Asymmetric Ligands of a Metal-Organic Framework on Enhanced Photocatalytic CO2 Reduction.

Metal-organic frameworks (MOFs) have been studied extensively in the catalytic field. However, the role of ligands in catalysis has been less well investigated. Here, an asymmetric ligand photocatalytic strategy for CO2 reduction in MOFs is first proposed. MOF-303(Al) with asymmetric ligands (pyrazolyldicarboxylic acid) exhibits synergistic catalytic effects. Specifically, pyrazoles participate in CO2 activation; i.e., pyrazole and µ2-OH form hydrogen bonds with CO2 to polarize C═O bonds. Furthermore, the lowest unoccupied molecular orbital (LUMO; A pyrazole) and highest occupied molecular orbital (HOMO; B pyrazole) act as the electron donor and acceptor to spatially separate the excited electron-hole, with A and B pyrazoles for CO2 and H2O adsorption to avoid competition, respectively. Owing to its advantages, MOF-303-modified g-C3N4 achieves nonsacrificial and transition-metal-free photocatalytic CO2 reduction to CO of 16.19 µmol·g-1·h-1, significantly higher than that of g-C3N4. This work provides fresh insights into asymmetric ligands in photocatalytic CO2 reduction.

Oxidation of Toluene over Mesoporous MnO2/CeO2 Nanosphere Catalysts: Effects of the MnO2 Precursor and the Type of Support.

Toluene is the most common volatile organic compound (VOC), and the MnO2-based catalyst is one of the excellent nonprecious metal catalysts for toluene oxidation. In this study, the effects of MnO2 precursors and the support types on the oxidation performance of toluene were systematically explored. The results showed that the 15MnO2/MS-CeO2-N catalyst with Mn(NO3)2·4H2O as the precursor and the mesoporous CeO2 nanosphere (MS-CeO2) as the support exhibited the most excellent performance. To reveal the reason behind this phenomenon, the calcination process of the catalyst precursor and the reaction process of toluene oxidation were investigated by in situ DRIFTS. It was found that the MnO2 precursor and the type of catalyst support could have a large effect on the reaction pathway and the produced intermediates. Therefore, the roles of the MnO2 precursor and the type of support should be key considerations when developing the high-performance MnO2-based toluene oxidation catalyst.

Facile H2O-Contributed O2 Activation Strategy over Mn-Based SCR Catalysts to Counteract SO2 Poisoning.

Mn-based catalysts preferred in low-temperature selective catalytic reduction (SCR) are susceptible to SO2 poisoning. The stubborn sulfates make insufficient O2 activation and result in deficient reactive oxygen species (ROS) for activating reaction molecules. H2O has long been regarded as an accomplice to SO2, hastening catalyst deactivation. However, such a negative impression of the SCR reaction was reversed by our recent research. Here, we reported a H2O contribution over Mn-based SCR catalysts to counteract SO2 poisoning through accessible O2 activation, in which O2 was synergistically activated with H2O to generate ROS for less deactivation and more expected regeneration. The resulting ROS benefited from the energetically favorable route supported by water-induced Ea reduction and was actively involved in the NH3 activation and NO oxidation process. Besides, ROS maintained high stability over the SO2 + H2O-deactivated γ-MnO2 catalyst throughout the mild thermal treatment, achieving complete regeneration of its own NO disposal ability. This strategy was proven to be universally applicable to other Mn-based catalysts.

Metal-Free Photocatalytic CO2 Reduction to CH4 and H2 O2 under Non-sacrificial Ambient Conditions.

Photocatalytic CO2 reduction to CH4 requires photosensitizers and sacrificial agents to provide sufficient electrons and protons through metal-based photocatalysts, and the separation of CH4 from by-product O2 has poor applications. Herein, we successfully synthesize a metal-free photocatalyst of a novel electron-acceptor 4,5,9,10-pyrenetetrone (PT), to our best knowledge, this is the first time that metal-free catalyst achieves non-sacrificial photocatalytic CO2 to CH4 and easily separable H2 O2 . This photocatalyst offers CH4 product of 10.6 µmol ⋅ g-1 ⋅ h-1 under non-sacrificial ambient conditions (room temperature, and only water), which is two orders of magnitude higher than that of the reported metal-free photocatalysts. Comprehensive in situ characterizations and calculations reveal a multi-step reaction mechanism, in which the long-lived oxygen-centered radical in the excited PT provides as a site for CO2 activation, resulting in a stabilized cyclic carbonate intermediate with a lower formation energy. This key intermediate is thermodynamically crucial for the subsequent reduction to CH4 product with the electronic selectivity of up to 90 %. The work provides fresh insights on the economic viability of photocatalytic CO2 reduction to easily separable CH4 in non-sacrificial and metal-free conditions.

Advantageous Interfacial Effects of AgPd/g-C3 N4 for Photocatalytic Hydrogen Evolution: Electronic Structure and H2 O Dissociation.

Bimetallic AgPd nanoparticles have been synthesized before, but the interfacial electronic effects of AgPd on the photocatalytic performance have been investigated less. In this work, the results of hydrogen evolution suggest that the bimetallic AgPd/g-C3 N4 sample has superior activity to Ag/g-C3 N4 and Pd/g-C3 N4 photocatalysts. The UV/Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, CO adsorption diffuse reflectance FTIR spectroscopy, and FTIR results demonstrate that in the AgPd/g-C3 N4 , the surface electronic structures of Pd and Ag are changed, which is beneficial for faster photogenerated electron transfer and greater H2 O molecule adsorption. In situ ESR spectra suggest that, under visible light irradiation, there is more H2 O dissociation to radical species on the AgPd/g-C3 N4 photocatalyst. Furthermore, DFT calculations confirm the interfacial electronic effects of AgPd/g-C3 N4 , that is, Pdδ- ⋅⋅⋅Agδ+ , and the activation energy of H2 O molecule dissociation on AgPd/g-C3 N4 is the lowest, which is the main contributor to the enhanced photocatalytic H2 evolution.

Biochar amendment improves crop production in problem soils: A review.

Problem soils are referred to as those with poor physical, chemical, and biological properties that inhibit or prevent plant growth. These poor properties may be a result of soil formation processes but are largely due to inappropriate farming practices or anthropogenic pollution. The world has lost a third of its arable land due to erosion and pollution in the past 40 years. Thus, there is an urgent need for improving and remediating problem soils. As a novel multifunctional carbon material, biochar has been widely used as a soil amendment for improving soil quality. Previous reviews have summarized the characteristics of biochar, the interactions with various soil contaminants, and the effects on soil quality, soil productivity, and carbon sequestration. Relatively limited attention has been focused on the effects of biochar amendment on plant growth in problem soils. As a result, a comprehensive review of literature in the Web of Science was conducted with a focus on the effects of biochar amendment on plant growth in problems soils. The review is intended to present an overview about problem soils, biochars as functional materials for soil amendment, how amended biochars interact with soils, soil microbes, and plant roots in remediation of problem soil and improve plant growth. Additionally, existing knowledge gaps and future directions are discussed. Information gathered from this review suggests that biochar amendment is a viable way of improving the quality of problem soils and enhancing crop production. It is anticipated that further research on biochar amendment will increase our understanding on the interactions of biochar with components of problem soils, speed up our effort on soil remediation, and improve crop production in problem soils.

Crystal-plane-dependent metal-support interaction in Au/TiO2.

Metal-support interactions between Au and TiO2 are studied based on Au/TiO2 catalysts with different TiO2 crystal planes exposed. With ex situ XPS, TEM and in situ DRIFTS, we have investigated the crystal-plane-dependent metal-support interaction effects on the physiochemical properties of Au/TiO2 catalysts. Based on the structural characterization and spectroscopic results, we can observe chemical oscillations (including the electronic structures of Au nanoparticles and the interaction between Au/TiO2 catalysts and CO molecules) during alternate H2 and O2 pre-treatments. Their variation tendencies of oscillations are greatly dependent on the crystal planes of TiO2 and the pre-treatment temperature. Furthermore, their surface and electronic changes after H2 and O2 pre-treatments can be well correlated with their catalytic activities in CO oxidation. Electron-transfer processes across the Au-TiO2 interface are proved to be the origin accounting for their changes after H2 and O2 pre-treatments. The different electronic structures of different TiO2 crystal planes should have relationships with the crystal-plane-dependent metal-support interaction effects in Au/TiO2.

Enhancing Photosynthesis Efficiency of Hydrogen Peroxide by Modulating Side Chains to Facilitate Water Oxidation at Low-Energy Barrier Sites.

Hydrogen peroxide (H2O2) is a crucial oxidant in advanced oxidation processes. In situ, photosynthesis of it in natural water holds the promise of practical application for water remediation. However, current photosynthesis of H2O2 systems primarily relies on oxygen reduction, leading to limited performance in natural water with low dissolved oxygen or anaerobic conditions found in polluted water. Herein, a novel photocatalyst based on conjugated polymers with alternating electron donor-acceptor structures and electron-withdrawing side chains on electron donors is introduced. Specifically, carbazole functions as the electron donor, triazine serves as the electron acceptor, and cyano acts as the electron-withdrawing side chain. Notably, the photocatalyst exhibits a remarkable solar-to-chemical conversion of 0.64%, the highest reported in natural water. Furthermore, even in anaerobic conditions, it achieves an impressive H2O2 photosynthetic efficiency of 1365 µmol g-1 h-1, surpassing all the reported photosynthetic systems of H2O2. This remarkable improvement is attributed to the effective relocation of the water oxidation active site from a high-energy carbazole to a low-energy acetylene site mediated by the side chains, resulting in enhanced O2 or H2O2 generation from water. This breakthrough offers a new avenue for efficient water remediation using advanced oxidation technologies in oxygen-limited environments, holding significant implications for environmental restoration.

Edge-Rich Bicrystalline 1T/2H-MoS2 Cocatalyst-Decorated {110} Terminated CeO2 Nanorods for Photocatalytic Hydrogen Evolution.

Developing all-solid-state Z-scheme systems with highly active photocatalysts are of huge interest in realizing long-term solar-to-fuel conversion. Here we reported an innovative hybrid of {110}-oriented CeO2 nanorods with edge-enriched bicrystalline 1T/2H-MoS2 coupling as efficient photocatalysts for water splitting. In the composites, the metallic 1T phase acts as an excellent solid state electron mediator in the Z-scheme, while the 2H phase and CeO2 are the adsorption sites of the photosensitizer and reactant (H2O), respectively. Through optimal structure and phase engineering, 1T/2H-MoS2@CeO2 heterojunctions simultaneously achieve high charge separation efficiency, proliferated density of exposed active sites, and excellent affinity to reactant molecules, reaching a superior hydrogen evolution rate of 73.1 µmol/h with an apparent quantum yield of 8.2% at 420 nm. Furthermore, density functional theory calculations show that 1T/2H-MoS2@CeO2 possesses the advantages of intensive electronic interaction from the built-in electric field (negative MoS2 and positive charged CeO2) and reduced H2O adsorption/dissociation energies. This work sheds light on the design of on-demand noble-metal-free Z-scheme heterostructures for solar energy conversion.

Advantageous Role of Ir0 Supported on TiO2 Nanosheets in Photocatalytic CO2 Reduction to CH4: Fast Electron Transfer and Rich Surface Hydroxyl Groups.

Ir-based heterogeneous catalysts for photocatalytic CO2 reduction have rarely been reported and are worthy of investigation. In this work, TiO2 nanosheets with a higher specific surface area and more oxygen vacancies were employed to support Ir metal by impregnation (Imp) and ethylene glycol (EG) reduction methods. In comparison with Ir/TiO2 (Imp) and TiO2, Ir/TiO2 (EG) exhibited excellent photocatalytic performance toward CO2 reduction, especially for CH4 production on account of the oxygen defect of TiO2 and rich surface hydroxyl groups produced from the interaction between TiO2 nanosheets and metallic Ir. In situ ESR suggested that the oxygen defect was significant for CO2 adsorption/activation. Furthermore, metallic Ir was beneficial for photogenerated electron transfer, surface hydroxyl generation, and adsorption of the CO intermediate, generating more available electrons and reducing agents for CH4 production. In situ CO2 DRIFTS confirmed the key synergistic interaction between the oxygen defect and metallic Ir in the photoreduction from CO2 to CH4.

Facile Ball-Milling Synthesis of CuO/Biochar Nanocomposites for Efficient Removal of Reactive Red 120.

With the goal of improving the removal of anionic contaminants, copper oxide (CuO)-modified biochar (BC) nanocomposites were successfully prepared through simply ball milling CuO particles with BC. The physicochemical properties of the fabricated CuO/BC nanocomposites were systematically characterized by a series of techniques; their adsorption performances were assessed, and the main adsorption mechanism was revealed. X-ray powder diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses of the nanocomposites showed the strong interaction between CuO and BC and confirmed the success of the ball-milling syntheses. Because of strong electrostatic attraction between the embedded CuO nanoparticles and reactive red (RR120), the composited adsorbents exhibited excellent RR120 removal. The 10%-CuO/BC nanocomposite achieved the best RR120 removal efficiency (46%), which is much higher than that of pristine BC (20%). In addition, the adsorption was insensitive to the change of solution initial pH (4-10). The 10%-CuO/BC also showed fast adsorption kinetics (equilibrium time < 3 h) and extremely high adsorption capacity (Langmuir maximum capacity of 1399 mg g-1) to RR120 in aqueous solutions. Findings from this study demonstrate not only the strong feasibility of ball-milling synthesis of BC-based nanocomposites but also the promising potential of the CuO/BC nanocomposites to remove aqueous anionic contaminants.

Biochar technology in wastewater treatment: A critical review.

Biochar is a promising agent for wastewater treatment, soil remediation, and gas storage and separation. This review summarizes recent research development on biochar production and applications with a focus on the application of biochar technology in wastewater treatment. Different technologies for biochar production, with an emphasis on pre-treatment of feedstock and post treatment, are succinctly summarized. Biochar has been extensively used as an adsorbent to remove toxic metals, organic pollutants, and nutrients from wastewater. Compared to pristine biochar, engineered/designer biochar generally has larger surface area, stronger adsorption capacity, or more abundant surface functional groups (SFG), which represents a new type of carbon material with great application prospects in various wastewater treatments. As the first of its kind, this critical review emphasizes the promising prospects of biochar technology in the treatment of various wastewater including industrial wastewater (dye, battery manufacture, and dairy wastewater), municipal wastewater, agricultural wastewater, and stormwater. Future research on engineered/designer biochar production and its field-scale application is discussed. Based on the review, it can be concluded that biochar technology represents a new, cost effective, and environmentally-friendly solution for the treatment of wastewater.

Adsorption of acetone and cyclohexane onto CO2 activated hydrochars.

Most of the volatile organic compounds (VOCs) are toxic and harmful to human health and environment. In this study, hydrochars activated with CO2 were applied to remove VOCs. Two typical VOCs, acetone and cyclohexane, were used as the 'model' adsorbates to evaluate hydrochars' performance. Specific surface areas of pristine hydrochars were small (<8 m2/g), whereas activated hydrochars showed much higher values (up to 1308 m2/g). As a result, the adsorption of VOCs onto the pristine hydrochars (13.24-24.64 mg/g) was lower than that of the activated ones (39.42-121.74 mg/g). The adsorption of the two VOCs onto the hydrochars was exothermal. In addition, there were significant correlations (R2 > 0.91) between the VOC removal and hydrochars' specific surface area. These results suggest that the governing mechanism was mainly physical adsorption. Increasing experimental temperature (80-139 °C) desorbed the VOCs from the hydrochars. Due to its higher boiling point, cyclohexane desorption required a higher temperature than acetone desorption. The reusability of the activated hydrochars to the two VOCs was confirmed by five continuous adsorption-desorption cycles. The overall results indicated that hydrochars, particularly after CO2 activation, are sufficient for VOC abatement.

Integrated adsorption and photocatalytic degradation of volatile organic compounds (VOCs) using carbon-based nanocomposites: A critical review.

Volatile organic compounds (VOCs) are harmful for human and surrounding ecosystem, and a great number of VOC abatement technologies have been developed during the past few decades. However, the single method has some problems such as high energy consumption, unfriendly environment, and low removal efficiency. Recently, the integration of adsorption and photocatalytic degradation of VOCs is considered as a promising one. Carbon material, with large surface area, high adsorption capacity, and fast electron transfer ability, is widely used in integrated adsorptive-photocatalytic removal of VOCs. It is thus crucial to digest and summarize recent research advances in carbon-based nanocomposites as the adsorbent-photocatalyst for VOC removal. To satisfy this need, this work provides a critical review of the related literature with focuses on: (1) the advantages and disadvantages of various carbon-based nanocomposites for the applications of VOC adsorption and photocatalytic degradation; (2) models and mechanisms of adsorptive-photocatalytic removal of VOCs according to the material properties; and (3) major factors controlling adsorption-photocatalysis processes of VOCs. The review is aimed to establish the "structure-property-application" relationships for the development of innovative carbon-supported nanocomposites and to promote future research on the integrated adsorptive and photocatalytic removal of VOCs.

Ultrafine Bi3TaO7 Nanodot-Decorated V, N Codoped TiO2 Nanoblocks for Visible-Light Photocatalytic Activity: Interfacial Effect and Mechanism Insight.

Bi3TaO7 is a potential photocatalyst because of its high chemical stability, defective fluorite-type structure, and superior mobility of photoinduced holes. However, few studies have focused on the interfacial effects of Bi3TaO7-based photocatalysts. In this work, 0D Bi3TaO7 nanodot-hybridized 3D V and N codoped TiO2 nanoblock (B/VNT) composites were first synthesized for the photocatalytic removal of oxytetracycline hydrochloride, 2,4,6-trichlorophenol, and tetrabromobisphenol A. The fabricated B/VNT had a photocatalytic performance superior to that of pristine components, and probable degradation pathways were proposed according to the primary intermediates identified by a gas chromatography-mass spectrometer. Interestingly, on B/VNT, the transfer of interfacial electrons was observed from V/N-TiO2 to Bi3TaO7, and the formed built-in electronic field led to a direct Z-scheme structure, rather than type II, as confirmed by the generated •OH and •O2- radicals and band structures from the density functional theory calculation. Therefore, the strong interfacial electronic interaction on the B/VNT was significant, which drove faster photogenerated charge transfer, more visible-light adsorption, and active •OH and •O2- generation, thus improving the photocatalytic activity.

Chemically activated hydrochar as an effective adsorbent for volatile organic compounds (VOCs).

Hydrochars derived from hickory wood and peanut hull through hydrothermal carbonization were activated with H3PO4 and KOH to improve their performance as a volatile organic compound (VOC) adsorbent. Polar acetone and nonpolar cyclohexane were used as representative VOCs. The VOC adsorptive capacities of the activated hydrochars (50.57-159.66 mg⋅g-1) were greater than that of the nonactivated hydrochars (15.98-25.36 mg⋅g-1), which was mainly caused by the enlargement of surface area. The significant linear correlation (R2 = 0.984 on acetone, and R2 = 0.869 on cyclohexane) between BET surface areas of hydrochars and their VOC adsorption capacities, together with the obvious adsorption exothermal peak of differential scanning calorimetry curve confirmed physical adsorption as the dominating mechanism. Finally, the reusability of activated hydrochar was tested on H3PO4 activated hickory hydrochar (HHP), which had higher acetone and cyclohexane adsorption capacities. After five continuous adsorption desorption cycles, the adsorptive capacities of acetone and cyclohexane on HHP decreased by 6.2% and 7.8%, respectively. The slight decline in adsorption capacity confirmed the reusability of activated hydrochar as a VOC sorbent.

Pore Size Expansion Accelerates Ammonium Bisulfate Decomposition for Improved Sulfur Resistance in Low-Temperature NH3-SCR.

Sulfur poisoning has long been recognized as a bottleneck for the development of long-lived NH3-selective catalytic reduction (SCR) catalysts. Ammonium bisulfate (ABS) deposition on active sites is the major cause of sulfur poisoning at low temperatures, and activating ABS decomposition is regarded as the ultimate way to alleviate sulfur poisoning. In the present study, we reported an interesting finding that ABS decomposition can be simply tailored via adjusting the pore size of the material it deposited. We initiated this study from the preparation of mesoporous silica SBA-15 with uniform one-dimensional pore structure but different pore sizes, followed by ABS loading to investigate the effect. The results showed that ABS decomposition proceeded more easily on SBA-15 with larger pores, and the decomposition temperature declined as large as 40 °C with increasing pore size of SBA-15 from 4.8 to 11.8 nm. To further ascertain the real effect in NH3-SCR reaction, the Fe2O3/SBA-15 probe catalyst was prepared. It was found that the catalyst with larger mesopores exhibited much improved sulfur resistance, and quantitative analysis results obtained from Fourier transform infrared and ion chromatograph further proved that the deposited sulfates were greatly alleviated. The result of the present study demonstrates for the first time the vital role of pore size engineering in ABS decomposition and may open up new opportunities for designing NH3-SCR catalysts with excellent sulfur resistance.

Synthesis of CrO x /C catalysts for low temperature NH3-SCR with enhanced regeneration ability in the presence of SO2.

Chromium oxide nano-particles with an average diameter of 3 nm covered by amorphous carbon (CrO x /C) were successfully synthesized. The synthesized CrO x /C materials were used for the selective catalytic reduction of NO x by NH3 (NH3-SCR), which shows superb NH3-SCR activity and in particular, satisfactory regeneration ability in the presence of SO2 compared with Mn-based catalysts. The as-prepared catalysts were characterized by XRD, HRTEM, Raman, FTIR, BET, TPD, TPR, XPS and in situ FTIR techniques. The results indicated presence of certain amounts of unstable lattice oxygen exposed on the surface of CrO x nano-particles with an average size of 3 nm in the CrO x /C samples, which led to NO being conveniently oxidized to NO2. The formed NO2 participated in NH3-SCR activity, reacting with catalysts via a "fast NH3-SCR" pathway, which enhanced th NH3-SCR performance of the CrO x /C catalysts. Furthermore, the stable lattice of the CrO x species made the catalyst immune to the sulfation process, which was inferred to be the cause of its superior regeneration ability in the presence of SO2. This study provides a simple way to synthesize stable CrO x nano-particles with active oxygen, and sheds light on designing NH3-SCR catalysts with highly efficient low temperature activity, SO2 tolerance, and regeneration ability.

Improved low temperature NH3-SCR performance of FeMnTiO(x) mixed oxide with CTAB-assisted synthesis.

FeMnTiOx mixed oxide is prepared by the CTAB-assisted co-precipitation method, and the transformation of anatase into rutile is inhibited by CTAB to some extent. The catalyst obtained in the present work shows nearly 100% NO conversion at 100-350 °C, more than 80% N2 selectivity at 75-200 °C, and excellent H2O durability for the selective catalytic reduction of NO by NH3 with a space velocity of 30,000 mL g(-1) h(-1).