Comparison of children and adults in deep brain stimulation for Tourette Syndrome: a large-scale multicenter study of 102 cases with long-term follow-up.

BACKGROUND: Deep brain stimulation (DBS) is a promising therapy for refractory Gilles de la Tourette syndrome (GTS). However, its long-term efficacy, safety, and recommended surgical age remain controversial, requiring evidence to compare different age categories. METHODS: This retrospective cohort study recruited 102 GTS patients who underwent DBS between October 2006 and April 2022 at two national centers. Patients were divided into two age categories: children (aged < 18 years; n = 34) and adults (aged ≥ 18 years; n = 68). The longitudinal outcomes as tic symptoms were assessed by the YGTSS, and the YBOCS, BDI, and GTS-QOL were evaluated for symptoms of obsessive-compulsive disorder (OCD), depression, and quality of life, respectively. RESULTS: Overall, these included patients who finished a median 60-month follow-up, with no significant difference between children and adults (p = 0.44). Overall, the YGTSS total score showed significant postoperative improvements and further improved with time (improved 45.2%, 51.6%, 55.5%, 55.6%, 57.8%, 61.4% after 6, 12, 24, 36, 48, and ≥ 60 months of follow-up compared to baseline, respectively) in all included patients (all p < 0.05). A significantly higher improvement was revealed in children than adults at ≥ 60 months of follow-up in the YGTSS scores (70.1% vs 55.9%, p = 0.043), and the time to achieve 60% improvement was significantly shorter in the children group (median 6 months vs 12 months, p = 0.013). At the last follow-up, the mean improvements were 45.4%, 48.9%, and 55.9% and 40.3%, 45.4%, and 47.9% in YBOCS, BDI, and GTS-QOL scores for children and adults, respectively, which all significantly improved compared to baseline (all p < 0.05) but without significant differences between these two groups (all p > 0.05), and the children group received significantly higher improvement in GTS-QOL scores than adults (55.9% vs. 47.9%, p = 0.049). CONCLUSIONS: DBS showed acceptable long-term efficacy and safety for both children and adults with GTS. Surgeries performed for patients younger than 18 years seemed to show acceptable long-term efficacy and safety and were not associated with increased risks of loss of benefit compared to patients older than 18 at the time of surgery. However, surgeries for children should also be performed cautiously to ensure their refractoriness and safety.

Role of imbalanced gut microbiota in promoting CRC metastasis: from theory to clinical application.

Metastasis poses a major challenge in colorectal cancer (CRC) treatment and remains a primary cause of mortality among patients with CRC. Recent investigations have elucidated the involvement of disrupted gut microbiota homeostasis in various facets of CRC metastasis, exerting a pivotal influence in shaping the metastatic microenvironment, triggering epithelial-mesenchymal transition (EMT), and so on. Moreover, therapeutic interventions targeting the gut microbiota demonstrate promise in enhancing the efficacy of conventional treatments for metastatic CRC (mCRC), presenting novel avenues for mCRC clinical management. Grounded in the "seed and soil" hypothesis, this review consolidates insights into the mechanisms by which imbalanced gut microbiota promotes mCRC and highlights recent strides in leveraging gut microbiota modulation for the clinical prevention and treatment of mCRC. Emphasis is placed on the considerable potential of manipulating gut microbiota within clinical settings for managing mCRC.

Discovery of piperine derivatives as inhibitors of human dihydroorotate dehydrogenase to induce ferroptosis in cancer cells.

Inhibition of human dihydroorotate dehydrogenase (hDHODH) represents a promising strategy for suppressing the proliferation of cancer cells. To identify novel and potent hDHODH inhibitors, a total of 28 piperine derivatives were designed and synthesized. Their cytotoxicities against three human cancer cell lines (NCI-H226, HCT-116, and MDA-MB-231) and hDHODH inhibitory activities were also evaluated. Among them, compound H19, exhibited the strongest inhibitory activities (NCI-H226 IC50 = 0.95 µM, hDHODH IC50 = 0.21 µM). Further pharmacological investigations revealed that H19 exerted anticancer effects by inducing ferroptosis in NCI-H226 cells, with its cytotoxicity being reversed by ferroptosis inhibitors. This was supported by the intracellular growth or decline of ferroptosis markers, including lipid peroxidation, Fe2+, GSH, and 4-HNE. Overall, H19 emerges as a promising hDHODH inhibitor with potential anticancer properties warranting development.

The value of intratumoral microbiota in the diagnosis and prognosis of tumors.

Intratumoral microbiota (ITM) are microorganisms present in tumor cells. ITM participate in tumor development by affecting tumor cells directly and the tumor microenvironment (TME), indirectly. Alterations in ITM instigate changes in tumor DNA, activate oncogenic pathways, induce tumor inflammatory responses, disrupt normal immune activity, and facilitate the secretion of effectors leading to tumor progression, metastasis, or diminished therapeutic effects. ITM varies significantly in different types of cancer cells and disease states. The presence of certain ITM serves as a predictor of various disease states. Thus, ITM predicts tumorigenesis, tumor grade, treatment efficacy, and prognosis, making it a potential tumor biomarker. The present study aimed to determine the mechanisms by which ITM affects tumor development, especially through the TME; highlight the significant potential of ITM in enhancing tumor diagnosis and prognosis; and outline future directions for ITM research, with a focus on the development of innovative tumor markers.

Adsorption and membrane separation for removal and recovery of volatile organic compounds.

Volatile organic compounds (VOCs) are a crucial kind of pollutants in the environment due to their obvious features of severe toxicity, high volatility, and poor degradability. It is particularly urgent to control the emission of VOCs due to the persistent increase of concentration and the stringent regulations. In China, clear directions and requirements for reduction of VOCs have been given in the "national plan on environmental improvement for the 13th Five-Year Plan period". Therefore, the development of efficient technologies for removal and recovery of VOCs is of great significance. Recovery technologies are favored by researchers due to their advantages in both recycling VOCs and reducing carbon emissions. Among them, adsorption and membrane separation processes have been extensively studied due to their remarkable industrial prospects. This overview was to provide an up-to-date progress of adsorption and membrane separation for removal and recovery of VOCs. Firstly, adsorption and membrane separation were found to be the research hotspots through bibliometric analysis. Then, a comprehensive understanding of their mechanisms, factors, and current application statuses was discussed. Finally, the challenges and perspectives in this emerging field were briefly highlighted.

Highly Efficient Electrocatalytic Upgrade of n-Valeraldehyde to Octane over Au SACs-NiMn2 O4 Spinel Synergetic Composites.

In this work, electrocatalytic upgrade of n-valeraldehyde to octane with higher activity and selectivity is achieved over Au single-atom catalysts (SACs)-NiMn2 O4 spinel synergetic composites. Experiments combined with density functional theory calculation collaboratively demonstrate that Au single-atoms occupy surface Ni2+ vacancies of NiMn2 O4 , which play a dominant role in n-valeraldehyde selective oxidation. A detailed investigation reveals that the initial n-valeraldehyde molecule preferentially adsorbs on the Mn tetrahedral site of NiMn2 O4 spinel synergetic structures, and the subsequent n-valeraldehyde molecule easily adsorbs on the Ni site. Specifically, Au single-atom surficial derivation over spinel lowers the adsorption energy (Eads ) of the initial n-valeraldehyde molecule, which will facilitate its adsorption on the Mn site of Au SACs-NiMn2 O4 . Furthermore, the single-atom Au surficial derivation not only alters the electronic structure of Au SACs-NiMn2 O4 but also lower the Eads of subsequent n-valeraldehyde molecule. Hence, the subsequent n-valeraldehyde molecules prefer adsorption on Au sites rather than Ni sites, and the process of two alkyl radicals originating from Mn-C4 H9 and Au-C4 H9 dimerization into an octane is accordingly accelerated. This work will provide an avenue for the rational design of SACs and supply a vital mechanism for understanding the electrocatalytic upgrade of n-valeraldehyde to octane.

Subthalamic nucleus-deep brain stimulation improves autonomic dysfunctions in Parkinson's disease.

BACKGROUND: To study the effects of subthalamic nucleus-deep brain stimulation (STN-DBS) on autonomic dysfunctions in Parkinson's disease (PD) patients. METHODS: A total of 57 PD patients who underwent bilateral STN-DBS from March to December 2018, were retrospectively analyzed. Preplanned assessments at baseline and postoperatively at 1, 3, and 6 months also included the Scales for Outcomes in Parkinson's Disease-Autonomic questionnaire (SCOPA-Aut), the Unified Parkinson's Disease Rating Scale (UPDRS) III score, levodopa equivalent day dose (LEDD), Parkinson's Disease Quality of Life Scale (PDQ-39), the Hamilton Anxiety Rating Scale (HAMA), and the Hamilton Depression Rating Scale (HAMD). RESULTS: The SCOPA-Aut scores improved significantly [14.59% (18.32%), 24.00% (27.05%), 22.16% (27.07%), all P < 0.001] at 1 month, 3 months, and 6 months of STN-DBS, respectively. Analysis of the SCOPA-Aut sub-items showed significant improvements only in urine and thermoregulation sub-items at 6 months after surgery (P < 0.001). There was no significant correlation between improvements of SCOPA-Aut scores and improvements of PDQ-39 scores (P > 0.05) at 6 months after surgery. SCOPA-Aut scores were positively correlated with age (r = 0.428, P = 0.001); the improvements of SCCOPA-Aut scores were positively correlated with improvements of HAMA and HAMD scores (HAMA: r = 0.325, P = 0.015; HAMD: r = 0.265, P = 0.049) at 6 months after surgery. CONCLUSION: STN-DBS improved autonomic dysfunction symptoms of PD patients, and urinary and thermoregulatory sub-items of autonomic dysfunction were improved in the short-term after surgery. There was a close relationship between improved autonomic symptoms and improved anxiety and depression 6 months after surgery. We should therefore direct more attention to autonomic dysfunctions in PD involving detailed preoperative evaluations and postoperative follow-ups, to improve the quality of life of patients.

Relationship between electrode position of deep brain stimulation and motor symptoms of Parkinson's disease.

BACKGROUND: To investigate the relationship between the position of bilateral STN-DBS location of active contacts and the clinical efficacy of STN-DBS on motor symptoms in Parkinson's disease (PD) patients. METHODS: Retrospectively analyze the clinical data of 57 patients with PD who underwent bilateral STN-DBS from March 2018 to December 2018. Unified Parkinson's Disease Rating Scale-Part III (UPDRS-III) score, levodopa equivalent day dose (LEDD), Parkinson's Disease Quality of Life Scale (PDQ-39) before operation and within 6 months after operation, determine the location of activated contacts and volume of tissue activated (VTA) in the Montreal Neurological Institute (MNI) space, and analyze their correlation with the improvement rate of motor symptoms (UPDRS-III score improvement rate). RESULTS: After 6 months of follow up, the UPDRS-III scores of 57 patients (Med-off) were improved by 55.4 ± 18.9% (P<0.001) compared with that before operation. The improvement rate of PDQ-39 scores [(47.4 ± 23.2)%, (P < 0.001)] and the reduction rate of LEDD [(40.1 ± 24.3)%, (P < 0.01)] at 6 months postoperation were positively correlated with the improvement rate of motor symptoms (Med-off)(PDQ-39:r = 0.461, P<0.001; LEDD: r = 0.354, P = 0.007), the improvement rate of UPDRS-III (Med-off) and the Z-axis coordinate of the active contact in the MNI space were positively correlated (left side: r = 0.349,P = 0.008;right side: r = 0.369,P = 0.005). In the MNI space, there was no correlation between the UPDRS-III scores improvement rate (Med-off) at 6 months after operation and bilateral VTA in the STN motor subregion, STN associative subregion and STN limbic subregion of the active electrode contacts of 57 patients (all P > 0.05). At 6 months after surgery, the difference between the Z-axis coordinate in the different improvement rate subgroups(<25, 25 to 50%, and>50%) in the MNI space was statistically significant (left side: P = 0.030; right side: P = 0.024). In the MNI space, there was no statistically significant difference between the groups in the VTA of the electrode active contacts (all P > 0.05). CONCLUSION: STN-DBS can improve the motor symptoms of PD patients and improve the quality of life. The closer the stimulation is to the STN dorsolateral sensorimotor area, the higher the DBS is to improve the motor symptoms of PD patients.

Stimulation-Induced Dyskinesia After Subthalamic Nucleus Deep Brain Stimulation in Patients With Meige Syndrome.

OBJECTIVES: Deep brain stimulation of the subthalamic nucleus (STN-DBS) is increasingly used to treat Meige syndrome (MS) and markedly improves symptoms. Stimulation-induced dyskinesia (SID), which adversely affects surgical outcomes and patient satisfaction, may, however, occur in some patients. This study attempts to explore possible causes of SID. MATERIALS AND METHODS: Retrospectively collected clinical data on 32 patients who underwent STN-DBS between October 2016 and April 2019 were analyzed. Clinical outcomes were assessed pre- and post-surgery, using the Burke-Fahn-Marsden dystonia rating scale (BFMDRS). Patients were divided into a dyskinesia group and a non-dyskinesia group, according to whether or not they experienced persistent SID during follow-up. The coordinates of the active contacts were calculated from post-operative computerized tomography or magnetic resonance imaging, using the inter-commissural line as a reference. At final follow-up, the main stimulatory parameters for further study included pulse width, voltage, and frequency. RESULTS: At final follow-up (mean = 16.3 ± 7.2 months), MS patients had improved BFMDRS total scores compared with pre-surgical scores (mean improvement = 79.0%, p < 0.0001). The mean improvement in BFMDRS total scores in the dyskinesia (n = 10) and non-dyskinesia (n = 22) groups were 81.6 ± 8.8% and 77.9 ± 14.2%, respectively. The mean minimum voltage to induce dyskinesia was 1.7 ± 0.3 V. The programmed parameters of both groups were similar. When compared with the non-dyskinesia group, active stimulatory contact coordinates in the dyskinesia group were inferior (mean left side: z = -2.3 ± 1.7 mm vs. z = -1.2 ± 1.5 mm; p = 0.0282; mean right side: z = -2.7 ± 1.9 mm vs. z = -2.3 ± 1.7 mm; p = 0.0256). The x and y coordinates were similar. CONCLUSION: STN-DBS is an effective intervention for MS, providing marked improvements in clinical symptoms; SID may, however occur in the subsequent programming control process. Comparing patients with/without dyskinesia, the active contacts were located closer to the inferior part of the STN in patients with dyskinesia, which may provide an explanation for the dyskinesia.

Novel Two-Dimensional AgInS2/SnS2/RGO Dual Heterojunctions: High Spatial Charge and Toxicity Evaluation.

A single semiconductor employed into photo(electro)catalysis is not sufficient for charge carrier separation. Designing a multiple heterojunction system is a practical method for photo(electro)catalysis. Herein, novel two-dimensional AgInS2/SnS2/RGO (AISR) photocatalysts with multiple junctions were prepared by a simple hydrothermal method. The synthesized AISR heterojunctions showed superior photoelectrochemical performance and photocatalytic degradation of norfloxacin, with a high degradation rate reaching 95%. More importantly, the toxicity of photocatalytic products decreased within the reaction process. High spatial separation efficiency of photogenerated electron-hole pairs was evidenced by optical and photoelectrochemical characterizations. Furthermore, a laser flash photolysis technique was carried on investigating the lifetime of the charge carrier of the fabricated dual heterostructures. In addition, sulfur and oxygen vacancies existed in AISR heterojunctions could largely constrain the recombination of electron-hole pairs. Density functional theory calculations were carried out to analyze the mechanism of photoinduced interfacial redox reactions, showing that reduced graphene oxide and AgInS2 act as electron and hole trappers in the photocatalytic reaction, respectively. Due to the interfacial electric field formed from AISR dual heterojunctions, the effective spatial charge separation and transfer contributed to the boosting photo(electro)catalytic performance.

Electrocatalytic reduction of furfural to furfuryl alcohol using carbon nanofibers supported zinc cobalt bimetallic oxide with surface-derived zinc vacancies in alkaline medium.

Electrocatalytic hydrogenation (ECH) reduction provides an environment-friendly alternative to conventional method for the upgrade of furfural to furfuryl alcohol. At present, exploring superior catalysts with high activity and selectivity, figuring out the reduction mechanism in aqueous alkaline environment are urgent. In this work, zinc cobalt bimetallic oxide (ZnMn2O4) with surface-derived Zn2+ vacancies supported by carbon nanofibers (d-ZnMn2O4-C) was fabricated. The d-ZnMn2O4-C exhibited excellent performance in electrocatalytic reduction of furfural, high furfuryl alcohol yield (49461.1 ± 228 µmol g-1) and Faradaic efficiency (95.5 ± 0.5 %) was obtained. In-depth research suggested that carbon nanofiber may strongly promoted the production of adsorbed hydrogen (Hads), and Zn2+ vacancies may significantly lowered the energy barrier of furfural reduction to furfuryl alcohol, the synergistic effect between carbon nanofiber and d-ZnMn2O4 probably facilitated the reaction between Hads and furfuryl alcohol radical, thereby promoting the formation of furfuryl alcohol. Furthermore, the reaction mechanism was clarified by inhibitor coating and isotope experiments, the results of which revealed that the conversion of furfural to furfuryl alcohol on d-ZnMn2O4-C followed both ECH and direct electroreduction mechanism.

Microbes in the tumor microenvironment: New additions to break the tumor immunotherapy dilemma.

Immunotherapies currently used in clinical practice are unsatisfactory in terms of therapeutic response and toxic side effects, and therefore new immunotherapies need to be explored. Intratumoral microbiota (ITM) exists in the tumor environment (TME) and reacts with its components. On the one hand, ITM promotes antigen delivery to tumor cells or provides cross-antigens to promote immune cells to attack tumors. On the other hand, ITM affects the activity of immune cells and stromal cells. We also summarize the dialog pathways by which ITM crosstalks with components within the TME, particularly the interferon pathway. This interaction between ITM and TME provides new ideas for tumor immunotherapy. By analyzing the bidirectional role of ITM in TME and combining it with its experimental and clinical status, we summarized the adjuvant role of ITM in immunotherapy. We explored the potential applications of using ITM as tumor immunotherapy, such as a healthy diet, fecal transplantation, targeted ITM, antibiotics, and probiotics, to provide a new perspective on the use of ITM in tumor immunotherapy.

Potential role of the intratumoral microbiota in colorectal cancer immunotherapy.

Colorectal cancer (CRC) has been one of the most common malignancies worldwide. Despite the advances in current therapies, the mortality rate of CRC remains high. Among them, immunotherapy has achieved satisfactory results in some CRC patients, however, how to expand the use of immunotherapy in CRC patients remains an urgent challenge. Surprisingly, the intratumoral microbiota has been found in multiple tumor tissues, including CRC. It has been demonstrated that the intratumoral microbiota is associated with the progression and treatment of CRC, and is able to enhance or decrease anti-tumor immune responses via different mechanisms as well as influence the immunotherapy efficacy, providing new potential therapeutic targets for CRC immunotherapy. In this review, we focus on the characteristics of the intratumoral microbiota, its roles in the genesis and development of CRC, its modulation of anti-tumor immune responses and immunotherapy, and propose potential applications of the intratumoral microbiota in CRC immunotherapy. Additionally, we propose possible directions for future research on the intratumoral microbiota related to CRC immunotherapy.

Construction of Monoatomic-Modified Defective Ti4+αTi3+1-αO2-δ Nanofibers for Photocatalytic Oxidation of HMF to Valuable Chemicals.

Efficiently upgrading 5-hydroxymethylfurfural (HMF) into high-value-added products, such as 2,5-diformylfuran (DFF) and 2,5-furan dicarboxylic acid (FDCA), through a photocatalytic process by using solar energy has been incessantly pursued worldwide. Herein, a series of transition-metal (TM = Ni, Fe, Co, Cu) single atoms were supported on Ti4+αTi3+1-αO2-δ nanofibers (NFs) with certain defects (Ov), denoted as TM SAC-Ti4+αTi3+1-αO2-δ NFs (TM = Ni, Fe, Co, Cu), aiming to enhance the photocatalytic conversion of HMF. A super HMF conversion rate of 57% and a total yield of 1718.66 µmol g-1 h-1 (DFF and FDCA) surpassing that of the Ti4+αTi3+1-αO2-δ NFs by 1.6 and 2.1 times, respectively, are realized when TM is Co (Co SAC-Ti4+αTi3+1-αO2-δ NFs). Experiments combined with density functional theory calculation (DFT) demonstrate that the TM single atoms occupy the Ti site of Ti4+αTi3+1-αO2-δ NFs, which plays a dominant role in the photo-oxidation of HMF. Raman, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) characterizations confirm the strong electron local exchange interaction in TM SAC-Ti4+αTi3+1-αO2-δ NFs and demonstrate the substitution of Ti by the TM SACs. The projected density of states and charge density difference reveal that the strong interaction between metal-3d and O-2p orbitals forms Ti-O-TM bonds. The bonds are identified as the adsorption site, where TM single atoms on the surface of Ti4+αTi3+1-αO2-δ NFs reduce HMF molecule adsorption energy (Eads). Furthermore, the TM single atom modulates the electronic structure of TM SAC-Ti4+αTi3+1-αO2-δ NFs through electron transfer, leading to narrow band gaps of the photocatalysts and enhancing their photocatalytic performance. This study has uncovered a newer strategy for enhancing the photocatalytic attributes of semiconducting materials.

Efficacy and safety of combined deep brain stimulation with capsulotomy for comorbid motor and psychiatric symptoms in Tourette's syndrome: Experience and evidence.

OBJECTIVES: To evaluate the efficacy and safety of combined deep brain stimulation (DBS) with capsulotomy for comorbid motor and psychiatric symptoms in patients with Tourette's syndrome (TS). METHODS: This retrospective cohort study consecutively enrolled TS patients with comorbid motor and psychiatric symptoms who were treated with combined DBS and anterior capsulotomy at our center. Longitudinal motor, psychiatric, and cognitive outcomes and quality of life were assessed. In addition, a systematic review and meta-analysis were performed to summarize the current experience with the available evidence. RESULTS: In total, 5 eligible patients in our cohort and 26 summarized patients in 6 cohorts were included. After a mean 18-month follow-up, our cohort reported that motor symptoms significantly improved by 62.4 % (P = 0.005); psychiatric symptoms of obsessive-compulsive disorder (OCD) and anxiety significantly improved by 87.7 % (P < 0.001) and 78.4 % (P = 0.009); quality of life significantly improved by 61.9 % (P = 0.011); and no significant difference was found in cognitive function (all P > 0.05). Combined surgery resulted in greater improvements in psychiatric outcomes and quality of life than DBS alone. The synthesized findings suggested significant improvements in tics (MD: 57.92, 95 % CI: 41.28-74.56, P < 0.001), OCD (MD: 21.91, 95 % CI: 18.67-25.15, P < 0.001), depression (MD: 18.32, 95 % CI: 13.26-23.38, P < 0.001), anxiety (MD: 13.83, 95 % CI: 11.90-15.76, P < 0.001), and quality of life (MD: 48.22, 95 % CI: 43.68-52.77, P < 0.001). Individual analysis revealed that the pooled treatment effects on motor symptoms, psychiatric symptoms, and quality of life were 78.6 %, 84.5-87.9 %, and 83.0 %, respectively. The overall pooled rate of adverse events was 50.0 %, and all of these adverse events were resolved or alleviated with favorable outcomes. CONCLUSIONS: Combined DBS with capsulotomy is effective for relieving motor and psychiatric symptoms in TS patients, and its safety is acceptable. However, the optimal candidate should be considered, and additional experience is still necessary.

Akkermansia muciniphila: a potential booster to improve the effectiveness of cancer immunotherapy.

Cancer immunotherapy has emerged as a groundbreaking method of treating malignancies. However, cancer immunotherapy can only benefit a small percentage of patients, and the numerous side effects that might develop during treatment reduce its effectiveness or even put patients' lives in jeopardy. Surprisingly, the gut microbiome Akkermansia muciniphila (A. muciniphila) can significantly inhibit carcinogenesis and improve anti-tumor effects, thus increasing the effectiveness of cancer immunotherapy and decreasing the likelihood of side effects. In this review, we focus on the effects of A. muciniphila on the human immune system and the positive impacts of A. muciniphila on cancer immunotherapy, which can build on strengths and improve weaknesses of cancer immunotherapy. The potential clinical applications of A. muciniphila on cancer immunotherapy are also proposed, which have great prospects for anti-tumor therapy.

Effect of Cu-Doped Co-Mn Spinel for Boosting Low-Temperature NO Reduction by CO: Exploring the Structural Properties, Performance, and Mechanisms.

Cobalt-manganese spinel catalysts performed unsatisfactory activity at low-temperature and narrow reaction temperature window, which greatly limited the application in NO reduction by CO. Herein, we synthesize a series of Cu-doped CoMn2O4 catalysts and apply to NO reduction by CO. The Cu0.3Co0.7Mn2O4 exhibited superior catalytic performance, reaching 100% NO conversion and 80% N2 selectivity at 250 °C. Detailed structural analysis showed that the introduced Cu replaces some Co in tetrahedral coordination to induce a strong synergistic effect between different metals. This endows the catalyst with the promotion of both electron transfer and oxygen vacancy generation on the catalyst surface. Importantly, the reaction mechanism and pathway were further revealed by in situ diffusion Fourier transform infrared spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results indicated that the cycle of oxygen vacancy mainly determines the catalytic activity of NO reduction by CO. Notably, Cu doping significantly lowered the energy barrier of the rate-determining step (*CO + O → *Ov + CO2), facilitating the desorption of the CO2 and exposing the active sites for efficient NO reduction with CO. This work offers an effective way for designing the catalyst in NO reduction by CO and provides a reference for exploring the catalytic mechanism of the reaction.

Trash to treasure: electrocatalytic upcycling of polyethylene terephthalate (PET) microplastic to value-added products by Mn0.1Ni0.9Co2O4-δ RSFs spinel.

Microplastic pollution has emerged as a pressing environmental issue of global concern due to its detrimental effects on the environment and ecology. Restricted to their characters of complex composition, it is a great challenge to propose a more cost-effective approach to achieve highly selective conversion of microplastic into add-value products. Here we demonstrate an upcycling strategy for converting PET microplastics into added-value chemicals (formate, terephthalic acid and K2SO4). PET is initially hydrolyzed in KOH solution to produce terephthalic acid and ethylene glycol, which is subsequently used as an electrolyte to produce formate at the anode. Meanwhile, the cathode undergoes hydrogen evolution reaction to produce H2. Preliminary techno-economic analysis suggests that this strategy has certain economic feasibility and a novel Mn0.1Ni0.9Co2O4-δ rod-shaped fiber (RSFs) catalyst we synthesized can achieve high Faradaic efficiency (> 95%) at 1.42 V vs. RHE with optimistic formate productivity. The high catalytic performance can be attributed to the doping of Mn changing the electronic structure and reducing the metal-oxygen covalency of NiCo2O4, reducing the lattice oxygen oxidation in spinel oxide OER electrocatalysts. This work not only put forward an electrocatalytic strategy for PET microplastic upcycling but also guides the design of electrocatalysts with excellent performance.

Rod-Like Nanostructured Cu-Co Spinel with Rich Oxygen Vacancies for Efficient Electrocatalytic Dechlorination.

Dichloromethane (CH2Cl2) hydrodechlorination to methane (CH4) is a promising approach to remove the halogenated contaminants and generate clean energy. In this work, rod-like nanostructured CuCo2O4 spinels with rich oxygen vacancies are designed for highly efficient electrochemical reduction dechlorination of dichloromethane. Microscopy characterizations revealed that the special rod-like nanostructure and rich oxygen vacancies can efficiently enhance surface area, electronic/ionic transport, and expose more active sites. The experimental tests demonstrated that CuCo2O4-3 with rod-like nanostructures outperformed other morphology of CuCo2O4 spinel nanostructures in catalytic activity and product selectivity. The highest methane production of 148.84 µmol in 4 h with a Faradaic efficiency of 21.61% at -2.94 V (vs SCE) is shown. Furthermore, the density function theory proved oxygen vacancies significantly decreased the energy barrier to promote the catalyst in the reaction and Ov-Cu was the main active site in dichloromethane hydrodechlorination. This work explores a promising way to synthesize the highly efficient electrocatalysts, which may be an effective catalyst for dichloromethane hydrodechlorination to methane.

Cubic CuFe2O4 Spinel with Octahedral Fe Active Sites for Electrochemical Dechlorination of 1,2-Dichloroethane.

CuFe2O4 spinel has been considered as a promising catalyst for the electrochemical reaction, while the nature of the crystal phase on its intrinsic activity and the kind of active site need to be further explored. Herein, the crystal phase-dependent catalytic behavior and the main active sites of CuFe2O4 spinel for electrochemical dechlorination of 1,2-dichloroethane are carefully studied based on the combination of experiments and theoretical calculations. Cubic and tetragonal CuFe2O4 are successfully prepared by a facile sol-gel method combined with high temperature calcination. Impressively, CuFe2O4 with the cubic phase shows a higher activity and ethylene selectivity compared to CuFe2O4 with the tetragonal phase, suggesting a significant facilitation of electrocatalytic performance by the cubic crystal structure. Moreover, the octahedral Fe atom on the surface of cubic CuFe2O4(311) is the active site responsible to produce ethylene with the energy barrier of 0.40 eV. This work demonstrates the significance of crystal phase engineering for the optimization of electrocatalytic performance and offers an efficient strategy for the development of advanced electrocatalysts.