role in fertilizer production to support the ever-increasing population and serves as a renewable energy carrier as well as a zero-carbon emission fuel. Currently, NH3 is produced by a non-sustainable and highly energy-intensive process. Among the available alternatives, the electrochemical nitrogen reduction reactions (NRR) has attracted attention due to the compact and on-site electrolytic cells that can operate from solar or wind power under ambient conditions but still suffer from relatively low Faraday efficiency and NH3 yields. For the commercialization of electrocatalytic NRR, a catalytic material demonstrating a FE ∼50% and an NH3 yield rate of ∼10−6 mol s−1 cm−2 is suggested. Various strategies, including amorphization, structural engineering, catalyst-support interactions and hydrogen evolution suppression over catalytic materials, have been presented to enhance the electrocatalytic NRR. In this review, the current progress of various identified NRR electrocatalysts (including metal carbides, nitrides, oxides, phosphides, sulfides, selenides, borides, bimetallic materials, metal-organic frameworks, and metal-free materials) is summarized by collectively focusing on both theoretical analysis and experimental investigations. For further development of rational catalysts, a collaboration of theoretical and experimental studies, advanced characterization techniques, understanding of the electrocatalytic mechanism, efficient screening systems, and precise detection methods are needed. Specially designed electrocatalysts can improve NRR activity by regulating the cathodic reactions. The challenges and future perspectives have been described with special emphasis on various transition metal-based electrocatalysts for N2 fixation.

Visible-light-driven photoelectrochemical (PEC) catalysis has been widely studied as a promising technique for the degradation of organic pollutants in wastewater. Herein, we report a sulfite-enhanced PEC degradation process for the degradation of organic pollutant. The degradation rate was significantly enhanced by ～30 times with the addition of 16 mM sulfite. The Electron Spin Resonance (ESR), Transient Absorption (TA) and hole scavenger studies showed that sulfite radicals ( S O 3 ⦁ - ) were the main reactive species in the reactions. The pollutant degradation pathway was studied by in-situ techniques and mass spectrometer, showing that the sulfite addition can promote the cleavage of aromatic ring C C bond and C N bond.

SO2 and CO2 emitted from using of fossil fuels are causing serious environmental issues. Herein we put forward a promising strategy to realize CO2 reduction and SO2 removal simultaneously through a photoelectrochemical (PEC) process based on nanoelectrodes. In the present work, SO2 was oxidized to SO42− on BiVO4 photoanode after being absorbed by NaHCO3 solutions. At the same time, CO2 reduction occurred on nanoflower-like copper-indium alloy cathode. The absorption efficiency of SO2 was greater than 95%, and SO32− was oxidized to SO42− with oxidation efficiency about 50% in 3 h. Moreover, the energy of SO2 was recycled to assist the CO2 reduction on the cathode, consequently, the photocurrent densities were increased at least 3 times after introducing SO2. CO2 reduction with CO and HCOOH as main products was improved significantly when SO2 removal was conducted simultaneously. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments were also performed to study the adsorption and conversion of SO2 on BiVO4 nanoparticles. The proposed approach could efficiently remove SO2 and recycle the energy of it to reduce CO2 into useful chemicals. This work provides a sustainable strategy for dealing with CO2 and SO2 in the flue gas by combining desulfurization and CO2 reduction in one PEC cell using nanoelectrodes.

Bisphenol A (BPA) is known as an endocrine-disrupting chemical, generally present in the environment. It has a harmful effect on aquatic lives and human health, therefore it is needful to exploit highly efficient innovative treatment methods for its removal. Herein, we report a Co-BiVO4 photoanode to activate peroxymonosulfate (PMS) for the complete removal of BPA via a photoelectrochemical (PEC) process. The Co-BiVO4 could degrade 99.16% of BPA in the presence of 2 mM PMS within 60 min, whereas the degradation rate constant is 0.08034 min−1, which was 20.86 times higher than the electrocatalytic (EC) and 5.35 times higher than the photocatalytic (PC) process. Notably, Co-BiVO4 showed significant activity toward PMS activation and BPA degradation as compared to other synthesized photocatalysts. Their photoelectrocatalytic performance followed the sequence Co-BiVO4 > Fe-BiVO4 > Ni-BiVO4 > pure-BiVO4 > without catalysts. Several influencing factors on the decomposition process, such as the effect of PMS concentration, applied potential, illumination time, initial pH, BPA concentration, Co loading, and co-existing anions were studied in detail. Radical scavenging experiment and transient absorption result showed that sulfate radicals (SO4•─) were the dominant reactive species. Moreover, a significant synergistic effect was noticed in Co-BiVO4/PEC/PMS system for BPA degradation. Degradation mechanism and reaction intermediates were studied by in-situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) and liquid chromatography-mass spectroscopy (LC-MS) presenting the enhanced bond cleavage in PEC activated PMS system. The BPA showed 92.47% and 87.27% removal in tap and river water samples after 60 min of reaction using Co-BiVO4/PMS PEC system. Our finding proposed an efficient method for wastewater treatment in an eco-friendly way.