Steering the Reaction Pathway of CO2 Electroreduction by Tuning the Coordination Number of Copper Catalysts.

Cu-based catalysts are optimal for the electroreduction of CO2 to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C2+ products, while low-CN Cu favors CH4 production. For instance, over the high-CN Pot-Cu, C2+ is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density (j) of 514.3 mA cm-2. Conversely, the low-CN Pul(3)-Cu favors the production of CH4, achieving the highest FECH4 value of 56.7% with a jCH4 value of 234.4 mA cm-2. In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO2RR.

Highly Efficient Electrosynthesis of Glycine over an Atomically Dispersed Iron Catalyst.

Glycine is a nonessential amino acid that plays a vital role in various biological activities. However, the conventional synthesis of glycine requires sophisticated procedures or toxic feedstocks. Herein, we report an electrochemical pathway for glycine synthesis via the reductive coupling of oxalic acid and nitrate or nitrogen oxides over atomically dispersed Fe-N-C catalysts. A glycine selectivity of 70.7% is achieved over Fe-N-C-700 at -1.0 V versus RHE. Synergy between the FeN3C structure and pyrrolic nitrogen in Fe-N-C-700 facilitates the reduction of oxalic acid to glyoxylic acid, which is crucial for producing glyoxylic acid oxime and glycine, and the FeN3C structure could reduce the energy barrier of *HOOCCH2NH2 intermediate formation thus accelerating the glyoxylic acid oxime conversion to glycine. This new synthesis approach for value-added chemicals using simple carbon and nitrogen sources could provide sustainable routes for organonitrogen compound production.

Polymer Modification Strategy to Modulate Reaction Microenvironment for Enhanced CO2 Electroreduction to Ethylene.

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO2 RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO2 solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method to structure electrocatalyst with a superhydrophobic surface microenvironment by one-step co-electrodeposition of Cu and polytetrafluoroethylene (PTFE) on carbon paper. The super-hydrophobic Cu-based electrode displayed a high ethylene (C2 H4 ) selectivity with a Faraday efficiency (FE) of 67.3 % at -1.25 V vs. reversible hydrogen electrode (RHE) in an H-type cell, which is 2.5 times higher than a regular Cu electrode without PTFE. By using PTFE as a surface modifier, the activity of eCO2 RR is enhanced and water (proton) adsorption is inhibited. This strategy has the potential to be applied to other gas-conversion electrocatalysts.

Lattice Strain Engineering Boosts CO2 Electroreduction to C2+ Products.

Regulating the binding effect between the surface of an electrode material and reaction intermediates is essential in highly efficient CO2 electro-reduction to produce high-value multicarbon (C2+) compounds. Theoretical study reveals that lattice tensile strain in single-component Cu catalysts can reduce the dipole-dipole repulsion between *CO intermediates and promotes *OH adsorption, and the high *CO and *OH coverage decreases the energy barrier for C-C coupling. In this work, Cu catalysts with varying lattice tensile strain were fabricated by electro-reducing CuO precursors with different crystallinity, without adding any extra components. The as-prepared single-component Cu catalysts were used for CO2 electro-reduction, and it is discovered that the lattice tensile strain in Cu could enhance the Faradaic efficiency (FE) of C2+ products effectively. Especially, the as-prepared CuTPA catalyst with high lattice tensile strain achieves a FEC2+ of 90.9% at -1.25 V vs. RHE with a partial current density of 486.1 mA cm-2.

Ternary Ionic-Liquid-Based Electrolyte Enables Efficient Electro-reduction of CO2 over Bulk Metal Electrodes.

Using bulk metals as catalysts to get high efficiency in electro-reduction of CO2 is ideal but challenging. Here, we report the coupling of bulk metal electrodes and a ternary ionic-liquid-based electrolyte, 1-butyl-3-methylimidazolium tetrafluoroborate/1-dodecyl-3-methylimidazolium tetrafluoroborate/MeCN to realize highly efficient electro-reduction of CO2 to CO. Over various bulk metal electrodes, the ternary electrolyte not only increases the current density but also suppresses the hydrogen evolution reaction to obtain a high Faradaic efficiency (FE) toward CO. FECO could maintain ∼100% over a wide potential range, and metal electrodes showed very high stability in the ternary electrolyte. It is demonstrated that the aggregation behavior of the ternary electrolyte and the arrangement of two kinds of IL cations with different chain lengths in the electrochemical double layer not only increase the wettability to electrode and CO2 adsorption but also extend the diffusion channel of H+, rendering the high current density and FECO.

Photo-thermal coupling to enhance CO2 hydrogenation toward CH4 over Ru/MnO/Mn3O4.

Upcycling of CO2 into fuels by virtually unlimited solar energy provides an ultimate solution for addressing the substantial challenges of energy crisis and climate change. In this work, we report an efficient nanostructured Ru/MnOx catalyst composed of well-defined Ru/MnO/Mn3O4 for photo-thermal catalytic CO2 hydrogenation to CH4, which is the result of a combination of external heating and irradiation. Remarkably, under relatively mild conditions of 200 °C, a considerable CH4 production rate of 166.7 mmol g-1 h-1 was achieved with a superior selectivity of 99.5% at CO2 conversion of 66.8%. The correlative spectroscopic and theoretical investigations suggest that the yield of CH4 is enhanced by coordinating photon energy with thermal energy to reduce the activation energy of reaction and promote formation of key intermediate COOH* species over the catalyst. This work opens up a new strategy for CO2 hydrogenation toward CH4.

Highly Stable Layered Coordination Polymer Electrocatalyst toward Efficient CO2 -to-CH4 Conversion.

Cu2+ -based materials, a class of promising catalysts for the electrocatalytic carbon dioxide reduction reaction (CO2 RR) to value-added chemicals, usually undergo inevitable and uncontrollable reorganization processes during the reaction, resulting in catalyst deactivation or the new active sites formation and bringing great challenges to exploring their structure-performance relationships. Herein, a facile strategy is reported for constructing Cu2+ and 3, 4-ethylenedioxythiophene (EDOT) coordination to stabilize Cu2+ ions to prepare a novel layered coordination polymer (CuPEDOT). CuPEDOT enables selective reduction of CO2 to CH4 with 62.7% Faradaic efficiency at the current density of 354 mA cm-2 in a flow cell, and the catalyst is stable for at least 15 h. In situ spectroscopic characterization and theoretical calculations reveal that CuPEDOT catalyst can maintain the Cu2+ -EDOT coordination structurally stable in CO2 RR and significantly promote the further hydrogenation of *CO intermediates, favoring the formation of CH4 instead of dimerization to C2 products. The strong coordination between EDOT and Cu2+ prevents the reduction of Cu2+ ions during CO2 RR. The finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO2 RR.

Role of exosomes in the development of the immune microenvironment in hepatocellular carcinoma.

Despite numerous improved treatment methods used in recent years, hepatocellular carcinoma (HCC) is still a disease with a high mortality rate. Many recent studies have shown that immunotherapy has great potential for cancer treatment. Exosomes play a significant role in negatively regulating the immune system in HCC. Understanding how these exosomes play a role in innate and adaptive immunity in HCC can significantly improve the immunotherapeutic effects on HCC. Further, engineered exosomes can deliver different drugs and RNA molecules to regulate the immune microenvironment of HCC by regulating the aforementioned immune pathway, thereby significantly improving the mortality rate of HCC. This study aimed to declare the role of exosomes in the development of the immune microenvironment in HCC and list engineered exosomes that could be used for clinical transformation therapy. These findings might be beneficial for clinical patients.

Optimizing copper nanoparticles with a carbon shell for enhanced electrochemical CO2 reduction to ethanol.

The electrochemical reduction of carbon dioxide (CO2RR) holds great promise for sustainable energy utilization and combating global warming. However, progress has been impeded by challenges in developing stable electrocatalysts that can steer the reaction toward specific products. This study proposes a carbon shell coating protection strategy by an efficient and straightforward approach to prevent electrocatalyst reconstruction during the CO2RR. Utilizing a copper-based metal-organic framework as the precursor for the carbon shell, we synthesized carbon shell-coated electrocatalysts, denoted as Cu-x-y, through calcination in an N2 atmosphere (where x and y represent different calcination temperatures and atmospheres: N2, H2, and NH3). It was found that the faradaic efficiency of ethanol over the catalysts with a carbon shell could reach ∼67.8%. In addition, the catalyst could be stably used for more than 16 h, surpassing the performance of Cu-600-H2 and Cu-600-NH3. Control experiments and theoretical calculations revealed that the carbon shell and Cu-C bonds played a pivotal role in stabilizing the catalyst, tuning the electron environment around Cu atoms, and promoting the formation and coupling process of CO*, ultimately favoring the reaction pathway leading to ethanol formation. This carbon shell coating strategy is valuable for developing highly efficient and selective electrocatalysts for the CO2RR.

Synergic adsorption performance of activated carbon prepared from Chinese prickly ash seeds.

Waste residue of Chinese prickly ash seeds were simply treated with aqueous ZnCl2 to prepared the high-performed activated carbon. It was characterized by the methods of XRD, SEM, EDX, FT-IR, BET and XPS. The synergetic adsorption performance of Chinese prickly ash seeds activated carbon for Pb2+, Ni2+ and Acid Orange IΙ (AO) was studied. In the single-component system, the adsorption capacity of Pb2+, Ni2+ and AO were 15.1, 10.7 and 188.4 mg/g, respectively. In the AO-Pb2+ system, the maximum adsorption capacity of Pb2+ and AO were 79.40 and 332.68 mg/g under temperature of 30°C and pH of 5.0, respectively. For AO-Ni2+ system, it was 375.6 and 38.3 mg/g, respectively. The adsorption kinetics was satisfactorily fitted by the pseudo-second-order model. The synergic adsorption process can be smoothly described by the non-modified Sips isotherm.

Immune-related keratitis is a rare complication associated with nivolumab treatment in a patient with advanced colorectal cancer: A case report.

Background: Immunotherapy has been widely used to treat Colorectal cancer but has also observe some immune-related adverse effects. With proper treatment, most irAE can be solved and the effect of immunotherapy will not be affected by temporary immunosuppression. However, there are few reports about corneal irAE, and the current understanding of irAE is incomplete. Here we report a metastatic colorectal cancer case of immune-related keratitis caused by nivolumab and to explore the occurrence of immune-related keratitis. Case description: Here we report the case of a 49-year-old man with mCRC who had no previous ocular disease but developed immune-related ulcerative keratitis after treatment with nivolumab. We summarize a large amount of literature to discuss the mechanism of immune-related keratitis. In addition, we conclude a method that may be used to detect the occurrence of immune keratitis, by monitoring MMPs and maspin in patients treated with nivolumab. We believe immune-related keratitis may be a rare complication of nivolumab in the treatment of mCRC. The effect of simple anti-infective therapy and repair-promoting drugs was not obvious, but the effect of glucocorticoid combined with autologous serum was significant. Conclusion: The mechanism of immune-related keratitis is that nivolumab destroys the immune microenvironment and ACAID, and affects corneal healing. Patients who use nivolumab can prevent immune keratitis by testing MMPs and maspin. The occurrence of immune keratitis may be a good indicator of the efficacy of ICI, and further study can be done in the follow-up.