Thermal suppression of charge disproportionation accelerates interface electron transfer of water electrolysis.

The sluggish electron transfer kinetics in electrode polarization driven oxygen evolution reaction (OER) result in big energy barriers of water electrolysis. Accelerating the electron transfer at the electrolyte/catalytic layer/catalyst bulk interfaces is an efficient way to improve electricity-to-hydrogen efficiency. Herein, the electron transfer at the Sr3Fe2O7@SrFeOOH bulk/catalytic layer interface is accelerated by heating to eliminate charge disproportionation from Fe4+ to Fe3+ and Fe5+ in Sr3Fe2O7, a physical effect to thermally stabilize high-spin Fe4+ (t2g3eg1), providing available orbitals as electron transfer channels without pairing energy. As a result of thermal-induced changes in electronic states via thermal comproportionation, a sudden increase in OER performances was achieved as heating to completely suppress charge disproportionation, breaking a linear Arrhenius relationship. The strategy of regulating electronic states by thermal field opens a broad avenue to overcome the electron transfer barriers in water splitting.

Trivalent Nickel-Catalyzing Electroconversion of Alcohols to Carboxylic Acids.

The comprehension of activity and selectivity origins of the electrooxidation of organics is a crucial knot for the development of a highly efficient energy conversion system that can produce value-added chemicals on both the anode and cathode. Here, we find that the potential-retaining trivalent nickel in NiOOH (Fermi level, -7.4 eV) is capable of selectively oxidizing various primary alcohols to carboxylic acids through a nucleophilic attack and nonredox electron transfer process. This nonredox trivalent nickel is highly efficient in oxidizing primary alcohols (methanol, ethanol, propanol, butanol, and benzyl alcohol) that are equipped with the appropriate highest occupied molecular orbital (HOMO) levels (-7.1 to -6.5 eV vs vacuum level) and the negative dual local softness values (Δsk, -0.50 to -0.19) of nucleophilic atoms in nucleophilic hydroxyl functional groups. However, the carboxylic acid products exhibit a deeper HOMO level (<-7.4 eV) or a positive Δsk, suggesting that they are highly stable and weakly nucleophilic on NiOOH. The combination (HOMO, Δsk) is useful in explaining the activity and selectivity origins of electrochemically oxidizing alcohols to carboxylic acid. Our findings are valuable in creating efficient energy conversions to generate value-added chemicals on dual electrodes.

Iron 3D-Orbital Configuration Dependent Electron Transfer for Efficient Fenton-Like Catalysis.

Transition metals are excellent active sites to activate peroxymonosulfate (PMS) for water treatment, but the favorable electronic structures governing  reaction mechanism still remain elusive. Herein, the authors construct typical d-orbital configurations on iron octahedral (FeOh ) and tetrahedral (FeTd ) sites in spinel ZnFe2 O4 and FeAl2 O4 , respectively. ZnFe2 O4 (136.58 min-1 F-1 cm2 ) presented higher specific activity than FeAl2 O4 (97.47 min-1 F-1 cm2 ) for tetracycline removal by PMS activation. Considering orbital features of charge amount, spin state, and orbital arrangement by magnetic spectroscopic analysis, ZnFe2 O4 has a larger bond order to decompose PMS. Using this descriptor, high-spin FeOh is assumed to activate PMS mainly to produce nonradical reactive oxygen species (ROS) while high-spin FeTd prefers to induce radical species. This hypothesis is confirmed by the selective predominant ROS of 1 O2 on ZnFe2 O4 and O2 •- on FeAl2 O4 via quenching experiments. Electrochemical determinations reveal that FeOh has superior capability than FeTd for feasible valence transformation of iron cations and fast interfacial electron transfer. DFT calculations further suggest octahedral d-orbital configuration of ZnFe2 O4 is beneficial to enhancing Fe-O covalence for electron exchange. This work attempts to understand the d-orbital configuration-dependent PMS activation to design efficient catalysts.

Synthesis of H2O2 to Self-Catalyzed Generation of •OH over ZnO/CuI/Cu Foam Electrode for the Self-Fenton Cleaning of Wastewater.

A novel ZnO/CuI/Cu foam electrode was constructed, which demonstrated excellent photoelectrocatalytic activity for the self-Fenton degradation of tetracycline in water. The H2O2 yield was 405.0 µmol L-1 over ZnO/CuI/Cu foam (CIZ-3) under light irradiation (100 mW cm-2) for 5 h at -1.23 V (vs NHE), which was 1.7 times higher than that of ZnO/Cu foam and 1.6 times higher than that of CuI/Cu foam, respectively. The 99.0% of tetracycline was degraded by CIZ-3 due to its efficient yield of H2O2 to self-catalyzed generation of •OH. The results of the open-circuit potential between CuI and ZnO displayed that the electrons from the conduction band of CuI flowed to ZnO and the holes from the valence band of ZnO migrated to CuI. As a result, the photogenerated electron-hole pairs of ZnO/CuI were efficiently separated, which greatly promoted the photoelectrocatalytic activity of ZnO/CuI/foam. The toxicity of the aqueous tetracycline solution was significantly reduced by observing the growth of Escherichia coli in the treated wastewater.

Strong Electronic Interaction Enables Enhanced Solar-Driven CO2 Reduction into Selective CH4 on SrTiO3 with Photodeposited Pt2+ Sites.

Targeting selective CO2 photoreduction into CH4 remains a challenge due to the sluggish reaction kinetics and poor hydrogenation ability of the unstable intermediate. Here, the active Pt2+ sites were photodeposited on the SrTiO3 photocatalyst, which was well demonstrated to manipulate the CH4 product selectivity. The results showed that SrTiO3 mainly yielded the CO (6.98 µmol g-1) product with poor CH4 (0.17 µmol g-1). With the Pt2+ modification, 100% CH4 selectivity could be obtained with an optimized yield rate of 8.07 µmol g-1. The prominent enhancement resulted from the following roles: (1) the strong electronic interaction between the Pt2+ cocatalyst and SrTiO3 could prompt efficient separation of the photoelectron-hole pairs. (2) The Pt2+ sites were active to capture and activate inert CO2 into HCO3- and CO32- species and allowed fast *COOH formation with the lowered reaction barrier. (3) Compared with SrTiO3, the formed *CO species could be captured tightly on the Pt2+ cocatalyst surface for generating the *CH2 intermediate by the following electron-proton coupling reaction, thus leading to the CH4 product with 100% selectivity.

Stable CO2reduction under natural air on Ni-Sn hydroxide photocatalyst with dynamic renewable oxygen vacancies.

Advanced photocatalysts are highly desired to activate the photocatalytic CO2reduction reaction (CO2RR) with low concentration. Herein, the NiSn(OH)6with rich surface lattice hydroxyls was synthesized to boost the activity directly under the natural air. Results showed that terminal Ni-OH could serve as donors to feed protons and generate oxygen vacancies (VO), thus beneficial to convert the activated CO2(HCO3-) mainly into CO (5.60µmol g-1) in the atmosphere. It was flexible and widely applicable for a stable CO2RR from high pure to air level free of additionally adding H2O reactant, and higher than the traditional gas-liquid-solid (1.58µmol g-1) and gas-solid (4.07µmol g-1) reaction system both using high pure CO2and plenty of H2O. The strong hydrophilia by the rich surface hydroxyls allowed robust H2O molecule adsorption and dissociation at VOsites to achieve the Ni-OH regeneration, leading to a stable CO yield (11.61µmol g-1) with the enriched renewable VOregardless of the poor CO2and H2O in air. This work opens up new possibilities for the practical application of natural photosynthesis.

Carbonized Polymer Dots/Bi/ß-Bi2O3 for Efficient Photosynthesis of H2O2 via Redox Dual Pathways.

A novel heterojunction photocatalyst of carbonized polymer dots (CPDs)/Bi/ß-Bi2O3 is successfully synthesized via a one-pot solvothermal method by adjusting the reaction temperature and time. As a solvent and carbon source, ethylene glycol not only supports the conversion of Bi3+ to ß-Bi2O3 but also undergoes its polymerization, cross-linking, and carbonization to produce CPDs. In addition, partial Bi3+ is reduced to Bi by ethylene glycol. As a result, the CPDs and Bi are deposited in situ on the surface of ß-Bi2O3 microspheres. There are four built-in electric fields in the CPDs/Bi/ß-Bi2O3 system, namely, the n-type semiconductor ß-Bi2O3/H2O interface, the p-type CPDs/H2O interface, the ohmic contact between Bi and ß-Bi2O3, and the Schottky junction between Bi and CPDs. Under the action of four built-in electric fields, the Z-type charge separation mechanism is formed. It promotes the effective separation of the photogenerated electron-hole and greatly improves the yield of H2O2. Under irradiation for 2 h, the H2O2 production is 1590 µmol g-1 h-1. The solar energy to H2O2 conversion efficiency is 0.11%.

Multifunctional Au/Hydroxide Interface toward Enhanced C-C Coupling for Solar-Driven CO2 Reduction into C2H6.

The high-grade C2+ products from CO2 photoreduction are limited by the kinetic bottleneck. Herein, a multifunctional Au/hydroxide interface was put forward to improve the C-C coupling. As a prototype, the synthesized Au/ZnSn(OH)6 tuned the CO generation and afforded about 50% electrons toward C2H6 selectivity. The prominent enhancement resulted from the following effects: (1) strong metal-support electronic interactions built an electric field at the interface of ZnSn(OH)6 nearby the Au nanoparticles, leading to fast transfer of electrons for the C-H and C-C bonding reactions. (2) The surface solid-state Sn-OH and Zn-OH lattice hydroxyls served as donors to feed rich H+ and oxygen vacancies (OVs) via hole-induced oxidation for the boosted C2H6 formation. (3) The synergetic OVs and Au sites allowed efficient e-/H+ to boost *CO hydrogenation toward *CH3 and *CH3*CH3 formation into the C2H6 product.

Synergy Effect of the Enhanced Local Electric Field and Built-In Electric Field of CoS/Mo-Doped BiVO4 for Photoelectrochemical Water Oxidation.

Bismuth vanadate is a promising material for photoelectrochemical water oxidation. However, it suffers from a low quantum efficiency, poor stability, and slow water oxidation kinetics. Here, we developed a novel photoanode of CoS/Mo-BiVO4 with excellent photoelectrochemical water oxidation performance. It achieved a photocurrent density of 4.5 mA cm-2 at 1.23 V versus the reversible hydrogen electrode, ∼4 times that of BiVO4. The CoS/Mo-BiVO4 photoanode also exhibited good stability, and the photocurrent density generated by the CoS/Mo-BiVO4 photoanode did not significantly decrease after light irradiation for 2 h. Upon replacement of part of the V with Mo doping in BiVO4, the local electric field around the Mo-O bond was enhanced, thus promoting carrier separation in BiVO4. The CoS was deposited on the surface of Mo-BiVO4, forming a built-in electric field at the interface. Under the action of the bias electric field and the built-in electric field, the carriers of CoS/Mo-BiVO4 were efficiently separated in the direction of the inverse type II heterojunction. In addition, CoS improved the light absorption and charge injection efficiency of the CoS/Mo-BiVO4 photoanode.

Heat-Induced Magnetic Transition for Water Electrolysis on NiFeN@NiFeOOH Core-Shell Assembly.

The overpotentials of electrochemical oxygen evolution reaction (OER) inherently originate from high electron transfer barriers of the redox couple driven water oxidation. Here, we propose a heat-induced magnetic transition strategy to reduce the spin-related electron transfer barriers. Coupling heat into electrochemical OER on a ferro-antiferromagnetic core-shell NiFeN@NiFeOOH, the heat-induced ferro-to-paramagnetic transition for NiFeN core at 55 °C and antiferro-to-paramagnetic transition for NiFeOOH shell at 70 °C significantly accelerate and accordingly achieve a cascaded Ni2+/Ni3+ driven water oxidation reaction. In addition, paramagnetic Niδ+ (δ ≥ 3) in NiFeN@NiFeOOH can thermochemically react with water to produce oxygen. The heat-induced magnetic transition concomitantly triggers the electrochemical redox couple driven water oxidation and the thermochemical water oxidation due to that heat-induced paramagnetic spin reduces the barriers of electricity driving the spin flipping. Our findings offer new insights into constructing the heat-electricity coupling water splitting.

Deficit drip irrigation based on crop evapotranspiration and precipitation forecast improves water- use efficiency and grain yield of summer maize.

BACKGROUND: Limited and erratic precipitation with inefficient irrigation scheduling often leads to an unstable crop yield and low water-use efficiency (WUE) in semi-arid and semi-humid regions. A 2-year field experiment was conducted to evaluate the effect of three irrigation strategies (conventional irrigation (CK), full-drip irrigation (FI), based on crop evapotranspiration and precipitation forecast, and deficit drip irrigation (DI) (75% FI)) on photosynthetic characteristics, leaf-to-air temperature difference (∆T), grain yield, and the WUE of summer maize. RESULTS: The results showed that the daily average net photosynthetic rate (Pn) of DI and FI increased by 25.4% and 25.8% at jointing stage in 2018, and 26.3% and 26.5% at grain-filling stage in 2019 compared with CK, respectively. At jointing stage in 2018 and grain-filling stage in 2019, the transpiration rate (Tr) of DI was significantly lower than that of FI (P < 0.05) but there was insignificant difference in Pn value (P > 0.05). The ∆T between 12:00-14:00 of DI and FI was significantly lower than that of CK at jointing stage in 2018 and grain-filling stage in 2019 (P < 0.05). The 2-year average grain yields of DI and FI were 11.4 and 11.5 t ha-1 , which increased by 32.4% and 32.8% compared with CK, respectively. The WUE of DI was 2.82 kg m-3 , which was 17.9% and 33.8% higher than that of FI and CK, respectively. CONCLUSION: Deficit drip irrigation based on crop evapotranspiration and precipitation forecast improves crop WUE and maintains high grain yields in semi-arid and semi-humid regions. © 2021 Society of Chemical Industry.

Direct Electrochemical Protonation of Metal Oxide Particles.

Metal oxides with surface protonation exhibit versatile physical and chemical properties suitable for use in many fields. Here, we develop an electrochemical route to directly protonize the physically assembled oxide particles, such as TiO2, Nb2O5, and WO3, in a Na2SO4 neutral electrolyte, which is a result of electrochemically induced oxygen vacancies reacting with water molecules. With no need of electric connection among particles or between particles and conductive substrate, the electrochemical protonation follows a bottom-up particle-by-particle surface protonation mechanism due to the fact that the protonation inducing high surface conductivity creates an efficient electron transfer pathway among particles. Our results show that electrochemical protonation of particles provides a chance to finely functionalize the surface of a single particle by only adjusting electrode potentials. Such a facile, cost-efficient, and green route is easy to run for a large-scale production and unlocks the potential of semiconductor oxides for various applications.

Selectively triggering photoelectromacro for CO2to CH4reduction over SrTiO3{110} facet with dual-metal sites.

In this article, the roles of surface-active sites in dominating photoelectron selectivity for CO2reduction products are well demonstrated over photocatalyst models of SrTiO3{100} and {110} facets. On the easily exposed {100} facets terminated with Sr-O atoms, photoelectrons are of 8 mol % for CH4and 92 mol % for CO generation. The Sr-O-Ti configuration in the {110} facets could enrich the surface charge density due to the lower interface resistance for higher photocatalytic efficiency (1.6 fold). The dual sites of Ti and adjacent Sr atoms are active for strong adsorption and activation of the generated CO* species from primary CO2reduction on the surface, thus kinetically favoring the activity of photoelectrons (73 mol %) in hydrogenation for CH2* species and hence CH4product. Inversely, the poor CH4selectivity is due to difficulty in the subsequent photoelectron reduction reaction by the weak adsorption of CO* at the single-Sr site on the {100} facets, independent of the electron and proton concentration. Our results may offer some illuminating insights into the design of a highly efficient photocatalyst for selective CO2reduction.

The charge carrier dynamics, efficiency and stability of two-dimensional material-based perovskite solar cells.

Perovskites have been firmly established as one of the most promising materials for third-generation solar cells. There remain several great and lingering challenges to be addressed regarding device efficiency and stability. The photovoltaic efficiency of perovskite solar cells (PSCs) depends drastically on the charge-carrier dynamics. This complex process includes charge-carrier generation, extraction, transport and collection, each of which needs to be modulated in a favorable manner to achieve high performance. Two-dimensional materials (TDMs) including graphene and its derivatives, transition metal dichalcogenides (e.g., MoS2, WS2), black phosphorus (BP), metal nanosheets and two-dimensional (2D) perovskite active layers have attracted much attention for application in perovskite solar cells due to their high carrier mobility and tunable work function properties which greatly impact the charge carrier dynamics of PSCs. To date, significant advances have been achieved in the field of TDM-based PSCs. In this review, the recent progress in the development and application of TDMs (i.e., graphene, graphdiyne, transition metal dichalcogenides, BP, and others) as electrodes, hole transporting layers, electron transporting layers and buffer layers in PSCs is detailed. 2D perovskites as active absorber materials in PSCs are also summarized. The effect of TDMs and 2D perovskites on the charge carrier dynamics of PSCs is discussed to provide a comprehensive understanding of their optoelectronic processes. The challenges facing the PSC devices are emphasized with corresponding solutions to these problems provided with the overall goal of improving the efficiency and stability of photovoltaic devices.

Combined application of soluble organic and chemical fertilizers in drip fertigation improves nitrogen use efficiency and enhances tomato yield and quality.

BACKGROUND: Sustainable greenhouse tomato production requires optimal fertilizer management to achieve the double-win strategy of producing high yields and maximizing profits with less environmental pollution. The objective of this study was to seek an optimal fertilization strategy maintaining high productivity of greenhouse tomato, improving nitrogen use efficiency and reducing nitrate leaching risk. RESULTS: The combined application of soluble organic and chemical fertilizers for topdressing (SOSC) not only produced more fruit yield (75.18 Mg ha-1 ) and plant dry matter (10 449.12 kg ha-1 ), but also enhanced plant nutrients uptake, nitrogen recovery efficiency (39.22%), nitrogen agronomic efficiency (176.78 kg kg-1 ), soluble solids, vitamin C and lycopene content in tomato fruits compared with the other treatments, that is chicken manures for basal application and chemical fertilizer for topdressing (CC), soluble organic fertilizer for topdressing (SO) and soluble chemical fertilizer for topdressing (SC). In terms of soil nutrients residue, SOSC had no obvious NO3 - -N accumulation area in the 0-60 cm soil layer, unlike large accumulation in the soil layer below 30 cm in SO and SC. CONCLUSION: The combined application of soluble organic and chemical fertilizers is highly recommended to sustain fruit yield, improve nitrogen use efficiency and reduce soil degradation risks in commercial greenhouse tomato production.

Optimization of Controlled Water and Nitrogen Fertigation on Greenhouse Culture of Capsicum annuum.

This study investigated the effects of different combinations of irrigation and nitrogen levels on the growth of greenhouse sweet peppers, assessing yield, quality, water use efficiency (WUE), and partial factor productivity from applied N (PFPN). By using controlled drip irrigation, the optimal conditions for efficient, large-scale, high-yield, and high quality production of sweet peppers in Northwest China were determined. Using the local conventional irrigation and nitrogen regime as a control (105% ET0, N: 300 kg·hm-2), three alternative irrigation levels were also tested, at 90%, 75%, and 60% ET0. These were combined with nitrogen levels at 100%, as the control, and 75%, 50%, and 25%, resulting in 16 combination treatments. The results show that different supplies of water and nitrogen nutrition had a significant impact on the growth, yield, WUE, PFPN, and quality of fruit. The treatments of W0.90N0.75, W0.90N0.50, W0.75N0.75, and W0.75N0.50 can better maintain the "source-sink" relationship of peppers. They increased the economic yield, WUE, and PFPN. A principal component analysis was performed to evaluate indicators of fruit quality, revealing that the treatment of W0.75N0.50 resulted in the best fruit quality. For greenhouse sweet peppers produced in Northwest China, the combination of W0.90N0.75 resulted in the highest economic yield of 34.85 kg·hm-2. The combination of W0.75N0.75 had the highest WUE of 16.50 kg·m-3. The W0.75N0.50 combination treatment had the highest fruit quality score. For sustainable ecological development and in view of limited water resources in the area, we recommend the W0.75N0.50 combination treatment, since it could obtain the optimal fruit quality, while its economic yield and WUE were 9% and 4% less than the maximum, respectively. This study provides a theoretical basis for the optimal management of water and nitrogen during production of greenhouse sweet peppers in Northwest China.

Solution-chemical route to generalized synthesis of metal germanate nanowires with room-temperature, light-driven hydrogenation activity of CO2 into renewable hydrocarbon fuels.

A facile solution-chemical route was developed for the generalized preparation of a family of highly uniform metal germanate nanowires on a large scale. This route is based on the use of hydrazine monohydrate/H2O as a mixed solvent under solvothermal conditions. Hydrazine has multiple effects on the generation of the nanowires: as an alkali solvent, a coordination agent, and crystal anisotropic growth director. Different-percentage cobalt-doped Cd2Ge2O6 nanowires were also successfully obtained through the addition of Co(OAc)2·4H2O to the initial reaction mixture for future investigation of the magnetic properties of these nanowires. The considerably negative conduction band level of the Cd2Ge2O6 nanowire offers a high driving force for photogenerated electron transfer to CO2 under UV-vis illumination, which facilitates CO2 photocatalytic reduction to a renewable hydrocarbon fuel in the presence of water vapor at room temperature.

MnO2 nanolayers on highly conductive TiO(0.54)N(0.46) nanotubes for supercapacitor electrodes with high power density and cyclic stability.

Pseudo-capacitive MnO2 supercapacitors are attracting intense interest because of the theoretically high specific capacitance (1370 F g(-1)) and low cost of MnO2. For the practical application, the power density and the cyclic stability of MnO2-based supercapacitors are expected to be improved. Increasing the efficiency of the current collection is an effective method to improve the power density for a given supercapacitor. Here, the highly conductive and electrochemically stable material, titanium oxynitride (TiO0.54N0.46), is used as the current collector. Uniform amorphous MnO2 nanolayers were deposited on metal-phase TiO0.54N0.46 nanotube arrays using a modified electrochemical deposition method. The resulting MnO2 supercapacitors exhibited a high power density of 620 kW kg(-1) at an energy density of 9.8 W h kg(-1). This is comparable to high-performance carbon-based electrochemical double layer capacitors in aqueous electrolytes. The high electron transport was enhanced with a highly conductive TiO0.54N0.46 scaffold. Ion transport was promoted in the nanotube structures that had porous walls. In addition, the close interfacial connection between MnO2 and TiO0.54N0.46 contributed to the excellent cyclic stability (ca. 92.0% capacitance retention after 100 000 cycles). These results indicated that the highly conductive and electrochemically stable titanium oxynitride is an excellent candidate for use as an electrode material in high performance supercapacitors.

Thermal Migration to Recover Spent Pt/C Catalyst.

Recovery of spent Pt/C catalyst is a sustainable low-cost route to promote large-scale application of hydrogen fuel cells. Here, we report a thermal migration strategy to recover the spent Pt/C. In this route, the ZIF-8 is used to produce nitrogen doped porous carbon (NC) with abundant pyrimidine nitrogen sites as the new support. Subsequently, the spent Pt/C, NC, and NH4Cl etching reagent are mixed and heated at 900 oC to thermally migrate Pt from Pt/C onto NC with the help of NH4Cl etching reagent. The thermal-volatilized Pt tends to be captured by the pyrimidine nitrogen sites of NC support, thus producing the Pt clusters or 4 - 5 nm Pt particles. The recovered Pt/NC catalyst exhibits the highly stable oxygen reduction activities with a mass activity of 0.6 A mgPt-1 after 30000-cycle accelerated durability test.

Thermal-Stabilized Protonated TiO2 for Heat-Accelerated Photoelectrochemical Water Splitting.

Enhancing the charge separation efficiency is a big challenge that limits the energy conversion efficiency of photoelectrochemical (PEC) water splitting. Surface states generated by protonation of TiO2 are the efficient charge separation passageways to massively accept or transfer the photogenerated electrons. However, a challenge is to avoid the deprotonation of a protonated TiO2 photoelectrode at the operation temperature. Here, we found that the terminal hydroxyl group (OHT) as surface states on the TiO2 surface generated via electrochemical protonation of TiO2 at 90 °C [90-TiO2-x-(OH)x] is thermally stable. As a result, the thermally enhanced photocurrent of the 90-TiO2-x-(OH)x electrode reached 1.05 mA cm-2 under 80 °C, and the stability was maintained up to 10 h with a slight photocurrent decrease of 3%. The thermally stable surface states as charge separation paths provide an effective method to couple the heat field with the PEC process via thermal-stimulating hopping of polarons.