Regulating Cu Oxidation State for Electrocatalytic CO2 Conversion into CO with Near-Unity Selectivity via Oxygen Spillover.

Cu-based catalysts are the most intensively studied in the field of electrocatalytic CO2 reduction reaction (CO2RR), demonstrating the capacity to yield diverse C1 and C2+ products albeit with unsatisfactory selectivity. Manipulation of the oxidation state of Cu sites during CO2RR process proves advantageous in modulating the selectivity of productions, but poses a formidable challenge. Here, an oxygen spillover strategy is proposed to enhance the oxidation state of Cu during CO2RR by incorporating the oxygen donor Sb2O4. The Cu-Sb bimetallic oxide catalyst attains a remarkable CO2-to-CO selectivity approaching unity, in stark contrast to the diverse product distribution observed with bare CuO. The exceptional Faradaic efficiency of CO can be maintained across a wide range of potential windows of ≈700 mV in 1 m KOH, and remains independent of the Cu/Sb ratio (ranging from 0.1:1 to 10:1). Correlative calculations and experimental results reveal that oxygen spillover from Sb2O4 to Cu sites maintains the relatively high valence state of Cu during CO2RR, which diminishes the binding strength of *CO, thereby achieving heightened selectivity in CO production. These findings propose the role of oxygen spillover in CO2RR over Cu-based catalysts, and shed light on the rational design of highly selective CO2 reduction catalysts.

Maskless photolithography based on ultraviolet micro-LEDs and direct writing method for improving pattern resolution.

Ultraviolet micro-LEDs show great potential as a light source for maskless photolithography. However, there are few reports on micro-LED based maskless photolithography systems, and the studies on the effects of system parameters on exposure patterns are still lacking. Hence, we developed a maskless photolithography system that employs micro-LEDs with peak wavelength 375 nm to produce micrometer-sized exposure patterns in photoresists. We also systematically explored the effects of exposure time and current density of micro-LED on static direct writing patterns, as well as the effects of stage velocity and current pulse width on dynamic direct writing patterns. Furthermore, reducing the size of micro-LED pixels enables obtaining high-resolution exposure patterns, but this approach will bring technical challenges and high costs. Therefore, this paper proposes an oblique direct writing method that, instead of reducing the micro-LED pixel size, improves the pattern resolution by changing the tilt angle of the sample. The experimental results show that the linewidths of the exposed lines decreased by 4.0% and 15.2%, respectively, as the sample tilt angle increased from 0° to 15° and 30°, which confirms the feasibility of the proposed method to improve the pattern resolution. This method is also expected to correct the exposure pattern error caused by optical distortion of the lens in the photolithography system. The system and method reported can be applied in various fields such as PCBs, photovoltaics, solar cells, and MEMS.

Earthworm gut digestion drives the transfer behavior of antibiotic resistance genes in layers of extracellular polymeric substances during vermicomposting of dewatered sludge.

Gut digestion by earthworms (GDE) is a crucial step in vermicomposting, affecting the fate of antibiotic resistance genes (ARGs) in vermicompost sludge. The extracellular polymeric substance (EPS) matrix of sludge is an important space for ARG transfer. However, the effect of GDE on EPS-associated ARGs remains unclear. Therefore, this study explored the role of GDE in driving the transfer of ARGs within different EPS layers in sludge. For this, the changes in intracellular ARGs and EPS-associated ARGs in sludge were analyzed after 5 days of the GDE process. The results showed that after the GDE process, both nitrate and dissolved organic carbon significantly increased in all EPS layers of sludge, while the proteins and polysaccharides only enhanced in soluble and loosely bound EPS of sludge. In addition, a 7.0% decrease in bacterial diversity was recorded after the GDE process, with a functional bacterial community structure emerging. Moreover, the absolute abundance of total ARGs and mobile genetic elements decreased by 90.71% and 61.83%, respectively, after the GDE process. Intracellular ARGs decreased by 92.1%, while EPS-associated ARGs increased by 4.9%, indicative of intracellular ARG translocation into the EPS during the GDE process. Notably, the ARGs exhibited significant enrichment in both the soluble and loosely bound EPS, whereas they were reduced in the tightly bound EPS. The structural equation modeling revealed that the GDE process effectively mitigated the ARG dissemination risk by modulating both the EPS structure and microenvironment, with the organic structure representing a primary factor influencing ARGs in the EPS.

Two-dimensional Keitz method for the radiant power measurement of planar ultraviolet excilamps.

Planar X e B r ∗ and X e C l ∗ excilamps emitting noncoherent narrowband UVB light (280-315 nm) are now widely used to cure psoriasis and vitiligo as well as to improve vitamin D synthesis. The two-dimensional integral formula has been deducted in this study, which is a good method and has great practical significance to calculate the total radiant power and assess the energy efficiency of a planar UV lamp. The measured radiant power of planar white LED lamps through a two-dimensional Keitz formula has been compared to that of gonio-photometer, verifying the applicability of the formula. The optimum measurement distance is dependent on the lamp length (1.5L≤D≤3.5L) for which the derivation from the two methods can be controlled within 10%. The planar X e B r ∗ excilamps have been measured and compared to coaxial excilamps, which show similar patterns of change for the radiant characteristics. Since the planar radiant power formula only needs to measure normal illuminance at a certain distance from the symmetric center of the lamp, it is more convenient to use and is a low-cost method to promote the development of large-sized planar ultraviolet lamps.

Effect of conventional and biodegradable microplastics on earthworms during vermicomposting process.

The potential effect of microplastics is an increasingly growing environmental issue. However, very little is known regarding the impact of microplastics on the vermicomposting process. The present study explored the effect of non-biodegradable (low density polyethylene; LDPE) and biodegradable (polybutylene succinate-co-adipate; PBSA) microplastics on earthworm Eisenia fetida during vermicomposting of cow dung. For this, earthworms were exposed to different concentrations (0, 0.5, 1 and 2%) of LDPE and PBSA of 2 mm size. The cow dung supported the growth and hatchlings of earthworms, and the toxicity effect of both LDPE and PBSA microplastics on Eisenia fetida was analyzed. Microplastics decreased the body weight of earthworms and there was no impact on hatchlings. The body weight of earthworm decreased from 0 to 60th day by 18.18% in 0.5% of LDPE treatment, 5.42% in 1% of LDPE, 20.58% in 2% of LDPE, 19.99% in 0.5% of PBSA, 15.09% in 1% of PBSA and 16.36% in 2% of PBSA. The physico-chemical parameters [pH (8.55-8.66), electrical conductivity (0.93-1.02 (S/m), organic matter (77.6-75.8%), total nitrogen (3.95-4.25 mg/kg) and total phosphorus (1.16-1.22 mg/kg)] do not show much significant changes with varying microplastics concentrations. Results of SEM and FTIR-ATR analysis observed the surface damage of earthworms, morphological and biochemical changes at higher concentrations of both LDPE and PBSA. The findings of the present study contribute to a better understanding of microplastics in vermicomposting system.

Genome-Wide Identification, Evolution, and Expression Analyses of AP2/ERF Family Transcription Factors in Erianthus fulvus.

The AP2/ERF transcription factor family is one of the most important gene families in plants and plays a vital role in plant abiotic stress responses. Although Erianthus fulvus is very important in the genetic improvement of sugarcane, there are few studies concerning AP2/ERF genes in E. fulvus. Here, we identified 145 AP2/ERF genes in the E. fulvus genome. Phylogenetic analysis classified them into five subfamilies. Evolutionary analysis showed that tandem and segmental duplication contributed to the expansion of the EfAP2/ERF family. Protein interaction analysis showed that twenty-eight EfAP2/ERF proteins and five other proteins had potential interaction relationships. Multiple cis-acting elements present in the EfAP2/ERF promoter were related to abiotic stress response, suggesting that EfAP2/ERF may contribute to adaptation to environmental changes. Transcriptomic and RT-qPCR analyses revealed that EfDREB10, EfDREB11, EfDREB39, EfDREB42, EfDREB44, EfERF43, and EfAP2-13 responded to cold stress, EfDREB5 and EfDREB42 responded to drought stress, and EfDREB5, EfDREB11, EfDREB39, EfERF43, and EfAP2-13 responded to ABA treatment. These results will be helpful for better understanding the molecular features and biological role of the E. fulvus AP2/ERF genes and lay a foundation for further research on the function of EfAP2/ERF genes and the regulatory mechanism of the abiotic stress response.

Temperature impacts fate of antibiotic resistance genes during vermicomposting of domestic excess activated sludge.

Effect of temperature on antibiotic resistance genes (ARGs) during vermicomposting of domestic excess sludge remains poorly understood. Vermicomposting experiment with excess sludge was conducted at three different temperatures (15 °C, 20 °C, and 25 °C) to investigate the fate of ARGs, bacterial community and their relationship in the process. The vermicomposting at 25 °C did not significantly attenuate the targeted ARGs relative to that at 15 °C and 20 °C. The dynamics of qnrA, qnrS, and tetM genes during vermicomposting at 15 °C and 20 °C followed the first-order kinetic model. Temperature remarkably impacted bacterial diversity of the final products with the lowest Shannon index at 25 °C. The presence of the genus (Aeromonas and Chitinophagaceae) at 25 °C may contribute to the rebound of the genes (qnrA, qnrS and tetM). The study indicates that 20 °C is a suitable vermicomposting temperature to simultaneously reach the highest removal efficiency of the ARGs and the good biostability of the final product.

Identification of intermediates of a molecular ruthenium catalyst for water oxidation using in situ electrochemical X-ray absorption spectroscopy.

This is the first study on a Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylic acid) catalyst in solution using a home-built electrochemical cell, in combination with an energy-dispersive X-ray absorption spectroscopy setup. The oxidation state and coordination number of the catalyst during electrocatalysis could be estimated, while avoiding radiation damage from the X-rays.

Baseline correction method based on improved adaptive iteratively reweighted penalized least squares for the x-ray fluorescence spectrum.

To solve the problem of baseline drift in the detection of soil samples by x-ray fluorescence spectrum, an improved adaptive iterative weighted penalized least squares (IairPLS) method is proposed to estimate the baseline of x-ray fluorescence spectrum signals. We improved the original exponential weight function to solve the problem of baseline underestimation caused by adaptive iterative weighted penalized least squares. The improved function effectively reduces the risk of baseline underestimation and speeds up the weighting process, achieving good results. In this paper, the MC simulation spectrum and soil real analysis spectrum are used to verify the performance of the algorithm. Finally, the algorithm is compared with previous penalized least squares methods (asymmetric least squares, adaptive iterative reweighted penalized least squares, and multiple constrained reweighted penalized least squares), with the results showing that the proposed method has the least root-mean-square error after baseline correction for optimal smoothing parameters λ and the best relative error of baseline estimation accuracy. Meanwhile, the IairPLS method can effectively improve the quantitative analysis ability of the x-ray fluorescence spectrum. The proposed method can be successfully applied to the actual x-ray fluorescence spectrum, which provides a powerful basis for quantitative analysis.

Photosynthetic spectral response curves of saffron leaves.

Saffron (Crocus sativus L.) is an herb with outstanding medicinal functions and commercial value. Light is an important factor in plant growth, and the sensitivity of plant photosynthesis to light quality can be characterized by photosynthetic spectral response curves. This study aims to measure the spectral response curves of saffron leaves so as to provide theoretical guidance for a supplemental lighting spectrum to increase saffron production. The measurement results show the peaks of spectral response curves of saffron leaves are at 480 nm and 660 nm, which provides a reference for the peak wavelengths of supplemental lighting spectrum. Full-spectrum white light with low color temperature or red light mixed with a little blue light might be most beneficial for saffron biomass accumulation.

A Cobalt@Cucurbit[5]uril Complex as a Highly Efficient Supramolecular Catalyst for Electrochemical and Photoelectrochemical Water Splitting.

A host-guest complex self-assembled through Co2+ and cucurbit[5]uril (Co@CB[5]) is used as a supramolecular catalyst on the surface of metal oxides including porous indium tin oxide (ITO) and porous BiVO4 for efficient electrochemical and photoelectrochemical water oxidation. When immobilized on ITO, Co@CB[5] exhibited a turnover frequency (TOF) of 9.9 s-1 at overpotential η=550 mV in a pH 9.2 borate buffer. Meanwhile, when Co@CB[5] complex was immobilized onto the surface of BiVO4 semiconductor, the assembled Co@CB[5]/BiVO4 photoanode exhibited a low onset potential of 0.15 V (vs. RHE) and a high photocurrent of 4.8 mA cm-2 at 1.23 V (vs. RHE) under 100 mW cm-2 (AM 1.5) light illumination. Kinetic studies confirmed that Co@CB[5] acts as a supramolecular water oxidation catalyst, and can effectively accelerate interfacial charge transfer between BiVO4 and electrolyte. Surface charge recombination of BiVO4 can be also significantly suppressed by Co@CB[5].

Identification of M-NH2 -NH2 Intermediate and Rate Determining Step for Nitrogen Reduction with Bioinspired Sulfur-Bonded FeW Catalyst.

The multimetallic sulfur-framework catalytic site of biological nitrogenases allows the efficient conversion of dinitrogen (N2 ) to ammonia (NH3 ) under ambient conditions. Inspired by biological nitrogenases, a bimetallic sulfide material (FeWSx @FeWO4 ) was synthesized as a highly efficient N2 reduction (NRR) catalyst by sulfur substitution of the surface of FeWO4 nanoparticles. Thus prepared FeWSx @FeWO4 catalysts exhibit a relatively high NH3 production rate of 30.2 ug h-1 mg-1cat and a Faraday efficiency of 16.4 % at -0.45 V versus a reversible hydrogen electrode in a flow cell; these results have been confirmed via purified 15 N2 -isotopic labeling experiments. In situ Raman spectra and hydrazine reduction kinetics analysis revealed that the reduction of undissociated hydrazine intermediates (M-NH2 -NH2 ) on the surface of the bimetallic sulfide catalyst is the rate-determing step for the NRR process. Therefore, this work can provide guidance for elucidating the structure-activity relationship of NRR catalysts.

Photocatalytic Generation of π-Allyltitanium Complexes via Radical Intermediates.

The addition of π-allylmetal complexes to carbonyls is the most important route to homoallylic alcohols. This study reports the first photocatalytic generation of π-allyltitanium complexes by a radical strategy. This novel strategy enables the three-component allylation of carbonyls with 1,3-butadiene, providing rapid access to valuable homoallylic alcohols (over 60 examples). The exceptional regio- and diastereoselectivity provided by dual photoredox/Ti catalysis is comparable to that of the Cr-catalyzed Nozaki-Hiyama-Kishi allylation reaction.

An investigation on possible effect of leaching fractions physiological responses of hot pepper plants to irrigation water salinity.

BACKGROUND: The modification effect of leaching fraction (LF) on the physiological responses of plants to irrigation water salinity (ECiw) remains unknown. Here, leaf gas exchange, photosynthetic light-response and CO2-response curves, and total carbon (C) and nitrogen (N) accumulation in hot pepper leaves were investigated under three ECiw levels (0.9, 4.7 and 7.0 dS m- 1) and two LFs treatments (0.17 and 0.29). RESULTS: Leaf stomatal conductance was more sensitive to ECiw than the net photosynthesis rate, leading to higher intrinsic water use efficiency (WUE) in higher ECiw, whereas the LF did not affect the intrinsic WUE. Carbon isotope discrimination was inhibited by ECiw, but was not affected by LF. ECiw reduced the carboxylation efficiency, photosynthetic capacity, photorespiration rate, apparent quantum yield of CO2 and irradiance-saturated rate of gross photosynthesis; however, LF did not influence any of these responses. Total C and N accumulation in plants leaves was markedly increased with either decreasing ECiw or increasing LF. CONCLUSIONS: The present study shows that higher ECiw depressed leaf gas exchange, photosynthesis capacity and total C and N accumulation in leaves, but enhanced intrinsic WUE. Somewhat surprisingly, higher LF did not affect the intrinsic WUE but enhanced the total C and N accumulation in leaves.

Comparative Analysis of two Sugarcane Ancestors Saccharum officinarum and S. spontaneum based on Complete Chloroplast Genome Sequences and Photosynthetic Ability in Cold Stress.

Polyploid Saccharum with complex genomes hindered the progress of sugarcane improvement, while their chloroplast genomes are much smaller and simpler. Chloroplast (cp), the vital organelle, is the site of plant photosynthesis, which also evolves other functions, such as tolerance to environmental stresses. In this study, the cp genome of two sugarcane ancestors Saccharum officinarum and S. spontaneum were sequenced, and genome comparative analysis between these two species was carried out, together with the photosynthetic ability. The length is 141,187 bp for S. officinarum and that is 7 bp longer than S. spontaneum, with the same GC content (38.44%) and annotated gene number (134), 13 with introns among them. There is a typical tetrad structure, including LSC, SSC, IRb and IRa. Of them, LSC and IRa/IRb are 18 bp longer and 6 bp shorter than those in S. spontaneum (83,047 bp and 22,795 bp), respectively, while the size of SSC is same (12,544 bp). Five genes exhibit contraction and expansion at the IR junctions, but only one gene ndhF with 29 bp expansion at the border of IRb/SSC. Nucleotide diversity (Pi) based on sliding window analysis showed that the single copy and noncoding regions were more divergent than IR- and coding regions, and the variant hotspots trnG-trnM, psbM-petN, trnR-rps14, ndhC-trnV and petA-psbJ in the LSC and trnL-ccsA in the SSC regions were detected, and petA-psbJ with the highest divergent value of 0.01500. Genetic distances of 65 protein genes vary from 0.00000 to 0.00288 between two species, and the selective pressure on them indicated that only petB was subjected to positive selection, while more genes including rpoC2, rps3, ccsA, ndhA, ndhA, psbI, atpH and psaC were subjected to purifying or very strong purifying selection. There are larger number of codons in S. spontaneum than that in S. officinarum, while both species have obvious codon preference and the codons with highest-(AUG) and lowest frequency (AUA) are same. Whilst, the most abundant amino acid is leucine in both S. officinarum and S. spontaneum, with number of 2175 (10.88% of total) and 2228 (10.90% of total) codons, respectively, and the lowest number is cysteine, with only 221 (1.105%) and 224 (1.096%), respectively. Protein collinearity analysis showed the high collinearity though several divergences were present in cp genomes, and identification of simple sequence repeats (SSRs) were included in this study. In addition, in order to compare cold tolerance and explore the expanding function of this environmental stress, the chlorophyll relative content (SPAD) and chlorophyll fluorescence Fv/Fm were measured. The significantly higher SPAD were observed in S. spontaneum than those in S. officinarum, no matter what the control conditions, exposure to low temperature or during recovery, and so was for Fv/Fm under exposure to low temperature, together with higher level of SPAD in S. spontaneum in each measurement. Aforementioned results suggest much stronger photosynthetic ability and cold tolerance in S. spontaneum. Our findings build a foundation to investigate the biological mechanism of two sugarcane ancestor chloroplasts and retrieve reliable molecular resources for phylogenetic and evolutionary studies, and will be conducive to genetic improvement of photosynthetic ability and cold resistance in modern sugarcane.

Residual chemical oxygen demand (COD) fractionation in bio-treated coking wastewater integrating solution property characterization.

The refractory nature of residual COD in bio-treated coking wastewater (BTCW) creates barriers for its further treatment and reclamation. It is necessary to fractionate the residual COD in BTCW associated with characterization of solution properties. In this paper, a stepwise process composed of membrane filtration, coagulation, adsorption and ozonation was proposed to fractionate residual COD in the BTCW, in which the COD was stepwise reduced to near zero. In addition, the correlation between COD and water quality indexes as well as solution properties were discussed together with a safety assessment of the water quality. Results showed that the residual COD fractionation percentage contributed by suspended solids, colloids, dissolved organics and reductive inorganic substances in the BTCW was 43.7%, 22.1%, 26.2% and 4.9%, respectively. By stepwise fractionating of these substances, the residual COD was reduced from 168.8 to 5.2 mg L-1, and the UV254 value decreased from 1.90 to 0.15 cm-1. In addition, the particle size of the dominant substances contributing to the residual COD was smaller than 450 nm. Among these substances, the hydrophobic fraction accounted for 78.66% (in the term of TOC). Three-dimensional excitation-emission matrix (3D-EEM) analysis showed that hydrophobic neutral substances (HON) were the main fluorescence constituent in the BTCW, which was highly removable by adsorption. The residual COD after adsorption was mainly composed of reductive inorganic substances. Apart from pursuit of high COD removal rates, more emphasis should be given to the removal of toxic COD. Correlations were observed between the residual COD and water quality indicators as well as solution properties, providing a guideline for optimized removal of residual COD in the BTCW. In summary, these results gave a referential information about the nature of residual COD in the BTCW for the selection of advanced treatment technologies and the management of water quality safety.

Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source.

The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni3+ intermediates involved in electrocatalytic water oxidation by nickel-based materials, we prepared NiBx as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiBx was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the simultaneous hydrogenation of p-nitrophenol to p-aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand-alone reactor in response to sunlight.

Enhancing microbial fuel cell (MFC) performance in treatment of solid potato waste by mixed feeding of boiled potato and waste activated sludge.

The effects of mixed feeding of boiled potato and waste activated sludge (WAS) on the performance of a microbial fuel cell (MFC) in treating solid potato waste were investigated. The coulombic efficiency (CE) of four MFCs fed with potato cubes containing 0, 48.7, 67.3 and 85.6% of boiled potato was 53.5, 70.5, 92.7 and 71.1%, respectively, indicating enhanced electricity generation and the existence of an optimum mixing ratio. The hydrolysis rate estimated using a first-order sequential hydrolysis model increased from 0.061 to 0.191 day-1, leading to shortening of the startup time for current density reaching its maximum from 25 to 5 days. The final chemical oxygen demand (COD) removal reached 85%. The CE of seven MFCs, fed with raw potato alone, sterilized/unsterilized WAS alone, and four mixed samples of raw potato with sterilized WAS at ratios of 2:1 and 4:1 and unsterilized WAS at 2:1 and 4:1, was found to be 6.1, 43.6, 0.3, 31.0, 16.5, 0.9 and 31.1%, respectively. The hydrolysis rate increased from 0.056 to 0.089 day-1, and the final COD removal changed from 39.5 to 89.6% following the order: potato alone > mixture of potato & WAS > sterilized WAS alone > unsterilized WAS alone.

Vaccination With Heterologous HIV-1 Envelope Sequences and Heterologous Adenovirus Vectors Increases T-Cell Responses to Conserved Regions: HVTN 083.

BACKGROUND: Increasing the breadth of human immunodeficiency virus type 1 (HIV-1) vaccine-elicited immune responses or targeting conserved regions may improve coverage of circulating strains. HIV Vaccine Trials Network 083 tested whether cellular immune responses with these features are induced by prime-boost strategies, using heterologous vectors, heterologous inserts, or a combination of both. METHODS: A total of 180 participants were randomly assigned to receive combinations of adenovirus vectors (Ad5 or Ad35) and HIV-1 envelope (Env) gene inserts (clade A or B) in a prime-boost regimen. RESULTS: T-cell responses to heterologous and homologous insert regimens targeted a similar number of epitopes (ratio of means, 1.0; 95% confidence interval [CI], .6-1.6; P = .91), but heterologous insert regimens induced significantly more epitopes that were shared between EnvA and EnvB than homologous insert regimens (ratio of means, 2.7; 95% CI, 1.2-5.7; P = .01). Participants in the heterologous versus homologous insert groups had T-cell responses that targeted epitopes with greater evolutionary conservation (mean entropy [±SD], 0.32 ± 0.1 bits; P = .003), and epitopes recognized by responders provided higher coverage (49%; P = .035). Heterologous vector regimens had higher numbers of total, EnvA, and EnvB epitopes than homologous vector regimens (P = .02, .044, and .045, respectively). CONCLUSIONS: These data demonstrate that vaccination with heterologous insert prime boosting increased T-cell responses to shared epitopes, while heterologous vector prime boosting increased the number of T-cell epitopes recognized. CLINICAL TRIALS REGISTRATION: NCT01095224.

Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven-coordinate Ru(IV) species was isolated as a reaction intermediate, shedding light on the reaction mechanisms of Ru-catalyzed water oxidation chemistry. Auxiliary ligands have dramatic effects on the water oxidation catalysis in terms of the reactivity and the reaction mechanism. For instance, Ru-bda (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts catalyze Ce(IV)-driven water oxidation extremely fast via the radical coupling of two Ru(V)═O species, while Ru-pda (H2pda = 1,10-phenanthroline-2,9-dicarboxylic acid) water oxidation catalysts catalyze the same reaction slowly via water nucleophilic attack on a Ru(V)═O species. With a number of active Ru catalysts in hands, light driven water oxidation was accomplished using catalysts with low catalytic onset potentials. The structures of molecular catalysts could be readily tailored to introduce additional functional groups, which favors the fabrication of state-of-the-art Ru-based water oxidation devices, such as electrochemical water oxidation anodes and photo-electrochemical anodes. The development of efficient water oxidation catalysts has led to a step forward in the sustainable energy system.