Intermetallics have attracted considerable research interests in a variety of electrocatalysis reactions due to their specific activity, selectivity, and stability arising from more severe alternation of electronic structure than substitutional alloys. Herein, we report one free-standing trimodal porous β1-NiZn intermetallic and Ni heterostructure on Ni foam (TMP NiZn-Ni/NF) for hydrogen evolution reaction (HER) via electrochemical water-alkali splitting through one convenient and scalable dealloying strategy. Benefitting from high density reactive sites and fluent mass transfer as a result of trimodal porous architecture and strong electronic modulation from NiZn intermetallic, TMP NiZn-Ni/NF primely overcomes the sluggish hydrogen evolving kinetics with superior catalytic performances comparable to Pt/C and many other reported similar electrocatalysts. TMP NiZn-Ni/NF only required the low overpotential of 233 mV at high rate of 600 mA cm−2 with the small Tafel slope at 47.3 mV dec−1 in 1.0 M KOH solution. TMP NiZn-Ni/NF also exhibits exceptional catalytic durability toward HER with almost no current loss under the overpotential of 100 mV for 50 h. Theoretical calculations reveal that β1-NiZn intermetallic itself has low Gibbs free energy for H adsorption (ΔGH*), while it can also greatly decrease the ΔGH* of heterojuncted Ni. This work presents one powerful and scalable protocol to screen self-supporting nonprecious intermetallic nanocatalysts with high density active sites and outstanding catalytic efficiency.

Pigmented villonodular synovitis (PVNS) is a rare pre-malignant disease that require aggressive treatment as surgical synovectomy, eventually followed by radiosynovectomy. Nevertheless, the disease often reoccurs after these treatments. To determine the safety and efficacy of intra-articular (IA) TNF-a blockade with etanercept (ETN), before extended arthroscopic synovectomy, in severe PVNS of the knee, two patients, (a 26-year-old man with B27+ undifferentiated spondylarthropathy and a 32-year-old femal with seronegative olygoarthritis), affected by diffuse knee PVNS (diagnosis made by histological examination), resistant to IA corticosteroid injections and to repeated arthroscopic synovectomy, were submitted, after protocol approval by human research committee and patient’s written informed consent to intra-articular etanercept (IA-ETN) treatment with a different dosage schedule: 12.5 mg weekly IA-ETN injection for 4 weeks, followed by extended arthroscopic synovectomy and of 25 mg IA-ETN injection for 4 weeks, respectively. Previous DMARDs treatment was continued in stable appropriate doses. Any adverse events were recorded throughout the study. The following parameters were considered as clinical endpoints: 1) Knee Joint Index (KJI: range 0-14); 2) Thompson index (THI: range 0-9) At the study entry and at the end of follow-up, high frequency ultrasound grey scale synovial thickening (US-ST) was also assessed. No adverse events were observed due to IA-ETN and to arthroscopic synovectomy. Marked improvement of knee disease activity over time and sustained functional recover was obtained. US-ST evaluation before treatment initiation and at the end of follow-up confirmed the regression of knee joint synovial proliferation

Pigmented villonodular synovitis (PVNS) is a rare pre-malignant disease that require aggressive treatment as surgical synovectomy, eventually followed by radiosynovectomy. Nevertheless, the disease often reoccurs after these treatments. To determine the safety and efficacy of intra-articular (IA) TNFalpha blockade with etanercept (ETN), before extended arthroscopic synovectomy, in severe PVNS of the knee, two patients, (a 26-year-old man with B27+ undifferentiated spondylarthropathy and a 32-year-old femal with seronegative oligoarthritis), affected by diffuse knee PVNS (diagnosis made by histological examination), resistant to IA corticosteroid injections and to repeated arthroscopic synovectomy, were submitted, after protocol approval by human research committee and patient's written informed consent to intra-articular etanercept (IA-ETN) treatment with a different dosage schedule: 12.5 mg weekly IA-ETN injection for 4 weeks, followed by extended arthroscopic synovectomy and of 25 mg IA-ETN injection for 4 weeks, respectively. Previous DMARDs treatment was continued in stable appropriate doses. Any adverse events were recorded throughout the study. The following parameters were considered as clinical endpoints: 1) Knee Joint Index (KJI: range 0-14); 2) Thompson index (THI: range 0-9) At the study entry and at the end of follow-up, high frequency ultrasound grey scale synovial thickening (US-ST) was also assessed. No adverse events were observed due to IA-ETN and to arthroscopic synovectomy. Marked improvement of knee disease activity over time and sustained functional recover was obtained. US-ST evaluation before treatment initiation and at the end of follow-up confirmed the regression of knee joint synovial proliferation.