Efficient photoreduction of carbon dioxide to ethanol using diatomic nitrogen-doped black phosphorus.

Successful conversion of CO2 into C2 products requires the development of new catalysts that overcome the difficulties in efficient light harvesting and CO-CO coupling. Herein, density functional theory (DFT) is used to assess the photoreduction properties of nitrogen-doped black phosphorus. The geometric structure, redox potential, first step of hydrogenation activation, CO desorption, and CO-CO coupling are systematically calculated, based on which the diatomic nitrogen-doped black phosphorus (N2@BPV) stands out. The calculated results of the CO2RR pathway demonstrate that N2@BPV has excellent selectivity and high activity for CH3CH2OH production. The results of the time-dependent ab initio nonadiabatic molecular dynamics simulation show that the diatomic N active sites of N2@BPV facilitate charge separation and inhibit electron-hole recombination. In addition, the activation mechanism of CO2 is studied. The main reason for CO2 activation is attributed to the imbalance in electron transfer that destroys the symmetry of CO2. We expect that our study will offer some theoretical guidance in CO2 conversion.

Characterization of Type I/II g-C3N4/MoS2 van der Waals Heterostructures: A New Theoretical Insight.

The charge transfer mechanism of the g-C3N4/MoS2 heterojunction is still disputed. Some regard it as a type I pathway, some regard it as a type II pathway, and still some regard it as a Z-scheme pathway. Especially, the results obtained by density functional theory (DFT) calculations are not totally in agreement. Here, we constructed four g-C3N4/MoS2 heterojunctions on the basis of the aperture alignment modes of g-C3N4 and MoS2. Their morphology and photocatalytic activity were investigated via first-principles and excited state dynamics simulations. By systemically comparing the interfacial binding energy and electronic structure (e.g., band structure, electrostatic potential, and band edge positions) of g-C3N4/MoS2 heterojunctions, we found that both type I and type II band alignment structures could be obtained. Moreover, the calculated lifetimes of interlayer photogenerated electrons and holes show that type II g-C3N4/MoS2 tends to favor a general type II pathway rather than a Z-scheme pathway. This study could provide a deep understanding of the photocatalytic mechanism of g-C3N4/MoS2 van der Waals heterostructures, which will be of great use for applications in photocatalysis.

Safety, antitumor activity and biomarkers of sugemalimab in Chinese patients with advanced solid tumors or lymphomas: results from the first-in-human phase 1 trial.

BACKGROUND: This first-in-human phase 1 trial is to evaluate the safety, pharmacokinetics, preliminary efficacy, and biomarkers of sugemalimab, a full-length, fully human anti-PD-L1 monoclonal antibody, in Chinese patients with advanced malignancies. METHODS: Eligible patients with unresectable advanced or metastatic solid tumors or lymphomas were enrolled in phase 1a to receive sugemalimab following a modified 3 + 3 design. The primary endpoints included safety, tolerability, and the recommended Phase 2 dose (RP2D). In phase 1b, patients with 7 selected types of tumor received sugemalimab at the RP2D alone (monotherapy cohorts) or in combination with standard-of-care (SOC) chemotherapy (combination cohorts). The primary endpoint of phase 1b was investigator-assessed objective response rate (ORR). RESULTS: As of 19 February 2020, 29 and 178 patients were treated in phase 1a and 1b, respectively. No dose-limiting toxicities were observed in phase 1a, and the RP2D of sugemalimab was determined as 1200 mg fixed dose once every 3 weeks. Sugemalimab-related adverse events (AEs) were mostly (75.9%) grade 1-2 in phase 1a. Antitumor activity was observed across dose levels with an ORR of 24.1%. In phase 1b, 15.9% and 40.4% of patients in the monotherapy and combination cohorts, respectively, reported grade 3-5 sugemalimab-related AEs. Promising efficacy was observed in all combination cohorts, with ORRs ranging from 47.6 to 75.0%. Exploratory biomarker analysis did not indicate significant differences in responses at different PD-L1 expression/tumor mutation burden levels. CONCLUSIONS: Sugemalimab was well-tolerated and showed promising antitumor activity as monotherapy or in combination with SOC chemotherapy in advanced malignancies. This trial was registered with ClinicalTrials.gov on Oct 18, 2017, number NCT03312842.

First-principles calculations of 0D/2D GQDs-MoS2 mixed van der Waals heterojunctions for photocatalysis: a transition from type I to type II.

The fabrication of type II heterojunctions is an efficient strategy to facilitate charge separation in photocatalysis. Here, mixed dimensional 0D/2D van der Waals (vdW) heterostructures (graphene quantum dots (GQDs)-MoS2) for generating hydrogen from water splitting are investigated based on density functional theory (DFT). The electronic and photocatalytic properties of three heterostructures, namely, C6H6-MoS2, C24H12-MoS2 and C32H14-MoS2 are estimated by analyzing the density of states, charge density difference, work function, Bader charge, absorption spectra and band alignment. The results indicated that the built-in electric fields from GQDs to MoS2 boost charge separation. Meanwhile, all the GQDs-MoS2 exhibit strong absorption in the visible light region. Surprisingly, the transition of heterojunctions from type I to type II is realized by tuning the size of GQDs. In particular, C32H14-MoS2 with enhanced visible-light absorption and an appropriate band edge position, as a type II heterostructure, may be a promising photocatalyst for generating hydrogen from water splitting. Thus, in this work a novel type II 0D/2D nanocomposite as a photocatalyst is constructed that provides a strategy to regulate the type of heterostructure from the perspective of theoretical calculation.

Experimental and DFT studies on oxygen release and migration mechanisms of LaAl-type perovskites as catalyst supports in biomass-to-H2 conversion.

Perovskites are potential candidates for catalyst supports in biomass gasification to produce high-purity H2 due to their excellent redox properties. However, the significant mechanism of lattice oxygen release and migration in perovskites has not been clearly understood. In this work, the characteristics of surface oxygen release and subsurface oxygen migration in various LaAl-type perovskites were investigated by experiments and density functional theory calculations. Results show that the oxygen release capacity of La0.7Sr0.3AlO3-δ is considerable and that of Ni/La0.7Sr0.3AlO3-δ decreases slightly compared to the difficult occurrence of oxygen release in LaAlO3. Moreover, the rate-limiting step of oxygen release from pure LaAlO3 is determined to be the formation of O2 complex by two opposite O atoms. Sr doping reduces the charge of the outermost O atom, making oxygen release easy, and the desorption process of O2 becomes the rate-limiting step. After Ni loading, the strength of the surrounding Al-O bond increases, which raises the energy barrier and blocks the release of oxygen to some extent.

Theoretical Studies on the Oligomerization of Silicate Species in Basic Solution.

The possible reaction pathways of silicate species to linear- and ring-structure oligomers up to silicate hexamers in the basic medium have been studied using the density functional theory. The calculations were performed at the ωB97XD/6-31+G(d,p) level, and the integral equation formalism polarizable continuum model was employed to simulate the solvent effects, and it was found that they are appropriate in exploring the reaction mechanism of silicate species condensation. There are two steps in the anionic silicate condensation reactions: the SiO-Si bond formation step and the dehydration step. Moreover, the latter is the rate-limiting step for most of the reaction pathways except for the cyclization reaction of the linear pentamer to the 5-ring. The short linear oligomers would be likely formed from the reaction between monomers and oligomers, while the longer ones are easily formed through the reactions between short oligomers. The 4-ring and branched 5-ring oligomers are found to be formed very favorable both in kinetic and thermodynamic and could have great influences on the initial stage of zeolite synthesis. The intramolecular and intermolecular hydrogen bond effect of silicate species is an important factor affecting the reaction mechanism.

Loading-Driven Diffusion Pathway Selectivity in Zeolites with Continuum Intersecting Channels.

The diffusion processes in zeolites are important for heterogeneous catalysis. Herein, we show that unique zeolites with "continuum intersecting channels" (e.g., BEC, POS, and SOV), in which two intersections are proximal, are greatly significant to the diffusion process with spontaneous switching of the diffusion pathway under varied loading. At low loading, the synergy of strong adsorption sites and molecular reorientation in intersections contribute to almost exclusive molecular diffusion in smaller channels. With an increase in molecular loading, the adsorbates are transported preferentially in larger channels mainly due to the lower diffusion barrier inside continuum intersection channels. This work demonstrates the ability to adjust the prior diffusion pathway by controlling the molecular loading, which may be beneficial for the separation of the product and byproduct in heterogeneous catalysis.

Tuning the Carrier Transfer Behavior of Coaxial ZnO/ZnS/ZnIn2 S4 Nanorods with a Coherent Lattice Heterojunction Structure for Photoelectrochemical Water Oxidation.

Invited for this month's cover is the group of Feng Li at the Ningxia University. The image shows how the coherent lattice heterojunction interface can play a role in the efficient separation of photogenerated carriers of ZnO-based photoanode for photoelectrochemical water splitting. The Research Article itself is available at 10.1002/cssc.202201469.

Tuning the Carrier Transfer Behavior of Coaxial ZnO/ZnS/ZnIn2 S4 Nanorods with a Coherent Lattice Heterojunction Structure for Photoelectrochemical Water Oxidation.

Serious degradation and the short photogenerated carrier lifetime for the wide-bandgap semiconductor ZnO have become prominent issues that negatively affect photoelectrochemical (PEC) water splitting. Herein, a novel electron transport pathway was constructed by simple but effective coaxial growth of ZnO/ZnS/ZnIn2 S4 heterostructure nanoarrays to increase the carrier separation efficiency. This new photoanode fulfilled the requirements of both favorable band alignment and stability, achieving a stable photocurrent density of 1.146 mA cm-2 at 1.2 VRHE , which was approximately twice that of pristine ZnO. Detailed experimental studies revealed that the improved PEC activity was due to the lattice-matching interface coherency that activated the carrier transport pathway, giving rise to an optimized interfacial electronic structure for promoted charge separation by the built-in electric field and strengthened water oxidation activity. This design may provide a new approach to fabricating various efficient lattice-matching coherent interface photoanodes for PEC water splitting.

Diffusive Skin Effect in Zeolites.

Effective contact and collision between reactants and active sites are essential for heterogeneous catalysis. Herein, we investigated molecular diffusion in more than 200 kinds of zeolites, and an intriguing "diffusive skin effect" was observed, whereby molecules migrated along the pore walls of zeolites (i.e., diffusion trajectories) because of the effect of the guest-host interaction and diffusion barrier. Furthermore, it was found that such a "diffusive skin effect" of zeolites would strongly promote the contacts and collisions between reactants and active sites in the reaction process, which might effectively promote the zeolite-catalyzed performance. These new findings will provide some new fundamental understanding of zeolite catalytic mechanisms under confinement effect.

One-step fabricated Zr-supported, CaO-based pellets via graphite-moulding method for regenerable CO2 capture.

Calcium looping (CaL) belongs to a promising high-temperature CO2 capture technology because of adopting cheap and extensive source CaO-based sorbents. However, CaO-based sorbents are prone to occur the issues of sintering and elutriation in the fluidized-bed reactors. To further enhance the practicability, the Zr-supported, CaO-based sorbent pellets were produced using the graphite-moulding method. Different synthesis modes (i.e., sol-gel, hydration-mixing, and wet-mixing) were compared for preparing CaO-based composite slurry before pelletization. Sol-gel is the promising synthesis mode to prepare Zr-supported, CaO-based pellets with outstanding CO2 capture performance due to achieving a more uniform distribution of inert CaZrO3 spacer. Moreover, the Zr-based stabilizer content within sorbent pellets produced by the combined method of sol-gel and graphite-moulding was further studied. The higher content of Zr-based stabilizer promotes the enhancement of cyclic stability and mechanical strength of Zr-supported, CaO-based pellets. After 17 cycles, the sorbent pellets containing 20 wt% of Zr-based stabilizer display a high CaO carbonation conversion of 74.1 %. Moreover, CaO-based pellets with 20 wt% of Zr-based stabilizer possess a higher compression strength of 4.84 ± 1.08 MPa, which is as high as 1.8 times that of the pellets with 5 wt% of Zr-based stabilizer.

Gating control effect facilitates excellent gas selectivity in a novel Na-SSZ-27 zeolite.

A novel Na-SSZ-27 zeolite was demonstrated to possess excellent H2/CO2 diffusion selectivity of more than 100. This investigation highlights the crucial effect of the "gating control" of the 8-ring windows on the separation, where sodium cations act as gates to selectively control the diffusion of CO2 and promote the selectivity for H2.

Monomolecular Dehydration of Ethanol into Ethylene over H-MOR Studied by Density Functional Theory.

The framework effect of H-mordenite (H-MOR) zeolite on monomolecular dehydration of ethanol to ethylene has been simulated based on density functional theory. It is indicated that both the reaction mechanism and the activation energy barriers are significantly affected by the pore-confinement effect. In the 12-membered ring (12-MR), the energy barriers of the stepwise mechanism and the concerted mechanism are 35.0 and 42.4 kcal mol-1, respectively, suggesting that ethylene can be competitively formed through both pathways. While in the 8-membered ring (8-MR), the barrier of the concerted mechanism is 43.4 kcal mol-1, which is much lower than that of the stepwise mechanism with the ethoxy intermediate formation barrier of 53.7 kcal mol-1. Furthermore, the water molecule acts as the intermediate to stabilize the transition states (TSs) for both stepwise and concerted mechanisms and helps to transport protons during the reaction.

[In vitro chemo-sensitivity MTT assay guided intraperitoneal chemotherapy for malignant ascites].

OBJECTIVE: To evaluate the feasibility and efficacy of intraperitoneal chemotherapy for malignant ascites caused by different types of abdominal cancers guided by chemo-sensitivity methyl tetrojolium coloremetric (MTT) assay in vitro. METHODS: Cancer cells in the malignant ascites were collected for MTT assay to determine the chemo-sensitivity. The drug producing the highest or the second highest inhibition rate was selected for intraperitoneal chemotherapy. The correlation between the results of MTT assay and the response of malignant ascites, the clinical features, Karnofsky performance score (KPS) and prognosis were analyzed. RESULTS: MTT assay indicated that Taxotere (TXT) and Hydroxycamptothecin (HCPT) were the most effective to cancer cells in malignant ascites, and HCPT was mostly frequently used for intraperitoneal chemotherapy (56.9%). Twenty-four patients showed response by intraperitoneal chemotherapy (complete response: 7; partial response: 17) with a slightly significant correlation between the results of MTT assay and response of malignant ascites (P = 0. 014). The KPS of the responders was improved significantly (P < 0.001), and the response of malignant ascites to intraperitoneal chemotherapy was demostrated as an independent prognostic factor by multi-variate analysis in this series. CONCLUSION: In vitro chemo-sensitivity MTT assay guided intraperitoneal chemotherapy for malignant ascites is simple, effective and safe, which can improve the KPS and prognosis of the responders.

Hyperthermia combined with intra-thoracic chemotherapy and radiotherapy for malignant pleural mesothelioma.

BACKGROUND: Prognosis for patients with malignant pleural mesothelioma (MPM) remains poor and such patients require intensive treatment. Few studies have examined hyperthermia for MPM. The present study investigated the feasibility of hyperthermia combined with weekly chemo-radiotherapy for patients with MPM and estimated the efficacy of this regimen. METHODS: A total of 11 patients (median patient age was 67 and all had pleural effusion) with MPM were enrolled in this study. The treatment regimen comprised of weekly thermo-radiotherapy with intra-thoracic chemotherapy 2-5 times at initiation of treatment. Hyperthermia was performed once per week for approximately 60 min. Hemithorax external radiotherapy was administered once weekly on the same day as hyperthermia and just before thermochemotherapy. Median total radiation dose was 6 Gy (range, 2-10 Gy). Chemotherapy was administered into the thoracic cavity through a tube. Chemotherapeutic agents administered were CDDP for seven patients, carboplatinum (CBDCA) for three patients and both CDDP and CBDCA for one patient. Dose of CDDP was 50 mg/body and dose of CBDCA was 200-300 mg m-2. Response rate and median survival time (MST) and palliative effect were investigated. RESULTS: Complete response was not achieved in any of the 11 patients. Partial response was achieved in three of 11 patients (27.3%), SD in six patients (54.5%) and PD in two patients (18.2%). There was no correlational relationship between thermal parameters and response. MST was 27.1 months. Pleural fluid decreased in all patients after therapy, while all patients displayed improved performance status and could be discharged from hospital. Patients with partial response had a relatively longer survival time than SD or PD. All patients underwent the complete course of treatment and only one of 11 patients developed grade 4 thrombocytopenia. CONCLUSION: It was therefore concluded that hyperthermia combined with intra-thoracic chemotherapy using cisplatinum or carboplatinum may be tolerable. This approach appears effective and more acceptable for patients with MPM with pleural effusion than other multi-modality therapy.